Chemistry of Essential Oils and Perfumes Voll 1 & 2

VOLUME I.
THE CHEMISTRY OF
ESSENTIAL OILS
AND
ARTIFICIAL PERFUMES
BY
ERNEST J. PARRY B.Sc. (LOND.), F.I.C, F.C.S.

\ndf GRAY'S INN, BARRISTKK-AT-LAW
AUTHOR OF "FOOD AND DRUGS," "THE CHEMISTRY OF PIGMENTS," LTC.
FOURTH EDITION, REVISED AND ENLARGED
VOLUME I.
MONOGRAPHS ON ESSENTIAL OILS
WITH FIFTY.TWO ILLUSTRATIONS
LONDON
SCOTT, GREENWOOD AND SON
8 BROADWAY, LUDGATE, E.G. 4
1921
[All rights reserved]
NEW YORK
D. VAN NOSTRAND COMPANY
EIGHT WARREN STREET
BIBLIOGRAPHICAL NOTE.
First Edition (Demy 8vo) 1899
Second Edition, Revised and Enlarged (Demy 8vo) 1908
Third Edition, Revised and Enlarged to Two Volumes (Royal
8vo), of which this is Volume I May, 1918
Fourth Edition (Vol. I.), Revised a n d Enlarged . . . . April, 1921
PRINTED IN GREAT BRITAIN

BY THE A B E R D E E N UNIVERSITY
PRESS LTD., ABERDEEN.
PREFACE TO THE THIRD EDITION.
THE mass of accumulated information in regard to essential oils
and their constituents has necessitated the division of this work
into two volumes. The present volume deals entirely with the
essential oils themselves in a series of monographs.
The second volume covers the necessary ground relating to
the analyses of essential oils and the characters of their isolated
constituents. It also deals with artificial aromatic bodies which
are not present in essential oils, but which form the groundwork
of synthetic perfumery. It is believed* that this division of the
subject will be found more convenient than the arrangement of
the subject-matter in previous editions.
I have to acknowledge my indebtedness to Messrs. Baker and
Smith of the Technological Museum, Sydney, who have been
exceedingly kind in placing much information and several illustra-
tions at my disposal.
* I am also indebted to M. Gattefosse, Messrs. Eoure-Bertrand
Fils, the Monopoly Bureau of the Government of Formosa, the
Indian Forestry Department, the Editor of the Chemist and
Druggist, and the Editor of the Perfumery and Essential Oil
Record for permission to reproduce numerous illustrations and
much useful information.
EENEST J. PAEEY.
56A GREAT DOVER STREET,

LONDON, S.E., April, 1918.
74000
PKEFACE TO THE FOURTH EDITION.
THE rapid sale of the Third Edition of this work has necessi-
tated the publication of this, the Fourth Edition. No alteration
has been made in the arrangement of the subject-matter, which
has been brought up to date, so that all work of importance
published up to the end of 1920 has been included.
EKNEST J. PAKEY.
56A GREAT DOVER STREET,
LONDON, S.E., March, 1921.
CONTENTS OF VOLUME I.
PAGE
PARMELIACEJE 1
JUNGERMANNIACE^ • 1
•CONIFERS 2-60
N. 0. GRAMINE^ 60-88
PALMJE 88-89
N. Q. AROIDEÊ 89-91
N. 0. LILIACE.E 92-94
AMARYLLIDACE.E 94
IRIDEÊ 96-98
ZINGIBERACEÊ 98-108
PIPERACE.E . 109-116
CANNABINACE.E 116-118
JUGLANDACEJE 118
MYRICACE^ 119-120
SALICINE^ 120
URTICACEÊ 120-121
CHENOPODIACE^ 121-122
LAURACEÊ 122-172
PROTEACE^ 172
MYRISTICEÊ 172-176
MONIMIACEÊ 177-178
EUPHORBIACE^ 178-179
SANTALACEÊ 179-191
ARISTOLOCHIACE.E 191-192
LABIATE 192-270
VERBENACE.E 270-272
CONVOLVULACE^ . 272
PRIMULACE.E 272-273
RUBIACE^: 273-274
OLEACE.E 274-278
ERICACEAE 278-284
APOCYNACE^ 284
vii
viii CONTENTS OF VOLUME I.
PAGE
VALERIANACEÊ 284-285
COMPOSITE 285-304
UMBELLIFERE^l 304-329
MYRTAC.E 329-390
ROSACES 390-412
CALYCANTHACEÊ 412-413
RUTACE.E 413-461
ZYGOPHYLLACEÊ 461-462
ANACARDIACEÊ 462-464
BURSERACEÊ 464-475
LEGUMINOS^ 475-486
GERANIACE.E 486-493
TROPÊOLACE^ . * 494
MELIACEÊ 494
CRUCIFERÊ . 495-501
MAGNOLIACEÊ 501-512
ANONACEÊ 512-524
PITTOSPORACEÊ 524-525
HAMAMELIDACEÊ 525-526-
CISTINEÊ 526-527
RESEDACEÊ 527-528
TURNERACEÊ 528
CANELLACEÊ 528-529
DIPTEROCARPACEÊ 529-531
THEACEÊ 532
MALVACEAE 532
RANUNCULACE^ 532-53a'
FLACOURTIACEÊ 533
APPENDIX (Oil of Chenopodium) 534-536
INDEX 537-549
PARMELIACE/E.
OAK Moss OIL.
UNDER the name "Mousse de Chene " an extract of various lichens
growing on oak and other trees has been placed upon the market, and
is of the greatest value in perfumery. The principal plants yielding
this extract are Evernia furfuracea, Evernia prunastri and Ramalina
calicaris and numerous varieties of the latter. Various types of U$nea,
Alectoria, and Parmelia also yield a similar extract in less quantity and
of poorer odour. If the plants are extracted by means of a volatile
solvent, and the extract is steam distilled, a colourless essential oil is
obtained, which has an intense odour and, according to Gattefosse,1
consists almost entirely of a phenol which he has termed lichenol.
On standing the lichenol crystallises out, and when pure melts at 72° to
73°. Gattefosse originally considered this phenol to be identical with
carvacrol, but now (in a private communication to the author) con-
siders that io is of lower molecular weight, and closely related to
cetrarine, a phenol-ketone occurring in the oil from Cetraria islandica.
JUNGERMANNIACE>E.
OILS OF LIVERWORTS.
When the dry plant Mastigobryum trilobatum, one of the well-known
liverworts, is distilled, a small quantity of an orange-yellow essential
oil is obtained, having a powerful odour recalling those of sandal and
<eedar-wood oils. The oil has, according to Miiller, the following char-
acters :—2
Specific gravity 0'978 at 12°
Optical rotation + 12° 88'
Saponification value . . . . . . . . 5*4
The oil probably consists of sesquiterpenes or sesquiterpene alcohols.

Leioscyphus Taylori yields a thick green essential oil which has the
following characters:—
Optical rotation . . . - 3 ° 44'
It contains two sesquiterpene alcohols, C15H26O, one boiling at 265° and

the other at 275°.
Madotheca levigata yields an orange-yellow essential oil having the
1
Parfumerie Moderns 4, (1911), 4. *Jour. Pharm. Chim. (6), 22, 555.
VOL. I. 1
2 THE CHEMISTRY OF ESSENTIAL OILS
Optical rotation - 72° 14'
Saponification value . . . . . . . . 5'56
Alicularia scalaris yields a lemon-yellow essential oil having the fol-

lowing characters:—
Specific gravity 0-965 at 15°
Optical rotation — 33° 49'
It appears to contain a sesquiterpene alcohol.
CONIFERS.
CEDAR-WOOD OIL.
The oil usually known as cedar oil or cedar-wood oil is obtained by
distillatian of the wood of Juniperus virgmiana, the Virginia cedar, one
of the family of the Cupressinece. Other cedar-wood oils are occasion-
ally met with, and will be mentioned later, but the present remarks
apply to the above-mentioned oil.
Ths oil is generally distilled from the waste shavings from lead-
pencil manufacture, which are usually plentiful when the pencils are
cut from logs. When thin sawn boards are imported and used, the re-
iuse is much smaller in amount, and the price naturally rises. Owing
to the methods of distillation, the oil manufactured from pencil waste
is of less value to perfumers than normally prepared oil. The yield of
oil obtained varies from 2*5 to 5 per cent. Juniperus virginiana occurs
over a very wide area in America, and some of the finest oil is obtained
from the Florida cedar. This oil is one of those which are indispen-
sable in certain classes of perfumery, especially in fine soap-making,
where intensely " sweet" odours are not required. The wood in fine
powder finds its way into much of the incense and similar preparations
used either for ceremonial or fumigating purposes.
The oil is usually of a brownish colour, but it can be obtained al-
most water-white, and although we know nothing definitely of what
change occurs, it is certainly amongst those oils which improve in
quality by keeping. Occasionally samples will be found to deposit a
small amount of crystalline " cedar camphor ".
H Pure cedar-wood oil has a specific gravity of from O940 to 0*962,
and is always laevo-rotatory. The limits, however, are wide, the oil
varying from - 25° to - 47°. According to Schimmel, 80 per cent,
distils at between 125° and 155° at a pressure of 14 mm. The refrac-
tive index is very high, usually exceeding 1*5, and often rising to 1'51.
It is very insoluble in alcohol, 1 part requiring 10 to 20 parts of 90 per
cent, alcohol for solution. The acid value is from 0 to 2, and the ester
value from 2 to 7. A small amount of free alcohols is present, the
ester value of the acetylated product being from 15 to 44. The known
constituents of the oil are the sesquiterpene cedrene, C15H24, and the
oxygenated bodies cedar camphor, or cedrol, C15H26O, cedrenol C16H24O,
and pseudo-cedrol, C15H26O. Cedrol, when pure, is a silky crystalline
mass, with pleasant aromatic odour, melting at 84°. It is suggested by
Schimmel that cedrol is not a normal constituent of fresh wood, but is
formed in it by keeping it under favourable conditions. This supposi-
CONIFEBÊ 3
tion has not, however, been experimentally justified except in so far as
very old wood yields a semi-solid oil, which deposits much cedrol on
cooling. At all events, only a small quantity occurs in normal oils, as
is shown by the low acetylation figure. If the oil be acted upon by
acetic anhydride, and the resulting product saponified, no more than from
6 to 8 per cent, of cedrol will be indicated. It must be remembered,
however, that dehydration takes placet to a small extent with acetic an-
hydride, so that the result may be somewhat under-estimated. Ten per
cent, may be regarded as the maximum usually occurring in good oils.
The figures found by the author for four pure samples (percentage of
KOH to saponify the acetylated oils) are as follows: 2-32, 2-21, 2*13,
1-72.
Cedrenol, which was isolated from cedar-wood oil by Semmler1 and
his pupils is a primary sesquiterpene alcohol, having the following char-
acters :—
Boiling-point at 9-5 mm. 166° to 169°
Refractive index 1-5212
Specific gravity at 20° . 2-0083
Optical rotation ±0°
It forms an acetate of specific gravity 1-0168 at 20° and refractive index

1-5021.
According to Semmler cedrenol stands in the same relation towards
cedrene as the two primary alcohols of the santalol series towards the
sesquiterpenes, C16H24, the santalanes ; and as myrtenol and the ginger-
grass alcohol stand towards pinene and limonene. The primary
CH2OH group in the cedrenol molecule occupies the same position
which is occupied by the CH3 group in cedrene and in solid cedrol.
Hence the relation of cedrene towards cedrol and cedrenol is as
follows:—
(C13H20) (C13H20) (C13H20)
C:CH G(OH).CH 2 C:CH

CH., CH3 CH2OH
Cedrene, C15H24. Cedrol, C15H260. Cedrenol, C15H240.
Pseudo-cediol is a saturated alcohol, boiling at 1473 to 152° at 10

mm., and having a specific gravity 0*9964 at 20°, optical rotation + 21*5°,
and refractive index 1-5131. It appears to be a physical isomeride of
cedrol.
Bousset2 has studied the oxidation products of cedrene, from which
he obtained the ketone cedrone, C15H24O, by means of chromic acid.
On reduction this yields an alcohol, isocedrol, isomeric with cedrol.
Schimmel & Co.3 have examined a cedar-wood oil sent over from
Hayti, of whose botanical origin they were unable to ascertain anything
definite, but which according to microscopical results was derived from
a conifer, which gave on distillation a yield of 4*33 per cent., of oil of
lemon-yellow colour and the odour of the common cedar-wood obtained
from Juniperus virginiana L. But it differs from the latter by its
higher specific gravity (d 15° 0*9612), the lower rotation (a D - 14°58'),
l
Berichte, 45 (1912), 355, 786, 1553. *Bull. Soc. Chim., iii., 17 (1897), 4^5.
»Bericht, April, 1906, 10.
4 THE CHEMISTKY OF ESSENTIAL OILS
and the higher content of alcoholic constituents (ester number after
acetylation 64-0). The acid number was 2*7, the ester number 5*0.
The oil was not completely soluble in 10 volumes of 90 per cent, alcohol,
but dissolved in every proportion in 95 per cent, alcohol.
A cedar-wood oil has been distilled during the past few years from
the wood of Cedrus Atlantica, the so-called Atlas cedar, which is prob-
ably a variety of Cedrus Libani, the cedar of Lebanon. This oil has
the following characters :—
Specific gravity at 15° 0-950 to 0-970
Optical rotat on + 45° ,, + 62°
Refractive index 1-5119 „ 1-5175
Acid value . . . . . . . . . 0 to 2
Ester „ . 3 ,, 11
,, ,, (after acetylation) 30 „ 48
It is soluble in 1 to 10 volumes of 90 per cent, alcohol. According

to Grimal,1 the oil contains traces of acetone, and about 5 per cent, of
a ketone, C9H14O, which he terms libanone. This substance yields a
semi-carbazone, melting at 159° to 160°, and a liquid oxime, which on
bromination yields a dibromide melting at 132° to 133°. The principal
constituent of the oil is dextro-cadinene, which was obtained from it in
a sufficiently pure condition to have an optical rotation of 4- 48°.
The wood of the ordinary Lebanon cedar, Cedrus Libani, yields,
about 3 to 4 per cent, of oil, having an odour recalling those of methyl
heptenone and thujone. Its characters are as follows:—
Specific gravity at 15° . . . . . . . 0 940 to 0'950
Optical rotation + 66° „ + 86°
Refractive index at 20° 1-5120 „ 1-5140
Acid value 0 to 1-8
Ester „ 2 „4
„ „ (after acetylation) 18 „ 25
A sample examined by Messrs. Schimmel & Co. gave the following

results on fractionation :—
270° t o 275° . . . 3 0 p e r cent.
275° „ 280° 40
280° „ 285° 14
285°,, i90° 6
Residue . . . . . . . . . . 10 ,,
A cedar wood from East Africa, the product of Juniperus procera,,
yields an essential oil, which has been examined by Schimmel & Co.2
and found to have the following characters :—
Oil from
Sawdust. Boards.
Yield of essential oil 3*2 per cent. 3-24 per cent
Density at i 5° 0. . 0-9876 1-0289
Refractive index at 20° C. 1-50893 1-51011
Optical rotation -37° 10' - 32° 30'
Acid value . . . . 14-9 27-06
Ester „ . . . . 8-4 7-93
„ ,, (after acetylation) 70-0 89-6
Solubility in 60 per cent, alcohol 1-6 vol. 2 vols.
90 „ 0-5 vol. 0'5 vol.
1 2
Comptes rend., 185 (1902). £b2, 1067. Bericht, October, 1911, 110-
CONIFBE^ 5
The essential oil derived from the boards is filled with crystals
which have been identified as cedar camphor ; after purification they
melt at 86° to 87° C., and have a specific rotation of + 10-12°
Eoberts1 has examined the cedar oil distilled from the wood of the
Deodar tree, Cedrus deodara, a native of the Western Himalayas, which
is widely distributed in Northern India. The samples examined were
of a reddish colour and characteristic balsamic odour. They had the
Specific gravity 0-9549 0-9756
Optical rotation + 52° 16' + 34° 6'
Refractive index at 21° 1-5195 1-5225
Acid value 5-6 4-5
Ester 19-3 4-9
(after acetylation) 30-8 34-4
One was miscible in all proportions with 90 per cent, alcohol; the
other was not soluble in twenty volumes. A ketone was isolated which
did not combine with acid sulphites, but had an odour resembling amyl
acetate, and formed a semi-carbazone melting at 163° to 164°, and a di-
bromoxime melting at about 130°. Schimmel2 considers that it is
possibly j)-methyl-tetrahydroacetophenone. Decomposition of the semi-
carbazone by dilute sulphuric acid gave a ketone differing from the ori-
ginal, boiling at 220° to 224°, and forming a semi-carbazone melting at
204° to 205°, and forming p-toluic acid on oxidation. A phenol was iso-
lated which gave a blood-red colour with ferric chloride and possessed a
sweet phenolic odour. It yielded a benzoyl derivative which crystallised
from dilute alcohol in small needles melting at 70°. The quantity found
was less than 10 per cent, of the oil. On hydrolysis of the oil, hexoic,
heptoic, and stearic acids were obtained. The principal constituents of
this oil are sesquiterpenes, associated with a variable amount of sesquiter-
pene alcohols. The sesquiterpene fraction boiled at 151° to 153° at 19
mm., or 262° to 265° at ordinary pressure. It was a colourless, mobile
liquid, with a specific gravity of 0*9319, optical rotation (1) + 16° 51', (2) +
58° 34', and refractive index 1*5150 (23°). It gave a colour reaction with
sulphuric acid similar to that of cadinene. Attempts to prepare solid de-
rivatives were unsuccessful. The composition of the oil was as follows :
Ketone 2 per cent., phenol 0*07 to 0*4 per cent., esters of hexoic, heptoic,
and stearic acids 3 to 12 per cent., and sesquiterpenes 50 to 70 per cent.,
the remainder of the oil consisting chiefly of sesquiterpene alcohols, with
high boiling viscous decomposition products.
OIL OF CEYPTOMERIA.
The wood of the Japanese cedar, Cryptomeria japonica, yields about
1'5 per cent, of an essential oil having the following characters:—
Specific gravity 0-945
Optical rotation - 23°
Ester number . . . . . . . . . . 3'9
The oil contains about 60 per cent, of sesquiterpenes and 40 per
cent, of sesquiterpene alcohols. The principal sesquiterpene is prob-
ably cadinene, as indicated by the following figures in comparison with
those for cadinene obtained from oil of cade :—
1 2
Jour. Chem. Soc. (1916), 791. Bericht, 1917, 23.
6 THE CHEMISTEY OF ESSENTIAL OILS
Sesquiterpene from Cadinene from
Cryptom ria Oil. Oil of Cade.
Specific gravity . . . . 0-925 0-927
Optical rotation . . . . - 9 8 ° 45' - 9 7 ° 30'
Melting-point of dihydrochloride . 117° to 118° 117° to 118°
A second sesquiterpene is present, which only yields liquid halogen

acid derivatives. This body, to which the discoverer has given the
name suginene, has a specific gravity 0*918 and specific rotation
- 10° 34'. It yields a liquid hydrobromide, of specific gravity 0*988
and specific rotation - 11° 15'. One of the fractions obtained on
distillation was analysed and found to correspond with the formula
C15H25OH, and is apparently one or more sesquiterpene alcohols. • -
By conversion into the xanthogenic esters the alcoholic portion of
the oil was separated into two distinct portions, which on saponifica-
tion yielded two isomeric sesquiterpene alcohols. One of these, iso-
cryptomeriol, C15H25OH, is a liquid of specific rotation - 3° 25'. The
isomeric alcohol has been termed cryptomeriol, and is an oil of specific
rotation - 37° 5', and has a specific gravity 0'964.
By dehydration by means of formic acid, cryptomeriol yields a
sesquiterpene having a specific gravity 0*918, and a specific rotation
- 1° 5'. It boils at 143° to 144° at 12 mm. pressure. By dehydra-
tion by means of phosphorus pentoxide an entirely different sesquiter-
pene results, having a specific gravity 0*917 and a specific rotation
+ 56° 26'.
The essential oil from the leaves has been investigated by So Uchida.1
On distillation with steam the green leaves yielded 0*70 per cent, of
volatile oil, which was brownish-yellow in colour and had a fresh
aromatic odour. It has the following characters:—
„ rotation + 19-29°
Refractive index 1*4895
Acid value 1-0
Ester „ 6-56
„ „ (after acetylation) 14-35
On fractional distillation the following constituents were separated:

d-a-pinene, together with a small quantity of dipentene formed about
34 per cent, of the oil. An alcohol, CaoH18O, having a fresh odour re-
sembling that of camphor and peppermint, was found to the extent of
4-5 per cent., partly combined as the caprylic ester. It had a specific
gravity of 0'9414, refractive index 1-4832, and specific rotation -f 56*07°
in chloroform solution. This alcohol, though small in amount, is re-
garded as the chief odorous constituent of the oil. Sesquiterpenes were
present to the extent of about 30 per cent., consisting partly of cadinene
and partly of a sesquiterpene with two double linkings, boiling-point
266° to 268°, specific gravity 0*9335, refractive index 1*5041, and specific
rotation 4- 15*19° in chloroform solution. A sesquiterpene alcohol, oc-
curring to the extent of about 12 per cent., had boiling-point 284° to 286°,
specific gravity 0*9623, refractive index 1*5048, and specific rotation
4- 16*76° in chloroform solution. A new crystalline diterpene, repre-
senting about 18 per cent, of the oil, has been isolated, to which the
Uchida has given the name a-cryptomerene. On passing dry hydro-
1
Jour. Amer. Chem. Soc. (1916), 687.
CONIFEEJE 7
chloric acid into a well-cooled solution of this dipentene in ether a crys-
talline isomer was obtained, which is termed /2-cryptomerene. Traces
of a lactone, C20H32O2, free fatty acids, and a blue oil, azulene, were also
separated.
OIL OF TAXODIUM DISTICHUM.
The oil extracted from the wood of Taxodium distichum (" Southern
Cypress") by means of alcohol, has been examined by Odell.1 He
fractionated the resinous residue in vacuo and has thus isolated a hydro-
carbon C15H24 which he calls cypressene ; it is an inodorous oily liquid,
boiling-point (35 mm.) 218° to 220° C., boiling-point (778 mm.) 295° to
300° C.; [a]2D° + 6*53°. He has also extracted a compound C12 H20O, a
bright yellow oil with a strong odour, possessing the properties of an
aldehyde ; it has received the name of cypral (boiling-point, 35 mm.,
182° to 185° G.); it is dextro-rotatory.
Cypressene yields, on oxidation with nitric acid, an amorphous yel-
low product and an acid possessing the odour of isovaleric acid; the
amorphous product dissolves in alkalies with a red coloration.
Odell has also examined the oil from the cones of the same tree.
When harvested in September the cones yield 1 per cent, of a greenish-
yellow essential oil, with a strong odour of pinene, w7hilst the cones
harvested at a later period yield on distillation 1*5 to 2 per cent, of a
darker oil possessing an odour of lemon. These two oils possess the
Optical rotation +18° +35° 30'
They contain about 85 per cent, of J-a-pinene, 5 per cent, of rf-limonene,

and 2 per cent, of an alcohol. Small amounts of carvone, and of a ses-
quiterpene, which is probably cypressene, are also present.
CHAM.ECYPAKIS OIL.
Ghamcecyparis obtusata, the hinoki tree which is extensively grown
in Japan, furnishes a valuable timber wood, and the tree thrives well in
the mountainous districts of Formosa. Uchida 2 has examined a sample
of the crude oil obtained by the dry distillation of the wood in Formosa.
It is a reddish-brown mobile liquid possessing a woody and empyreu-
matic smell and containing tarry matter. The yield was 2-4 per cent,
of the wood. The rectified oil obtained by distillation with steam was
lemon yellow in colour, and after treatment with sodium carbonate solu-
tion to remove pyroligneous acids it had a specific gravity of 0*8821,
refractive index, 1-4990, and specific rotation + 50*37° in chlordform
solution. The constituents identified were d-a-pinene and cadinene,
with a small amount of oxygenated compounds, the amount of terpenes
being about 70 per cent., and that of the sesquiterpenes about 24 per
cent.
The leaves of Chamcecyparis Lawsoniana yield about 1 per cent, of
oil having the following characters :—
1 2
Jour. Amer. Chem. Soc., 33, 755. Jour. Amer. Chem. Soc. (1916), 699.
THE CHEMISTEY OF ESSENTIAL OILS
Acid value . . . . 3-7
Ester „ . . . . 61-6
„ ,, (after acetylation) 78-8
The oil contains laurinic aldehyde.
\The oil distilled from the wood of Chamc&cyparis Lawsoniana and
rectified by steam has been examined by Schorger.1 The oil has the
Refractive index . 1-4758 at 15°
Optical rotation +39-6°
Acid value 0-3
Ester „ 32-8
,, ,, (after acetylation) . . . . : . 7i-6
The oil behaved as follows on fractional distillation :—
(760 mm.) 155° to 157° 60-5 per cent.
157° , 170° 3-0
170° , 180° 4-0
(15 mm.) 100° , 130° 20-5
130° , 160° 7-0
160° , 190° 1-0
The oil contains d-a-pinene to the extent of 60 per cent., dipentene (6 to
7 per cent.), Z-borneol (11 per cent.), cadinene (6 to 7 per cent.), formic
and acetic acids in the free state, and formic and capric acids as esters.
OlL OF JUNIPEBUS OXYCEDEUS WOOD.
Juniperus oxycedrus is the juniper which furnishes the wood from
which the tarry empyreumatic 2oil, known as cade oil, is obtained by de-
structive distillation. Huerre has submitted the same material, suit-
ably comminuted, to ordinary steam distillation. The essential oil thus
obtained comes over very slowly; the yield varies from 1*6 to 3*4 per
cent. The higher yield was obtained from the autumn cut wood. The
oil is a dark yellow viscous liquid; having the following characters :—
Specific gravity 0-915 to 0-927
At normal atmospheric pressure it boils between 260° and 300° C.
Soluble 1 : 1 in 95 per cent, alcohol, and 1 : 12 in 90 per cent, alcohol.
On rectifying the crude oil in a current of steam, under reduced pressure,
70 per cent, of the original oil distilled as a bright yellow liquid with a
penetrating odour; it was much less viscous than the original oil. The
residue (30 per cent.) was very viscous, dark in colour, and had a feeble
sweet odour.
OlLS OF LlBEOCEDEUS DECUEEENS.
Librocedrus decurrens, a tree found in California and known as the
Incense cedar, yields a leaf and twig oil and a bark oil. The leaf and
twig oil has the following characters :—
l
2
Jour.Ind. Eng. Chem., 6 (1914), 631.
Jour. Pharm. Chim. (1915), 12, 273.
CONIFEE^ 9
Optical rotation - 3° 20' „ + 36-68°
Ester value 18-5 „ 27-8
„ „ (after acetylation) . . . . 28'6 „ 48-2
It contains furfural, a-pinene, sylvestrene, limonene, dipentene,
borneol, esters, and a sesquiterpene, which has been named librocedrene,
having the following characters:—
Specific gravity at 20° 0-929
Boiling-point 270° (approximate)
Refractive index. 1-4994
Optical rotation + 6-4°
The bark oil has the following characters :—
Refractive index 1-4716 at 15°
Optical rotation + 1'1°
Ester value 3-2
The oil contains furfural, a-pinene, dipentene, and borneol.
OIL OF TURPENTINE.
Numerous members of the family of the Conifera contain large
quantities of resin, and an oil consisting almost entirely of terpenes, in
well-characterised resin ducts in the wood. This is especially the case
with the various species of pine. The exudation from the wood, an
oleo-resin, is often known as crude turpentine. Oil of turpentine, or,
as it is generally called, turpentine or " turps," is the oil obtained by
distilling this, leaving the crude resin or " rosin " behind.
At the present time American turpentine is the chief commercial
variety, although a considerable amount is produced in France, Eussia,
and many other countries, and India produces a fair quantity which,
although at present consumed in the East, may before long find its way
to Western markets.
In the United States the turpentine (i.e. the oleo-resin) is obtained
either by what is known as the "box system" or by the "cup and
gutter " system. The box system, briefly, is carried out as follows : As
spring approaches, a- groove is cut diagonally across the trunk of the
tree, and inclined inwards, ending in a hollow excavation about 12 to
18 ins. above the ground level. This wound in the sapwood induces the
flow of the oleo-resin, and as the warmer weather approaches, the bark
above and on both sides of the excavation or " box " is peeled off and
shortly afterwards the flow of oleo-resin commences. Every two or
three weeks fresh cuts are made so as to open up fresh passages for the
exudation. The oleo-resin collects in the "box" and is baled out into
barrels and transferred to the distillery. Trees are not considered worth
tapping after four to six years. The cup and gutter system is a com-
bination of the older box system and of the usual method employed in
France. The cutting of a large hollow in the trunk is obviated, and its
place is taken by a receptacle which is suspended from a nail in the
trunk. As in the " box " system, here also the first work is cutting strips
in the bark, and as the work proceeds, the space above the receptacle is
gradually cleared of bark. In order to let the exuding resin collect in
the earthenware pots or vessels placed below, two strips or gutters of
galvanised sheet-iron about 2 ins. wide by 6 ins. to 12 ins. long are em-
ployed. These are placed in grooves cut into the trunk with a broad
axe in such manner, that each of the two cuts forms an angle of 60°
with the longitudinal axis of the itree, and the two together therefore
FIG. 1.—Still of a *• Turpentine Farm " in the " Landes ".

[Itoure ttertrand Fils.
form an angle of 120° open at the top. The two gutters, however, are
not placed at the same height, hut one about 1 in. or 2 ins. above the
other, so that the resin flowing along the upper gutter only passes the
other one when flowing down, and then passing through the lower gutter
CONIFEKJE 11
reaches the vessel placed below the latter. When the cuts in the trunk
and the peeling of the bark are continued in an upward direction, the
gutters and the vessel are also moved upwards. In older trees contain-
F IG> 2.—Collection of the crude turpentine in the «* Landes ".

[Roure Bertrand Fils.
ing more oleo-resin, several such vessels can of course be placed around
the tree.
The French turpentine industry is practically confined to the Lander
district, where the following method of collection is followed :—^
1
Vezes, Roure-Bertrand's Bulletin (1909), 2, 9, 3.
12 THE CHBMISTEY OF ESSENTIAL OILS
This crude material—the " gemme," to give it the name under which it
is known in the Landes—exudes during the warm season (from March to
October) from an incision made by the axe of the resin collector in the
stem of the maritime pine. Kept open by the removal of a thin slice
every week, this incision—the " carre "—rises gradually up the trunk of
the tree until it reaches, after five years' working, a height of nearly
4 metres. The tree is then left alone for two or three years, after which
time a fresh " carre " is made at another point of the base. The same
tree is tapped in this manner for about forty years, after which it is
" bled to death" (that is, it is worked by means of several "carres"
simultaneously), before being felled and delivered to the timber mer-
chants. The forest is, moreover, rapidly reconstituted, by means of
sowings made at the proper time, so that the resin production of the
Landes district is not diminished by the work of the wood-cutters and
the operations of the mechanical saw-mills. So far, this principle has
not been followed in the United States, where every tree was " tapped to
death " from the beginning, and every plot which was subjected to tap-
ping was thereby practically destroyed after four years' working, without
any steps being taken for its reconstitution. For some years, however,
a serious movement has been set on foot in America to save what re-
mains of the pine forests by a more rational and less destructive system
of exploitation ; and this appears to be producing good results.
From the top of the "carre," the drops of " gemme " as they exude
from the resin ducts of the tree, run down into the receiver placed to
collect them; this was in former times in the Landes (and was until
three or four years ago in America) a hole—the " crot "—hollowed out
of the stem of the tree itself, at the base of the " carre " ; at the present
day it is, both in America and in the Landes, an earthenware or metal
pot, suspended at the base of the " carre " and raised every year so as to
bring it near the upper part of the incision and reduce the distance over
which the drops of the exudation have to run. -The importance of this
change and why it is advantageous that the path of the " gemme " down
the " carre " should be as short as possible, is obvious when one remem-
bers how easily the turpentine is oxidised.
From the pots the " gemme" is transferred, about once a month,
into casks and carried from the forest to the factory ; this harvest,
" I'amasse," takes place in the Landes from five to eight times a year.
In India, the chir, as the Pinus longifolia is termed, is treated by a
method based on the French method.1
An initial blaze about 6 ins. long, 4 ins. broad and not more than
1 in. deep is cut near the base of the tree, and the blaze is freshened
every six or seven days throughout the summer, until it is about 18 ins.
long by the end of the year : if the freshening is carefully done the use
of a ladder is thus as a rule unnecessary till the fifth year. The resin
collects in a cup fixed at the base of the current years' blaze, and the
contents are emptied periodically. A curved channel, in place of the
former rectangular channel, is now universally adopted in the United
Provinces, as it works easily, does not injure the tree so much, gives a
cleaner cut, and so far shows promise of giving a higher out-turn.
There are two classes of tapping : (1) light tapping and (2) heavy tap-
ping, sometimes termed tapping to death. The latter is carried out in
1
Indian Forest Memoirs (Sylviculture series), Vol. I, Part I, p. 100.
FIG, 3.—" Turpentine Farm " in the '* Landes "—Interior. Bsrtraud Fils.
the case of trees due to be felled within five years, and consists in making
;as many blazes as the tree will hold • the former consists in making a
moderate number of blazes, and is carried out in the case of trees not
•due to be felled within the next few years. In the Naini Tal Division
light tapping under the present system' is commenced when the trees
xeach a girth of 3-J ft., and the following number of blazes are cut :—
(1) Trees over 6 ft. in girth 3 blazes
(2) „ „ 4J to 6 ft. in girth 2 „
(3) „ „ 3| to 4| ft. in girth . 1 blaze
In the maritime pine forests of Bordeaux no tree is tapped lightly till it

reaches a girth of 1*10 metres (3 ft. 7 ins.), when one blaze is made: the
itree is then about fifty years old. A second blaze is added when the tree
•reaches a girth of 1*30 metres (4 ft. 3 ins.). In the Chakrata Division
.tapping is confined to fire-protected forests of the first and second periodic
iblocks in Jaunsar-Bawar; no tapping is at present done in the Tehri-
Garhwal forests owing to the cost of carriage. At present no heavy tap-
ping is done in this Division : light tapping commences when the trees
reach 4J ft. in girth. In periodic block I. trees 4-J- to 6 ft. in girth have
tw<^ blazes, and those over 6 ft. in girth have four blazes. In periodic
block II. trees 4-J to 6 ft. in girth have one blaze, and those over 6 ft. in
girth have two blazes.
The object of heavy tapping is to obtain the largest possible out-turn
of resin before felling the tree, and for this purpose as many blazes are
made as there is room for. Experiments carried out so far show that
only a comparatively small proportion of trees tapped in this way die:
recent experiments in the Kangra Division showed a mortality of 6 per
cent, in two years. In the maritime pine forests of Bordeaux trees to be
removed in thinnings are heavily tapped as soon as they are large enorn h
to hold a cup : this ordinarily commences when they are fifteen years old.
In the United Provinces the season's tapping commences in March
and continues till November, after which the flow of resin practically
ceases. In order to promote the free outflow of resin, the blazes require
to be freshened with an adze at intervals. Eecent experiments carried
out by Mr. E. A. Smythies in the Naini Tal Division showed that the
out-turn increased steadily up to at least ten freshenings per month :
this is borne out by similar experiments made in the Punjab. In Naini
Tal, however, it was found that the yield did not increase in proportion
to the extra labour required beyond five freshenings per month, and this
number (i.e. once in about six days) is now universally adopted in that
Division in place of the four freshenings per month formerly in vogue.
As regards labour, in the Naini Tal Division the most economical work-
ing is found to be attained by an allotment of about 600 trees per man,
that is, 100 trees a day per man.
In the case of light tapping, it is customary in India to tap for a cer-
tain number of years and then to allow a period of rest before tapping is
recommenced. In the Naini Tal Division, and in Kumaon generally,
the rule hitherto has been to tap for five years and then to give a rest for
ten years before recommencing tapping : this complete period of fifteen
years may be termed the tapping-cycle. In the Chakrata Division a
similar procedure was in force till 1914, when a nine years' tapping-cycle
was introduced, with tapping for three years followed by a rest for six
CONIFEE^ 15
years. The cycle was shortened in order to avoid the use of a ladder,
which was found necessary in the fifth year. The highest yield of resin
is obtained in the third and fourth years of tapping, and thus by reducing
the tapping period to three years considerable loss is involved, which is
avoidable considering that a ladder is not required in the fourth season
if reasonable care is taken in freshening the blazes.
If a tapping-cycle at all is to be decided on, twelve years (i.e. four
years' tapping and eight years' rest) appears to be preferable to either nine
or fifteen years. The objection to the former has been mentioned, while
in the case of the latter it cannot be made to fit in with a suitable scheme
of thinnings.
In the maritime pine forests of Bordeaux light tapping, once begun,
continues without interruption, no rest being given unless a tapped tree
shows signs of becoming sickly, when a rest of five years is given : such
cases are rare. Now in the case of the chir pine, experiments have
shown that the tree possesses remarkable vitality even under the strain
of heavy tapping. There seems to be no reason, therefore, why the con-
tinuous light tapping system of France should not be employed in the
chir forests. Not only would it increase largely the out-turn of resin,
but it would avoid the complication in the general scheme of manage-
ment which is inevitable if a tapping-cycle is adopted.
Much has been written in reference to the adulteration of oil of tur-
pentine, most of which is of little more than historical interest to-day.
The chief difficulty the expert has to contend with at the present time is
the detection of the so-called wood or stump turpentine oil. This oil is
clearly entitled to the description " turpentine oil," on account of its
origin and character, which are exceedingly close to those of normal or
" gum " turpentine ; but it is generally conceded that it properly requires
the qualification " wood "or " stump," so that users may know exactly
what they are dealing with.
Wood turpentine, " stump turpentine," or " wood spirits of turpen-
tine," as the product is variously known, is turpentine oil made from cut
pine, fir, or spruce, by distilling the wood in closed retorts. When pro-
perly refined it closely resembles gum spirits of turpentine, obtained by
distilling the oleo-resin exuding from the cut surface of the living tree.
The turpentine made by distilling the wood with steam below a tempera-
ture of 150° C. more closely resembles gum spirits than that obtained by
destructively distilling the wood. The latter is always contaminated
with other oils derived from the breaking down of the wood and the re-
sins which it contains.
As a result of the reckless devastation of the pine forests which has
been practised for many years, in the United States, the tree-stumps
which have been left standing, and which are known as "light wood "
are now often distilled. The stumps which are being used up in America
at present have remained in the ground many years after the trunk had
been removed, and yield a pine wood which is very rich in resin. It
would appear that a chemical process is taking place in these stumps by
which oil is formed subsequent to the removal of the trunk, for the oil-
yield from new stumps is very low. This fact would also explain why
the oil thus obtained is somewhat different from ordinary oil of turpen-
tine, and why the percentage is so high.
The stumps which are mostly employed for distilling purposes are
those of Pinuspalustris (long leaf pine), whence the oil is called "long
leaf pine oil ". Similar products are brought to market under the names
of "light wood oil" and " oil of fir" ;. while the designations " white '*
and "yellow pine oil " appear to apply to separate fractions of the oil.
According to Teeple l ordinary commercial long leaf pine oil in its
crude state has a specific gravity 0-935 to 0*944, optical rotation - 11°,
and refractive index T4830. These values, however, are often exceeded,
and genuine samples may have a specific gravity 0*954 and may be
dextro-rotatory up to + 8°. A sample was examined by Schimmel &
Co.2 which had the following characters :—
Specific gravity . 0-9536
Optical rotation . - 3° 26'
Ester number . . . 14-2
Total alcohols (by acetylation) 58 per cent.
The bulk of the oil boiled between 190° and 220°. The following ter~
penes were identified in the oil: a-pinene, /3-pinene, Z-limonene, dipen-
tene, and A-terpinene. A considerable amount of a-terpinene was found
(this had previously been identified by Teeple), as well as borneol and
methyl-chavicol. Fenchyl alcohol was also found as a constituent of the
oil, and traces of camphor and cineol. The presence of fenchyl alcohol
is of particular interest as it occurs in the inactive variety. It is well
known that this body results from the reduction of fenchone, but it has
never before been discovered as a natural constituent of an essential oil.
The table below shows the character of the fenchyl alcohol occurring
in this oil and of those prepared by the reduction of active and inactive
fenchone.
FENCHYL ALCOHOL AND ITS DERIVATIVES.
From Yellow Pine Oil. From Active Fenclione. From Inactive Fenchone.
m.p. b.p. d. nD. m.p. b.p. d. nD. m.p. b.p. d. nD.
_ _
33 202 Fenchyl 45° 201 33 201
to to Alcohol to to to
35° 20 S° 202° 35° 202°
192 0-9501 1-47023 Fenchone + 6° 192 0-952 1-46337 — — —
— to (15°) (20°) to (15°) (17°)
193° 193°
159 — Fenchone 164 — — 153 — —
to Oxime to to —
160° 165° 160°
142 — Acid 145 —
— — — — — — — —
to Phthalic to
143° Ester 145-5°
154 0-8687 1-47240 Fenchene 154 0-8660 1-46733 — 154 0-8665 1-46733
to (15°) (20°) to to to to (15°) to
156° 156° 0-8665 1-46832 156° 1-46832
(15°) (17°)
93 — — Isofenchyl 106 94° — — —
— —
to Phenyl- to
94° urethane 107°
1 2
Jour. Amer. Chem. Soc., 30 (1908), 412. Report, April, 1910, 104.
CONIFEE^ 17
The crude oil obtained by any distillation process is redistilled or re-
fined before it is marketed. Crude oils from the destructive process
are agitated with alkali whereby the greater part of the phenols, cresols,
and related bodies are dissolved, and separated by settling from the
turpentine; rosin spirits and rosin oils are run off and separated by
redistillation with steam as steam-distilled wood turpentine is. This is
usually done in a copper-pot still of suitable size, live steam being con-
ducted directly into the crude oil. Ordinarily this distillation is not
conducted with care, and but little attempt is made to ensure that the
wood turpentine obtained does not contain considerable quantities of the
heavier " pine oils," as the heavier oils present in the crude product are
called.
The principal source of American turpentine is the long-leafed pine,
Pinus palustris (Pinus australis Mchx.) ; Pinus heterophylla and Pimis
echinata also furnish turpentine.
American oil of turpentine consists practically entirely of terpenes,
of which pinene is the chief. Dextro-a-pinene, laevo-a-pinene and fi-
pinene are all present, as well as small quantities of camphene. The
question as to whether firpene,1 which has been described as a consti-
tuent of the oil, is a distinct individual or not, is a matter of some doubt.
Crude wood turpentine differs from normal turpentine primarily in
that it contains additional terpenes, and terpene derivatives, together
with other non-terpene derivatives. In that obtained by the destructive
distillation of long-leaf yellow pine, dipentene, pentane, pentene, toluene,
heptine, etc., have been identified, in addition to pinene.
Steam-distilled wood turpentine consists essentially of pinene, to-
gether with camphene, limonene, dipentene, cineol, and (depending on
c^re of fractionating), terpineol, borneol, terpinene, etc.
The pine oils contain chiefly terpineol, borneol, and fenchyl alcohol,
with small quantities of limonene, dipentene, terpinene, cineol, and even
less pinene and camphene.
American oil of turpentine varies in character to a considerable ex-
tent, the optical rotation, especially, having steadily decreased in the
past few years. Such variations are to be expected when one remembers-
that the gathering grounds have been extended in various directions, the
methods of preparation alter from time to time, and the use of different
species of trees is not uncommon.
Any standards for these oils must therefore be understood to be fair
working figures, to which by care, oils can be made to attain, although pure
distillates may, obviously, give values widely outside the accepted figures.
The United States Department of Agriculture in 1911 issued sug-
gested standards for pure turpentine, of which that for No. 1 or " stand-
ard " turpentine is-the most important. The suggested standards are
as follows : Specific gravity at 20° = 0-862 to O870; refractive index
at 20° = 1-4680 to 1*4760; 95 percent, should distil below 170°. On
polymerisation with sulphuric acid (thirty-eight times normal) the re-
sidue should not exceed 1 per cent, and should have a refractive index
of 1-500 to 1-520.
The author,2 as the result of the examination of a very large number
of pure commercial samples, finds the following limits to embrace prac-
tically all genuine normal samples as met with in commerce :—
iFrankforter and Frary, Jour. Amer. Chem. Soc., 28 (1906), 1461.
2
E. J. Parry, Chemist and Druggist, 24 August, 1912.
VOL. I 2
Initial boiling-point 154° „ 155-5°
Distillate under 160° 72 „ 74-5 per cent.
„ 170° 95 ,,97-5 „
Bromine value 1-96 ,, 2-31
Iodine value (Hiibl) 360 , 375
„ (Wijs) 335 ,350
„ ,, of last 10 per cent, on distillation (Hiibl) 349 , 369
(Wijs) 350 ,365
Refractive index of 1st 20 per cent. . . . 1-4700 , 1-4722
2nd ,, . . . . 1-4700 , , 1-4724
3rd „ . . . . 1-4710 „ 1-4735
4th „ . . . . 1-4710 „ 1-4740
5th , , . . . . 1-4780 „ 1-4821
The characters of wood turpentine, and the effect of this and of other
adulterants onthess figures is shown in the folio wing table by the author
(toe. cit.):—
•1) (2 (3) (4) (5)

,p
§ p
£< *E "p
1
1"! § *&
II
'if
3*
IP"*
.^41* ^ H1* &J1 -§ ^
H
g^ ?H
g^
Specific Gravity . . . . 0-866 0-873 0-869 0-808 0-838
Refractive Index . . . . 1-4720 1-4745 1-4737 1-4490 1-4610
Initial Boiling-point 155° 159° 157° 98° 99°
Distillate under 160° 74°/0 61°/0 68°/0 48°/0 62°/0
„ 170° 94°/0 78°/0 84°/0 82°/0
Bromine Value * . . . . 2-2 1-46 1-82 0-05° 1-1
Iodine Value (Hiibl) 372 264 321 9-0 190*5
„ (Wijs) 350 240 298 8-4 179
„ of last 10 per cent. (Hiibl) . 360 251 304 9-0 184
„ „ (Wijs) . . 355 242 298 8-5 177
Refractive Index of 1st 20 per cent. 1-4719 1-4731 1-4728 1-448 1-4660
2nd „ . 1-4700 1-4730 1-4720 1-419 1-4675
„ 3rd „ . . . 1-4712 1-4734 1-4722 1-4481 1-4721
4th „ . 1-4712 1-4732 1-47-21 1-4470 1-4721
5th „ . 1-4781 1-4842 1-4821 1-4495 1-4735
As Hertz 1 has shown, the optical rotation of American oil of turpen-

tine is very variable. nM.j
The experiments on the opposite page by the United States Govern-
ment Chemists with the oil from named trees show how widely the
rotation may vary even with the product of the same tree :—
1
Jour. Amer. Chem. Soc., 30, 863.
CONIFEE^l 19
Optical
Tree Dia- Rotation
Designa- Species. meter Character of Chipping. 100 mm.
tion. (inches). Tube.
20° "C.
Al P. heterophylla 7-0 1st year, normal depth - 20° 50'

A2 >» 14-5 >» » + 0°15'
A3 »» 24-5 »t » - 15° 0'
A4 P. palustris . 7-3 + 15° 40'
A5 »» 15-0 >» > + 8° 9'
A6 »» 21-0 »» > + 18° 18'
01 P. heterophylla 12-3 2nd year, shallow . - 27° 11'
02 ?i 8-2 »• »> • - 26° 28'
C3 P. palustris . 13-0 »> »» • • - 7° 26'
04 11 • 8-7 >» i» • + 7° 31'
Dl •» 9-0 2nd year, normal depth + 10° 50'
D2 » 13-5 »» »» + 1°23'
D3 P. heterophylla 13-0 »' »» - 18° 35'
D4 " 9-0 »• - 29° 26'
In a general way the figures support the view that the oils of Pinus
palustris are dextro-rotatory and those from Pinus heterophylla laevo-
rotatory. That this is not strictly true, however, is evidenced by the
dextro-rotation of A2 (P. heterophylla), and more especially by the laevo-
rotation of 03 (P. palustris).
With these variations in the first collection from the several trees,
the question naturally arose, would the variations change as the season
advanced or would the figures prove constant for the individual trees ?
The rotations for the successive collections are as follows:—
OPTICAL KOTATION IN 100 MM. TUBE, 20° C.
Collection. Al. A2. A3. A4. A5. A6. 01.

1 - 20° 50' + 0° 15' - 15° 0' + 15° 40' + 8° 9' + 18° 18' - 27° 11'
2 - 22° 5' - 0° 30' - 14° 26' + 15° 22' + 8° 50' + 17° 43' - 26° 48'
3 - 21° 45' + 0° 15' - 15° 55' + 14° 15' + 8° 27' + 19° 30' - 26° 25'
4 - 21° 7' - 1° 15' - 15° 50' + 14° 20' + 8° 34' + 18° 46' - 23° 32'
5 - 20° 30' - 2° 5' - 15° 15' + 14° 21' + 8° 32' + 19° 24' - 21° 12'
6 - 20° 15' - 3° 30' - 15° 27' + 14° 35' + 8° 4' + IV 16' - 21° 46'
7 - 22° 15' - 5° 45' - 17° 52' + 12° 49' + 7° 6' + 14° 47' - 21° 35'
Collection. C2. 03. C4. Dl. D2. D3. D4.
1 - 26° 28' - 7° 26' + 7° 31' + 10° 50' + 1° 23' - 18° 35' - 29° 26'
2 - 25° 37' - 6° 42' + 7° 20' + 11° 23' + 2° 40' - 17° 0' - 27° 45'
3 - 26° 20' - 4° 45' + 13° 7' + 2° 25' - 15° 20' - 28° 19'
4 - 26° 30' - 4° 29' + lv°46' + 2° 22' - 15° 0' - 27° 38'
5 - 26° 7' - 3° 55' + 13° 0' + 1°13' - 14° 38' - 27° 48'
6 - 26° 0' - 4° 5' + 13° 0' + 1°15' - 14° 7' - 26° 11'
7 - 26° 28' - 6° 6' + 10° 48' - 0°55 - 14° 19' - 26° 12'
Wood turpentine can, however, be so rectified as to distil at tempera-

tures much closer to those of normal turpentine than is shown in the
table on p. 18, so that whilst positive results indicate the presence of wood
turpentine, negative results do not necessarily exclude its presence.
The lower iodine value, especially of the last 10 per cent, remaining
on distillation is very characteristic of wood turpentine, and is, in the
author's opinion, the most valuable evidence that can be obtained of its-
presence.
The fact that wood turpentine usually contains dipentene is also of
considerable assistance to the analyst in some cases. In normal turpen-
tine, if the successive fractions of 5 per cent, be examined, they will be
found to increase regularly in specific gravity and refractive index, with
each rise in the distillation temperature. Dipentene, however, has a
higher boiling-point than pinene, but a lower specific gravity. So that
in a wood turpentine containing dipentene, when about 70 per cent, has
distilled over, some of the fractions will be found to have increased in
boiling-point, increased in refractive index, but decreased in specific
gravity. In such a case, the presence of wood turpentine may safely
be assumed.
When adulterated with most types of petroleum products, the tem-
perature of distillation rises gradually, and no large fractions are obtained
at any definite temperature when the adulteration is at all excessive.
The presence of ordinary petroleum spirit lowers the flash-point of tur-
pentine. When pure it flashes at 92° to 95° F. when tested in Abel's
flash-point apparatus. With only 1 per cent, of ordinary petroleum
spirit this temperature is reduced by 10°.
According to Armstrong, a good indication of the presence of the
usual adulterants is obtained by distillation with steam. A current of
steam is allowed to pass into a definite volume of the turpentine con-
tained in a flask attached to a condenser. Unless it has been allowed
free access to the air for some time, the genuine oil leaves only traces
of non-volatile matter, but old samples may leave up to 2 per cent.
Usually, however, the presence of more than '5 per cent, after steam
distillation indicates the presence of unvolatilised petroleum oil. This
is easily recognised by its low specific gravity and its fluorescence when
dissolved in ether. If the residue consists of resin oil, it will form a.
bulky soap when rubbed with slaked lime. The specific gravity of the
fractions coming over with the steam will largely assist in determining
the presence of volatile adulterants.
For the approximate estimation of the amount of petroleum naphtha
in adulterated turpentine, Armstrong1 recommends the following pro-
cess : 500 c.c. of the sample is placed in a separator and treated with
about 150 c.c of sulphuric acid (2 volumes of acid to 1 of water).
The mixture is cautiously agitated, and, if much rise of temperature is
observed, the separator must be placed in cold water for a short time.
The turpentine is gradually converted into a viscid oil, and when this has.
taken place, and no more heat is developed on repeated agitation, the
acid is tapped off. The oily layer is then transferred to a flask and
subjected to steam distillation. When all that is volatile with steam
has passed over, the oily portion of the distillate is separated from the
aqueous layer, and heated with half its volume of sulphuric acid pre-
viously diluted with one-fourth of its measure of water. The mixture
is well agitated, the acid liquid separated, and the oily layer again dis-
tilled with steam. When genuine turpentine is operated upon, the
volatile portion of this second treatment consists merely of cymene-.
1
Jour. Soc. CJ em. Ind., 1882, 1, 480.
CONIFEE^ 21
and a small quantity of paraffinoid hydrocarbons. It never exceeds
4 to 5 per cent, of the volume of the original sample, and with care is
as low as 3* per cent. If the volume notably exceeds 5 per cent., it is
advisable as a precaution to repeat the treatment with the (4 to 1) acid.
When treated in this manner, petroleum naphtha is not appreciably
affected; hence the proportion may be fairly estimated by making an
allowance of 4 to 5 per cent, from the volume of volatile oil which has
survived the repeated treatment with sulphuric acid. A further puri-
fication may be effected by violently agitating the surviving oil with
several times its volume of concentrated sulphuric acid heated to 50° or
60°. This treatment can be repeated if necessary, after which the
residual hydrocarbon is separated, steam distilled and again measured,
when the surviving oil from pure turpentine oil will not exceed from
•J- to 1 per cent, of the original sample. Any excess over this will be
the minimum quantity of petroleum naphtha present. Shale naphtha
cannot be at all estimated in this way. The behaviour of the oil on
distillation is the best indication of the presence of rosin spirit, as the
temperature rises gradually, and no considerable fraction is obtained at
158° to 160° if much rosin spirit be present.
Allen (Commercial Organic Analysis) gives the table on page 22 as
indicating some of the properties of some substances which have been
used as adulterants for turpentine oil.
More empirical methods for detecting adulteration in turpentine have
been published than is the case for any other essential oil. These are
principally based on colour reactions, and are, in very many cases, quite
useless, especially when the adulterant is carefully purified. Many modi-
fications of processes described above have been published, but do not
appear to possess any advantages over those which have been described.
It is, therefore, considered unnecessary to reproduce so large a bulk of
published work, which has so little bearing on the practical examination
of this oil; but readers who wish for information on these or other little-
used processes or tests, or for details of methods which for any other
reason are not dealt with here, are referred to the following papers :—
J. M. McCandless (J. Amer. Chem. Soc., 1904 (26), 981).
Marcusson and Winterfeld (Chem. Zeit., 1909, 987).
W. Burton (/. Amer. Chem. Soc., 1890 (12), 102).
P. H. Conradson (J. Soc. Chem. Lid., 1897 (16), 519).
H. Wolff (Farbenzeit., 1912 (17), 1553).
Grimaldi (Chem. Zeit., 1908 (32), 8, and 1910 (34), 721).
Dunwody (Amer. Jour. Pharm., 1892 (33) 131).
H. Herzfeld (Chem. Zentralblatt, 1903 (1), 258).
P. van der Wielen (Pharm. Weekblad., 1911 (8), 35).
Nicolardot and Clement (Bull. Soc. Chim., iv. (1910), 7, 173).
V6zes (Bull. Soc. Chim., iii. (1903), 29, 896).
C. Piest (Chem. Zeit., 1912 (36), 198).
Utz (Chem. Zentralblatt, 1905 (1), 1673).
A. W. Schorger l has examined the oils from a number of pine-trees
1
U.S. Department of Agriculture, Bulletin 119.
Turpentine Oil. Rosin Spirit. Petroleum Naphtha. Shale Naphtha. Coal-tar Solvent
Naphtha.
1 . Optical Activity . . . . active usually none none none none s

2 . Specific Gravity . . . . •860 to -872 •856 to -880 •700 to -740 •700 to -750 •860 to ;875
3. Temperature of Distillation 156° to 180° gradual rise gradual rise gradual rise gradual rise
4. Action in the Cold on Coal-tar
Pitch
readily dissolves readily dissolves very slight action very slight action readily dissolves a
5. Behaviour with Absolute Phenol homogeneous homogeneous no apparent homogeneous mix- homogeneous
at 20° mixture mixture solution ture, crystallises mixture
on cooling
6. Behaviour on Agitating 3 vols. homogeneous homogeneous two layers like petroleum —
with 1 vol. Castor Oil mixture mixture of nearly equal naphtha
• volume
7. Bromine Absorption (Dry) . 203 to 236 184 to 203 10 to 20 60 to 80 —
b
o
hH
8. Behaviour with H2S04 almost entirely polymerised very little action considerable moderate action t*
polymerised action OQ
CONIFEEÊ 23
found in the Western parts of the United States, and Adams l has reported
upon similar " wood turpentines ". These results are as follows:—
TUKPENTINE FROM PlNUS PONDEROSA (LAWS).

The specific gravity of the oil was 0-8625; the index of refraction
1*4772; and the specific rotation [a]D '= - 14-39°. On fractionation of
500 grams of oil the following results were obtained:—
Distillate. Specific Index of

Temperature Specific
(corrected). Gravity Refraction Rotation
at 15°. at 15°. at 20°.
Observed. Cumulative.
°C. Per Cent. Per Cent.

164-0-168-2 5-01 5-01 0-8578 1-4740 - 13-81
168-6 9-94 14-95 •8595 1-4750 - 13-70
169-0 9-36 24-31 •8601 1-4752 - 13-17
169-2 9-20 33-51 •8606 1-4753 - 12-92
170-5 10-45 43-96 •8608 1-4754 - 12-73
171-0 10-71 54-67 8612 1-4757 - 12-98
171-6 10-28 64-95 •8615 1-4760 - 13-33
172-4 9-69 74-64 •8619 1-4762 - 14-17
175-0 10-36 85-20 •8621 1-4763 - 17-15
179-5 7-04 92-24 •8631 1-4775 - 24-13
179-5 + 7-74 99-98 •9186 1-5063 + 0-86
Laevo-a-pinene, /2-pinene, and laevo-limonene were detected in the oil.

TURPENTINE FROM PINUS PONDEROSA SCOPULORUM (ENGELM).
The oil had the following characters : specific gravity 0'8639 at 15°;
index of refraction 1*4727 at 15°.
The physical constants of the fractions obtained on distillation are as
follows:—
Distillate. dl5°. ND15°

Temperature Specific Index of
(corrected). Gravity Refraction
Observed. Cumulative. at 15°. at 15°.

157-6-158-5 2-03 2-03 0-8586 1-4686
159-5 9-69 11-72 -8621 1-4701
159-9 9-97 21-69 •8620 1-4702
160-1 10-21 31-90 •8620 1-4705
160-9 10-06 41-96 •8620 1-4706
161-7 9-39 51-35 -8620 14711
162-6 9-97 61-32 •8623 1-4714
165-2 9-12 70-44 •8626 1-4722
170-2 10-50 80-94 •8626 1-4735
173-0 5-94 86-88 •8615 1-4752
177-1 6-25 93-13 -8593 1-4758
183-3 2-19 95-32 •8576 1-4769
183-3 + 4-60 99-92 — "•~
a-Pinene, /3-pinene, and limonene were found in the oil.

1
Jour. Ind. Eng. Chem., 1915 (7), 957.
TURPENTINE FROM PINUS SABINIANA.
The oil had a pleasant orange-like odour; specific gravity, 0*6971;
and index of refraction, 1-3903. On fractional distillation of 500 grams
of the oil the following results were obtained :—
Distillate. <115° XD15-
(corrected). Gravity at Refraction
Observed. Cumulative. 15° C. at 15° C.

96-1-97*3 4-24 4-24 0-6889 1-3890
97-9 7-93 12-17 •6885 1-3898
98-3 9-04 , 21-21 j -6882 1-3898
98-3 8-44 29-65 •6882 1-3898
!
98-4 8-89 38-54 •6880 1-3898
98-4 8-97 47'51 •6881 1-3898
98-5 8-06 55-57 •6881 1-3898
98'5 7-13 62-70 -6882 1-3898
98'5 6-92 69-62 •6881 1-3898
98-5 6-94 76-56 •6880 1-3899
98-6 6-83 83-39 •6879 1-3899
98-7 6-19 ! 89-58 •6879 1-3899
98-8 5-66 95-24 •6881 1-3900
98-8 + 4-66 99-90 •7393 1-4140
This oil is very noteworthy, as it consists almost entirely of the hydro-

carbon heptane, a low boiling paraffin hydrocarbon, quite distinct from
the terpenes, which are the normal constituents of practically all other
turpentine oils.
TURPENTINE FROM PINUS OONTOBTA.
Two samples of this oil had the following characters :—
1. 2.
Rotation . - 20-12°
Refractive index 1-4862 1-4860
About 400 grams were submitted to fractional distillation with the
following results:—
Distillate. dl£»° ND5°

164-4-170 6 2-89 2-89 0-8547 1-4793
171-6 | 8-55 ! 11-44 •8546 1-4814
172-6 9-08 20-52 •8542 1-4823
173-6 10-77 31-29 •8534 1-4835
175-3 10-22 41-51 •8522 1-4852
177*2 9*79 51-30 •8514 1-4861
177-6 10-03 61-33 . -8507 1-4871
177-9 10-23 71-56 •8502 1-4880
178-4 9-26 80-82 •8498 1-4891
178-9 4-15 84-97 •8498 1-4894
178-9+ 14'83 99-80 — —
CONIFEE^ 25
The oil had a very characteristic odour; it was pungent when freshly
'distilled, and, after standing some time, was orange-like. The oil poly-
merised very considerably at its boiling-point. The 15 per cent, residue
remaining in the distilling flask solidified to a solid, amber-coloured mass
resembling colophony, insoluble in alcohol, but soluble in ether and
chloroform. To avoid loss of oil by polymerisation it must be distilled
under reduced pressure. The oil carefully purified and finally distilled
•over metallic sodium, had the following properties: Boiling-point, 60° at
21°
11 mm.; specific gravity, ^ 0*8460; refractive index, 1-4861; specific
J-O
rotation [a]D = - 12'36°.
This oil is also noteworthy, as it consists mainly of /2-phellandrene
which has.not previously been detected in any turpentine oil.
TURPENTINE FROM PINUS LAMBEKTIANA.

An oil obtained from oleo-resin collected during 1911 had the following
properties : specific gravity, 0'8663 ; index of refraction, 1-4728 ; specific
rotation [a]o = + 10*42°. Another sample of the oil had a specific
gravity of 0*8658 and an index of refraction of 1*4727, and gave the fol-
lowing results on fractionation :—
Distillate. d!5° ND15°

°C Per Cent.
155-8-157-3 2-98 2-98 0-9531 1-4657
158-6 9-33 12-31 •S620 1-4693
153-9 10*78 23-09 •8629 1-4698
159-3 10-34 33-43 •8632 1-4701
159-7 10-70 44-13 •8633 1-4703
160-3 9-79 53-92 •8633 1-4708
161*3 9*94 63-86 •8634 1-4716
162-5 9-54 73-40 •8633 1-4726
168-4 7-67 81-07 •8624 1-4736
178-8 5-11 86-18 •8548 1-4721
. 178-8 + 13-62 99-80 •9011 1-4912
The oil contains a-pinene, /?-pinene, a very small amount of phellan-

drene (?), a hydrocarbon, probably of the aliphatic series, and a sesqui-
terpene which is probably aromadendrene.
TUEPENTINE FROM PlNUS EDULIS.
The oil had the characteristic odour of thuja leaf oil, due to the pre-
sence of a sesquiterpene; the specific gravity was 0*8680; the index of
refraction, 1-4707; and the specific rotation, [O]D = + 19-26°.
The oil contains a-pinene, /3-pinene, and cadinene, a compound which
has not previously been recorded as occurring in turpentine oils.
On fractional distillation the following results were obtained :—
Distillate. 6/15° ND 15°

(corrected). ( ravity at Refraction

155-9-157-4 5-10 5-10 0-8617 1-4677
157-6 10-66 15-76 •8617 1-4683
157-9 10-28 26-04 •8621 1-4687
158-4 8-99 35-03 •8619 1-4689
158-9 10-54 45-57 •8616 1-4689
160-0 11-04 56-61 •8611 1-4693
162-4 8-76 65-37 •8609 1-4696
176-5 9-72 75-09 •8605 1-4713
194-9 3-87 78-96 •8616 ! 1-4723
194-9 + 20-74 99-70 •9129 1-4837
TURPENTINE FROM PINUS JEFFREYI.

l
Schorger states that the normal turpentine from this tree consists of
about 95 per cent, of heptane and 5 per cent, of an aldehyde, probably
citronellal. Schimmel & Co.2 have examined this oil and found it to have
Specific gravity 0*7051
Optical rotation 1-39653
Ester value 5-2
,, ,, (after acetylation) 8-7
They agree with Schorger that the principal constituent of the oil is
heptane. They do not agree, however, that citronellal is present, but
have identified decylic acid; possibly traces also of octylic and nonylic
aldehydes may be present. Linalol and m ethyl-chavicol are also pro-
bably present.
The " wood turpentine " of Pinus Jeffreyi was found to consist of 90
to 95 per cent, of heptane, with traces of limonene and citronellal. That,
from Pinus monophylla had a specific gravity 0*9702, rotation + 21-15°,
and refractive index 1*4771. In it were identified a-pinene, /3-pinene, and
cadinene. The corresponding oil from Pinus ponderosa had a specific
gravity 0*8626, rotation - 13*15°, and refractive index 1-4727. It contains
a-pinene, /3-pinene, and limonene.
Russian oil of turpentine is a product, the importance of which has
increased during the past few years, and appreciable quantities are now
imported into this country. The oil is obtained principally from Pinus
sylvestris, but Pinus Ledebourii also contributes to its production. The
crude oleo-resin is, whilst still mixed with a large percentage of impurities,
distilled over a naked fire without the use of water (essence de t^reben-
thine de resine) or the wood is crudely distilled directly (essence de t6r6-
benthine de four).
The resulting oil is brownish in colour with a most unpleasant odour,
due to the presence of decomposition products, which include phenols,
furfural, and benzenoid hydrocarbons.
The principal constituents of Eussian turpentine are, according to»
Sehindelmeiser,3 /2-pinene, sylvestrene, and dipentene. A little dextro-a-
l
Joiir. Ind. Eng. Chem.
3
6 (1914), 541. * Report, October, 1914, 45.
Chemiker Zeitung, 1908 (32), 8.
CONIFERS 27
1
pinene is also present. Zelinski and Alexandroff isolated a highly
laevo-rotatory hydrocarbon [OJD = - 70° 45', which they believed to be
laevo-pinene, but Schindelmeiser2 has shown it to be Zaevo-camphene
contaminated with some impurity. Acetone and a-terpineol have been
found in some samples of Eussian turpentine oil.
According to Schkatelow 8 the following trees yield " Eussian " turpen-
tine oils, having the following characters :—
Field of Oil. [«JD. Specific Gravity.
Pinus Sylvestris 15 to 16 per cent. + 22° to + 24° 0-867 at 15°

,, Abies 13-4 - 13-2° 0-873 „ 15°
(Abies excelsa)
Larix Sibirica . 14-1 - 14-3° 0-870 „ 19°
Pinus Cembra 6 + 14-04° 0-865 „ 15°
,, Taurica 20 - 75-9° 0-861 „ 19°
Abies Sibirica 28 - 35-6° 0-875 „ 19°
The oil of turpentine arriving on this market from Eussia does not
correspond in character wjth any of the above oils. This is due to two
facts; firstly, that the oil is a mixture derived from more than one species,
and, secondly, that the bulk of the exported oil has been deprived of its-
" middle runnings " in Eussia, the so purified middle fractions being used
in the country, so that much of the Eussian turpentine as we know it is-
a fractionated oil. The author 4 has examined samples of pure unfraction-
ated Eussian turpentine supplied to him by Prof. Schindelmeiser, and
found them to contain over 60 per cent, of oil distilling between 155° to
160°, which fractions are missing in nearly all the commercial oil ex-
ported. Two such typical samples had the following characters :—
1. 2.
Specific gravity 0-b67 0-865
Optical rotation + 7° 50' + 10°
Befractive index 1-4718 1-4736
Absorbed by 5 per cent. KOH 5 per cent. 6 per cent.
Distilled below 155° traces only traces only
155° to 160° 65 per cent. 63 per cent.
160° „ 165° 11 ,, 9 „
165° „ 170° 13 „ 15 „
170° „ 180° 7-5 „ 7 „
above 189° 3-5 „ 6 „
Sample No. 1, after removal of the acid bodies and tarry matter, gave
a rectified turpentine oil having the following characters :—
Specific gravity . . . 0*8646
- . .ical
Opt - *rotation
...' . +8°
Ref ractive index . • 1-4890
Absorbed by KOH . none
Dis bils below 155° none
, 155° to 160° 68 per cent.
160° „ 165° 13 „
165° 170° 10 „
170° 180° 7 „
, above 180° 2 ,,
1 2
Chemiker Zeitung, 1902 (26), 1224. Chem. Zentralblatt, 1908 (1), 2097.
*Moniteur
4
Scwntifique, 1908, iv., 22, i., 217.
Chemist and Druggist, 26 October, 1912,
These facts are recognised in the turpentine market, and users are
.content to accept the fractionated oil as Eussian turpentine. But it is
-considered necessary that it should be in a reasonably good condition and
as what is known as of good merchantable quality. The difficulty of fix-
ing empirical standards under these conditions is obvious, but as the re-
sult of considerable experience in disputes on shipments of this oil the
author is able to say that the points to which objection is taken are (1)
the presence of phenoloid bodies (absorbed by caustic potash); (2) the
presence of much oil boiling over 180° which renders the oil unremunera-
tive to refine, as these fractions are useless for most purposes; (3) the
presence of impurities distilling below 155°. As a result of this experi-
ence, the following values may be laid down as representing what is ac-
cepted on the London markets as Eussian turpentine of fair merchantable
quality. The figures relate to four typical samples :—
1. 2. 3. 4.
Initial boiling-point 157° 156° 157° 158°
Distils below 155° none none none none
155° to 160° 1 per cent. 1 per cent. 5 per cent. 11 per cent.
160° ,, 165° 44 „ 45 ,, 40 „ 18 „
165° „ 170° 37 „ 35 „ 42 „ 48 „
170° „ 180° 15 „ 16 „ 10 „ 19 ,,
„ above 180° 3 „ 3 3 „ 4
Specific gravity at 15° 0-863 0-8635 0-863 0-868
Refractive index at 20° 1-4730 1-4726 1-4725 1-4748
Optical rotation + 4° 28' + 4° 30' + 9° + 8°
Absorbed by 5 per cent. KOH nil nil nil nil
A very large number of samples, however, have been even more
largely deprived of their middle runnings, and contain a considerable
amount of hydrocarbons boiling over 180°, and also a considerable
amount of acid bodies, which are absorbed by caustic potash. Such
samples are quite useless to the rectifier, as their redistillation must en-
sure the removal of the acid bodies and also of the bodies boiling over
180°, with a resulting loss which, as mentioned above, causes the rectifi-
cation to be unremunerative.
The following are typical samples of this kind which represent
numerous deliveries on the London market:—
1. 2. 3. 4.
Initial boiling-point . . 148° 146° 146° 153°
Distils below 155° 2 per cent. 3 per cent. 5-5 per cent. 1 per cent.
155° to 160° 3 3 5 3 „
160° „ 165°\ 35 34 22 36 „
165° „ 170° J '
170° ,, 180° 48 50 46 50 „
above 180° 12 10 21-5 10 „
Specific gravity at 15 ° 0-863 0-8665 0-878 0-869
Refractive index at 20° 1-4762
(
1-4756 1-4780 1-4792
Optical rotation . + 88° +
+9°
9' + 11°
11° + 12°
12° 45'
Absorbed by KOH . 6 per cent. 8-5 per cent. 7 per cent. 3 per cent,
Finnish turpentine oil closely resembles Eussian oil. Aschan l has
identified it in the following compounds; diacetyl, furane, methyl-furane,
methyl-isobutyrate, benzene and its homologues, pinene, sylvestrene,
^-limonene, and dipentene. He has also recently isolated a new terpene
from this oil, boiling at 163° to 165°, specific gravity 0-8628 at 20°, and speci-
fic rotation + 7*7°. It is a saturated bicyclic terpene, closely related to
1
Farm. Notisblad., 1907, 93, and Chem. Zeit. (1919), 1, 284.
CONIFEEÊ 29
pinene. A terpene alcohol, and a sesquiterpene (cadinene ?) are also
present. A somewhat similar product is manufactured in Norway, as a
by-product in cellulose manufacture. It has a specific gravity 0*874
and optical rotation + 13°. It contains pinene, cadinene, and
sylvestrene.1
French oil of turpentine is characterised by a high laevo-rotation.
It is obtained principally from Pimis Pinoster (Pinus maritima Poir)>
(vide supra), and has the following characters :—
Specific gravity at 15° 0*863 to 0*875
Optical rotation - 20°,, -38°
Initiial boiling-point 152° „ 155°
Distillate below 165° 80 to 90 per cent.
It resembles American oil in other respects, the pinene present merely
differing by consisting more largely of the laevo-rotatory variety.
Normal Italian turpentine is the product of Pinus picea and Pinus
pinaster. Palazzo2 gives the following values for a typical pure com-
mercial sample:—
Refractive index . . . . . . . . 1*4678 a t 2 5 °
Eighty per cent, distilled between 155° and 165-5". The first fraction,,
distilling up to 159° had a specific gravity O8576 at 20°, optical rotation
- 46° 54', and refractive index 1'4653 at 25°. The pure samples from
Pinus pinaster only had the following characters :—
Specific gravity at 15° J
, 0-867 0-871
Befractive index at 20° . 1-4700 1-4707
Optical rotation . . . - 35° - 35°
The high optical rotation is stated to be due to the presence of
Z-limonene.
Greek turpentine oil is a commercial article in the South of Europe
and is obtained from the Aleppo pine (Pinus halepensis). It is produced
in nearly all the provinces of Greece. It is usual either to make deep
incisions in the trunks through which the resin quickly flows away, or in
the French manner to cut rather shallow notches and place a wooden
receptacle below these, in which the oleo-resin is collected. Pinus hale-
pensis is the only tree in Greece which is used for the production of
turpentine.
The crude oleo-resin contains from 20 to 25 per cent, of oil and 7O
per cent, of resin. The essential oil consists principally of dextro-a
pinene. Gildemeister and Kohler 3 isolated this body in a fairly pure
condition, but Tsakalotos and Papaconstantinou4 have more recently
separated it in an apparently purer condition. The characters of the
hydrocarbon so separated are as follows :—
Gildemeister. Tsakalotos.
Specific gravity . . 0'8642 at 15° 0-8548 at 25°
Refractive index . . 1-46565 „ 20° 1-4633 „ 25°
Optical rotation . . + 40-23° + 47-7°
Boiling-point . . . 156° at 760 mm. 155° to 156° at 760 mm,
Greek turpentine has the following characters :—
1
2
Fosse, Ber. Deuts-h. pharm. Ges., 25 (1915), 303.
:;
Ann. Chim. Applic. (1917), 7, 88.
4
Wallach-Festschr'ft, Gattingen, 1909, 429.
Jour, de Pharm. et de Chim., 1916, 4. 97.
Specific gravity 0'860 to 0-866
Optical rotation . + 34° „ + 47°
Refractive index . . . . . . . 1-4670 „ 1-4740
Distillate from 152° to 156° 5 to 10 per cent.
„ 156° ,,160° 80 „ 85
The turpentine oil from Pinus longifolia has recently been examined
by Simonsen.1 He found present \the following bodies : laevo-a-pinene,
/3-pinene, a new terpene for which he proposes the name d-carene, and a
new sesquiterpene which he terms longifolene. In the previous edition
of this work (p. 28) it was stated that 3-sylvestrene was present in com-
paratively large amount.
It is probable that this is incorrect, but that another terpene has been
mistaken for sylvestrene on account of the fact that by the action of
hydrochloric acid, a molecular rearrangement takes place, with the
formation of sylvestrene hydrochloride. This hydrocarbon is that
isolated by Simonsen and named by him d-carene. It is an oil having
Specific gravity @ 30° . 0-8586
Refractive Index @ 30° 1-4690
Optical Rotation + 7-69°
Boiling-point at 705 mm. 168° to 169°
It yields sylvestrene hydrochloride when treated with hydrogen chloride

in ethereal solution. It yields a crystalline nitrosate, decomposing at
141-5°.
Its constitution is not yet settled. The sesquiterpene ^-longifolene
boils at 150° to 151° at 36 mm., or at 254° to 256° at 706 mm. Its
specific gravity is 0*9284 at 30°, refractive index, 1-4950 at 30°, and optical
rotation + 42'73°.
It yields a hydrochloride melting at 59° to 60°, and having a specific
rotation + 7*1°. Its hydrobromide melts at 69° to 70°, and its hydrio-
dide at 71°.
The characters of this oil fall within the following limits :—
Specific gravity 0*865 to 0-875
Optical rotation 0° to + 4°
Initial boiling-point 165°
Two samples on fractionation by Eabak 2 and by Schimmel & Co.3

gave the following results :—
Rabak. Schimmel.
165° to 170° 56 per cent., aD = - 2 ° 33 per cent., aD = - 3° 30'
170° ,,175° 20 „ „ = + 2 ° 48' 31 „ ,. = + 0° 40
175° ,,180° 9 „ , , = + 6 ° 50' 14 „ „ = + 4° 32'
above 180° . 15 ,, „ = -}- 18° 12' 22 „ „ = + 16° 22'
Austrian turpentine oil is derived principally from Pinus laricio. Its

composition has not been exhaustively studied, but it consists of terpenes
and is similar in composition to French turpentine oil. Its characters
are as follows :—
iJour. Chem. Soc. (1920), 570.
*Pharm. Rev., 23 (1905), 229. s Report, April, 1906, 63.
CONIFERS 31
Specific gravity . 0-863 to 0-870
Optical rotation -35° „ -40°
Distillate from 155° to 158° 45 to 50 per cent.
„ 158° „ 160° about 30 „
,. 160° „ 165°
„ 165° ,, 175°
TURPENTINE FROM AGATHIS EOBUSTA.
The oleo-resinous exudation from this Australian tree, known as the
"Queensland Kauri," yields an essential oil, which has been examined
FIG. 4.—Tree of Agathis robusta, Queensland.

[P. 373, Pines of Australia.
by Baker and Smith.1 The yield of oil was 11*64 per cent, having the-
Specific gravity at f£° C 0-8629
Kotation aD in 100 mm. tube + 20-2°
Refractive index at 16° C. 1*4766
Thirty c.c. of the oil were distilled under atmospheric pressure, when
nothing came over below 155° C. ; between 155° and 156° C., 53'3 per
cent, distilled; and between 156° and 159° C., 33*3 per cent, more came
over. The residue in the flask, 13*3 per cent., was also determined.
The first fraction had the following characters :—
Specific gravity at fp C 0'8625
Kotation aD + 14-4°
Refractive index at 17° C. 1-4755
The second fraction had the following characters :—
Specific gravity at lf° C 0-8603
Rotation aD + 20*4°
Refractive index a t 17°C. . . . . . . . 1-4763
The portion remaining in the flask had the following characters :—
Specific gravity at $£° C 0-8610
Rotation aD + 38-6°
Refractive index at 17° C 1-4791
Pinene was the only constituent identified.
In addition to the above described turpentine oils, the following, al-
though not of considerable importance, are of some interest :—
Specific Rotation. Refractive
Origin. Gravity. Index. Constituents.
Spanish —
Pinus lialepensis . ) 0-860 - 9° 1-4654
2
„ pinaster . . /
Algerian—
Pinus halepensis 0-860-0-863 + 45° to +48° 1-4638-1-4660 d-pinene
Mexican . . . . . — + 34° — limonene (?)
3
Philippine —
Pinus insular is . 0'869 + 13° to + 28° 1-4700 d-a-pinene ;
Burmese — £-pinene
4
Pinus Khasyjb .
,, Merkiisii .
Japanese —
Pinus Thunbergii
0-863
0-861
—
+ 36°
+ 32°
—
=}
—
d-a-pinene
Various — —
Picea excelsa 0-863-0-870 + 3° to - 12° — a-pinene, di-
5
pentene,
" Strasburg Turpentine Oil " — limonene
6
Abies Alba . 0-860-0-861 — — a-pinene
Venetian Turpentine Oil —
Lariv decidua . 0-865-0-878 - 8° to - 12° 1-4700 a-pinene
7
Canada Balsam Oil —
Abies balsamea (and other 0-862-0-865 - 25° to - 38°1-4730-1-4765 /-a-pinene
species) . . . .
Oregon Balsam Oil —
Pseudotsuga Douglasii 0-858-0-882 - 30° to - 48° 1-4730 Z-a-pinene
1 2
3
The Pines of Australia, 386. 4
80 per cent, distils at 155° to 156°.
5
96 per cent, distils between 154° and 165-5°. Distils chiefly at 165°.
6
Distils chiefly at 162° to 163°.
60 per cent, distils from 157° to 161°; 20 per cent, from 161° to 164°, and 6 per cent,
from7 164° to 168°.
Distils chiefly between 160° and 167°.
CONIFEE^ 33
OIL OF JUNIPER.
The plant yielding this oil is Juniperus communis, a native of Greece,
and widely distributed over Europe. It is a small shrub or tree varying
from 2 to 6 ft. in height, but in parts of Norway it forms a forest tree
some 30 to 40 ft. in height. The Italian berries, however, are most
valued for oil. According to Pereira, the juniper of the Bible was a
leguminous plant, probably the broom or furze tree. Fraas considers
the /cc'Spos jjiiKpa of Dioscorides was our juniper. The plant is usually
dioecious, and the scales of the cones, when ripe, become succulent, and
cohere to form a kind of berry (galbulus). These berries are rich in
sugar, and by their fermentation and distillation the well-known beverage,
gin, is obtained, which owes its characteristic flavour to the oil of juniper.
It has been stated that the oil is distilled from the full-grown, but unripe,
fruit. But with reference to this point, Schimmel and Co.1 states that
" this is an error, at least no such oil is distilled on a large scale. It is
an antiquated idea, originating with Zeller, that unripe fruits render a
larger yield in oil than ripe ones. In any case, the oil distilled from
unripe berries in all essential qualities is inferior to normal oil of ripe
fruits." The following are given by Schimmel as the average yields of
oil from plants grown in certain districts :—
Bavarian . . 1/2 per cent. .
East Prussian •6
Thuringian •7
Swedish •5
Italian 1 to 1-5
Polish •9
Hungarian . •8 t o l
The oil is distilled on a very small scale in England, but, according
to the Perfumery and Essential Oil Record* hitherto it has not been
possible to produce the oil competitively with southern Europe, because
of the relative cheapness of labour and the vast tracts of land over which
the trees grow wild. It also must be remembered that the foreign oil is.
produced under somewhat different conditions, and may be almost con-
sidered a by-product. There is a considerable demand on the Continent,
for an aqueous extract of the berries, called " Boob," or " Bob of Juniper,""
and the distilled oil is in this case a by-product, the berries being first
crushed and macerated with water and then distilled with water, and the
residue in the still evaporated to a soft consistence.
Much of the oil met with in commerce also is probably not normal in
composition, but is obtained as a by-product in the manufacture of gin
and similar spirits.
There can be no reason why it should not be possible for our northern
dependencies to produce all that is required.
The juniper plant is a small shrub 4 to 6 ft. high, or in sheltered
woods growing higher, widely distributed throughout the northern hemi-
sphere, in Europe from the Mediterranean to Scandinavia, in Asia
northwards from the Himalaya Mountains, in North America from the
southern states to Greenland. It requires a certain amount of moisture,
with some drainage, and apparently prefers some lime in the soil. It
occurs freely on the slopes of the chalk downs near London, and on
healthy, and therefore silicious, soil where a little lime occurs. On
mountains in the Arctic regions a small form of the plant occurs, viz.,
1 2
Report, October, 1898, 30. P. and E.O.R., March, 1915, 63.
VOL. I. 3
Juniper us nana Willd., with rather longer berries and a prostrate habit.
Especially where bands jof limestone occur, as on some of the Scottish
mountains and on the limestone hills in the Lake district, it is a common
plant.
The berries take two years to come to maturity, so that there are
always mature and immature berries on the same plant, and the collec-
tion by hand, unless the branches are beaten over a tray, is, owing to
the sharp points of the leaves, rather a prickly matter. The blackish
berries that are imported are apparently all mature, indicating that the
green immature berries are separated. The immature berries, however,
darken on keeping.
Whether imported oil of juniper is always distilled from Juniperus
communis is open to question, since the oil of some red juniper berries
imported from Smyrna, and attributed to Juniperus phoznicea, has been
found to correspond in all its properties with those of Juniperus com-
munis. But on examination of an oil distilled in Cyprus from the berries
of Juniperus phanicea at the Imperial Institute, it was shown to differ
from that of Juniperus communis in optical rotation, which was + 5°,
whilst that of 0Juniperus communis distilled from the berries is usually
- 3° to - 15 .1
The yield of oil from imported berries varies from O5 to 1*5 per cent,
the Italian averaging 1 to 1*5 per cent., the Bavarian 1 to 1*2 per cent.,
the Hungarian O8 to 1 per cent. The berries imported from East Prussia,
Poland, and Thuringia average 0*6 to 0'9 per cent., and Swedish berries
only 0'5 per cent, of oil, the berries of the more southern plants yielding
the most oil. This indicates that sunny slopes are likely to be the best
places to cultivate the plant for the berries. The yield of oil, however,
varies considerably in different years.
The known constituents of juniper oil are the terpenes, a-pinene, and
camphene, the sesquiterpene cadinene, and a small amount of oxygenated
constituents. The principal of these bodies is terpinenol. A second
alcohol (or possibly a mixture of alcohols) has also been separated,
having the following characters: boiling-point, 218° to 226° ; specific
gravity, O9476; optical rotation, - 4° 30'; and refractive index, 1*4825.
In old oils a crystalline substance is sometimes to be found, which has
been described as juniper-camphor. Its constitution is unknown, but
it is possibly a sasquiterpene alcohol. Traces of esters are also present.
The physical characters of juniper oil vary so enormously according
to the age of the oil, that it is very difficult to suggest limit values. For
reasonably fresh oil that has been kept under proper conditions the fol-
lowing figures will usually apply :—
Specific gravity . . . 0-865 to 0-890
Optical rotation . . . - 3° ,, - 20° (rarely slightly dextro-rotatory)
Refractive index . . . 1-4750 to 1-4880
Acid value . . . 1 to 4
Ester ,, . . . 2 ,, 8
,, ,, (after acetylation) 15 ,, 25
The oil is usually soluble, when freshly distilled, in four volumes of
95 per cent, alcohol. But too much reliance must not be placed on this
test, as insolubility rapidly results from age. The approximate propor-
tions of pinene and cadinene should be determined by a fractional dis-
tillation. The results vary according to the fractionating apparatus
*P. and E.O.R., 1913, 291.
CONIFEEÊ 35
used, but with a series of bulbs, from 25 to 35 per cent, is obtained be-
tween 155° and 160°, and from 10 to 20 per cent, between 270° and 280°.
With our present knowledge of this oil, no further analytical methods
are yet available. A good juniper oil should contain sufficient cadinene
for the residue after distilling off 75 per cent, to have a refractive index
of 1-4950.
Umney 1 has reported on the effect of age on an English distilled
juniper oil, which is no doubt identical with what takes place with other
oils. The oil when distilled in 1898 had a specific gravity 0*871. In
1914, this figure had risen to 0*977, and the refractive index was 1*4960.
Jumper wood oil, as met with in commerce, is not a natural product
at all. It is usually a mixture of turpentine with sufficient juniper berry
oil to give it an odour of juniper oil.
The berries of Juniperus phanicea, which are found in Cyprus, yield
an oil having the following characters :—
Refractive index . . . . . . . . about 1'4710
The leaves of Juniperus phwnicea yield an oil iwhich has been in-
correctly offered in the market as oil of savin. —
The berries of Juniperus oxycedrus yield about 1*5 per cent, of essen-
tial oil having the following characters :—
Specific gravity 0-850 to 0856
Optical rotation - 4° „ -10°
The wood of this plant yields up to 3 per cent, of oil of specific gravity
0925, and optical rotation - 30°.
OIL OF CYPEESS LEAF.
Oil of cypress is distilled from the leaves of Cupressus sempervirens
(fastigatd), the yield being from 0*2 to 1*2 per cent. Cupressus lusi-
tanica also yields a similar essential oil.
This oil is popularly supposed to be a remedy for whooping-cough,
but its efficacy in this respect can scarcely be said to be soundly estab-
lished. The oils have the following characters :—
French Oils.
Cupressus Cupressus
sempervirens. lusitanica.
Specific gravity . . . . 0-868 t o 0'S84 0-872
Optical rotation + 12° + 31° + 9° 10'
Refractive index 1-4710 1-4760 —
Acid value 0-7 2 1
Saponification value 3 16 9-8
(after acetylatioii) 9 32 26-6
German Oils.
Cupressus
sempervirens.
Specific gravity 0-880 „ 0-900
Optical rotation + 4° ,, + 18°
Refractive index 1-4740 ,, 1-4800
Acid value 1-5 ,, 3
Ester ,. 13 „ 22
,, ,, (after asetylation) 36 „ 51
!P. and E.O.R., 1914, 5.
The oil contains d-a-pinene, d-camphene, d-sylvestrene, a ketone
resembling thujone, terpinyl esters, a sesquiterpene, cedrol, and alcohols
which have been investigated by Schimmel & Co.1 with the following
results:—
The principal constituent of the mixture is an alcohol, terpinenol-4
of the formula C10H18O. Sabinol is possibly present in the alcohol
mixture, but has not been characterised with certainty. A third alcohol
is present which has the following features :—
It is esterifiable with benzoyl chloride (using pyridine) and was re-
covered from the steam-distillation residue by saponification. For pur-
poses of purification it was again treated with phthalic anhydride at
an increased temperature. Unfortunately, in this manipulation part of
it was decomposed. The pure alcohol C10H18O has a pleasant, rose-
like odour. Its constants were as follows: boiling-point 76° to 77°
(4 to 5 mm.), 210° to 212° (ordinary pressure), d15o'O9422, aD + 43° 38'
WD20o i'46678.
With phenyl and naphthyl ^socyanates only liquid derivatives were
obtained. No diphenylurethane was formed. Judging by the odourr
oxidation with Beckmann's mixture appears to give rise to an aldehyde.
With regard to the cypress oil fractions with the highest boiling-point,,
which possess in a more pronounced degree the peculiar balsamic odour,
it would appear that they contain, besides cadinene and cypress-camphor,
a sesquiterpene alcohol, boiling at 13.6° to 138° at 5 mm. pressure.
THUJA-LEAF OIL.
This oil is obtained by distillation with steam of the leaves and pos-
sibly also the small twigs of Thuja occidentalis, the well-known Arbor-
vitce, sometimes also called the white cedar. The yield of oil is from
0*4 to 1 per cent. It is almost colourless, but by oxidation becomes,
slightly greenish or yellow. Its odour is not particularly pleasant,
somewhat recalling that of tansy oil. It is frequently adulterated with
cedar oil, pine-leaf oils, and turpentine. The earliest scientific investi-
gations of this oil are those of Schweizer and Jahns,2 but that of
Wallach,3 undertaken when our knowledge of the group of compounds
contained in the oil was a little more advanced, is now the standard
work. The chief constituents of the oil are a-pinene, laevo-fenchone
C10H16O, and the isomeric ketone, dextro-thujone, which also occurs in
the oils of tansy, wormwood, and sage. Traces of esters, probably of
acetic and formic acid, are also present. A small quantity of laevo-
borneol or its esters is also present. The highest boiling constituents
of the oil have not yet been thoroughly examined, but Wallach believes
them to contain the last-named body in the inactive form.
Carvotanacetone was isolated from the oil by Wallach during a
fractional distillation, but it is probable that this is the result of the
action of heat on the thujone present, and that it is not a natural con-
stituent of the oil.
Pure thuja-leaf oil has the following characters :—
Specific gravity 0-910 to 0'935
Optical rotation . . . . . . . - 5° ,, - 15°
Acid value 0 ,, 1
Ester „ 18 ,, 25
,, , , (after acetylation) ' . . . . . about 4 0
1
Report, April, 1913, 50.
2
Jour, prakt. Chem., 30 (1843), 376 ; Arch. Pharm., 221 (1883), 749.
3
Annalen, 272 (1892), 99.
CONIFERS 37
It is soluble in 3 to 4 volumes of 70 per cent, alcohol. The greater
part of the oil distils between 180° and 208°.
Eose and Livingstone J obtained about 1 per cent, of essential oil
from the leaves and young branches of Thuja plicata, the so-called
Washington cedar. This oil has the following characters :—
Optical rotation - 4*77°
Acid value . . . . . . . . . 0*5
Ester „ 2-28
„ ,, (after acetylation) . . . . . . . 8-8
About 85 per cent, of the oil distilled between 100° and 110° at
40 mm., and consisted of a-thujone. From 3 to 5 per cent, of d-a-pinene
is also present, as well as about 3 per cent, of tanacetyl alcohol, probably
in the form of its acetate. An oil distilled by Schimmel & Co. from the
dried leaves had an optical rotation + 5*4°, but as the sample examined
by Kose and Livingstone was prepared from fresh material in the country
of its origin, it may be taken to possess the normal characters of the oil.
SAVIN OIL.
Oil of Savin is obtained from the fresh twigs of Juniperus sabina.
It is an oil which finds but a limited employment in legitimate pharmacy
as a uterine stimulant and emmenagogue. It is of no value for per-
fumery purposes, as its odour is somewhat unpleasant. It is occasion-
ally used for criminal purposes, and one case is recorded of a medical
man being sentenced to transportation for having used it with the in-
tention of procuring abortion.2 It was official in the 1885 British
Pharmacopoeia, but it has been wisely omitted from the later editions.
The yield of oil from the twigs is fairly high, varying from 3 to 5 per
cent. An oil is distilled in the south of France from various other
species of Juniperus (Juniperus phosnicea and Juni/perus thurifera, for
example) and is incorrectly called savin oil.
The oil contains a number of constituents, of which Wallach first
characterised the sesquiterpene, cadinene. A considerable proportion of
terpenes is present, which appear to consist of sabinene, terpinene, and
traces of pinene. Fromm 3 separated the oil into three main portions
by fractional distillation. The earliest distillate, below 195°, contains
furfurol, di-acetyl, and methyl alcohol, but consists mainly of terpenes;
the middle portion, 195° to 235°, consists chiefly of ethereal salts, and
the last portion, 235° to 310°, consists of cadinene and some resinous
bodies, which are possibly the effects of heat on the terpenes. The
middle fraction yields an oil boiling at 222° to 224°, which was shown
to be the acetate of an alcohol C10H15OH, which the author terms
sabinol and which is present to the extent of 10 per cent. (Schimmel
had previously identified an alcoholic acetate, but the formula of the
alcohol was given as C10H17OH). The alcohol, obtained by hydrolysing
the acetate, is a colourless oil, boiling at 210° to 213° (but see below),
and with only a faint odour. In the higher boiling fraction of the esters,
Fromm also detected a liquid dibasic acid boiling at 255°, of the formula
C20H3605 and a solid acid, C14H1608, melting at 181°. According to
1
Jour. Amer. Chem. Soc.t 34 (1912), 201.
2
Medical Times and Gazette, 1852, 404.
*Bericht, 31 (1898), 2025; 33 (1900), 1210.
Schimmel,1 the amount of this ester present is about 40 per cent., and
there is in addition about 10 per cent, of the free alcohol in the oil.
There is also present a small amount of either an aldehyde or a ketone
boiling between 220° and 250°, yielding a hydrazone melting at 41° and
an oxime melting at 285°.
Schimmel & Co. have found citronellol in this oil, and Elze 3 has
detected geraniol and dihydrocumic alcohol, and also traces of normal
decyl-aldehyde. 'nnRJ
Agnew and Croad 4 have examined this oil and have isolated \ the
terpene sabinene from it in a pure condition. Contrary to Semmler 5
and Wallach6 these chemists found it to be present as the laevo-rotatory
variety, having a specific rotation -42*5°; the hydrocarbon isolateduby
Semmler had an optical rotation + 63° and that of Wallach + 67'5°. nnR.
According to Agnew and Croad the characters of sabinol arenas
follows :—
Boiling-point . . 208° to 209°
Specific gravity . . 0-9391
Specific rotation . . + 17-04 (= + 16° observed for 100 mm.)
But according to Pastini and Eetora,7 sabinol has the following char-
acters :—
Boiling-point 208°
Refractive index 1-4895'
Savin oil has the following characters :—
Optical rotation + 38° to + 63° (rarely to +
Refractive index 1-4720 to 1-4800
Acid value 0,, 3
Ester 105 „ 140
(after acetylation) 125 „ 155
From 25 to 30 per cent, distils under 175°. The oil is soluble in
5 to 15 volumes of 80 per cent, alcohol, but not always to a quite clear
solution.
According to Umney and Bennett,8 the French so-called savin oil is
probably distilled from the leaves and twigs of Jimiperus phcenicea which
accounts for its difference from the German and English distillates.
This French oil has a specific gravity about 0*890; rotation + 4° 30';
esters 9*3 per cent.; total alcohols as sabinol 17*1.
About 64 per cent, of this oil distils below 165°, due to the presence
of a large amount of pinene. Cadinene and traces of an aldehyde were
also found in this oil, which has also been investigated by Eodie 9 who
found that it contained over 90 per cent, of terpenes, which consisted of
pinene, Z-camphene and phellandrene. Acetic and capronic acids were
identified as constituents of the esters. The oil from the leaves and^twigs
of Juniper us phanicea has the following characters, which will indicate
the effect of its addition to the true oil of savin :—
1
8
Report, October, 1895, 44. ^Bericht, October, 1907, 80.
4
Chem. Zeit., 34 (1910), 767. fi
Analyst, 1912, 295.
*Bericht, 33 (1900), 1464.
7 8
Ibid., 40 (1907), 587.
9
Ait. E. Acad. Lincei, 1916, 25, ii., 377. Pharm. Jour., 75 (1905), 827.
Butt. Soc. Chim., iii., 35 (1906), 922.
CONIFEB.E 39
Optical rotation -f 2° , +i
Ester value 0 , 26
,, „ (after acetylation) 5 60
These figures have reference to samples of apparently authentic origin,
but it must be remembered that some admixture of the leaves of allied
species may have taken place before distillation. Most specimens of ab-
solutely authentic origin have a specific gravity below 0*875, an ester
value not exceeding 5, and ester value after acetylation below 20.
CEDAR-LEAF OIL.
The true cedar-leaf oil may be regarded as the distillate of the leaves
of Juniperus virginiana, the red cedar, but the confusion implied in the
name " cedar" is reflected in the enormous variations met with in com-
mercial samples of so-called cedar-leaf oils. No doubt the leaves of
Thuja occidentalis and Chamcecyparis spharoidea contribute largely to
the commercial oil. Brant, indeed, describes the oil as having a " pene-
trating, disagreeable odour," and as " therefore not suitable for perfumery
purposes". Cedar leaves yield about 0'2 per cent, of essential oil, of
pleasant aromatic odour, having the following characters :—
Optical rotation + 5 5 ° , , + ^62°
Saponification value 8 „ 14
„ ,, (after acetylation) . . . 35 ,, 45
It is not soluble in even 10 volumes of 80 per cent, alcohol.
The examination of a pure sample by Schimmell showed that it con-
tains a-pinene, limonene, cadinene, borneol, and bornyl esters, probably
including bornyl valerianate; other terpenes are also present. Com-
mercial oils have specific gravities of 0'860 to 0'920 and optical rotations
of - 3° to - 24°.
The true Juniper its virginiana leaf oil is more expensive than the
corresponding oil from cedar wood—being worth from three to five times
as much, in fact, and as the oils from thuja and other leaves are also less
costly, it is a matter of importance that the oil should be carefully ex-
amined. Six commercial samples and one pure sample, examined by
Schimmel & Co., gave the following results :—
Specific Optical Solubility in
Gravity. Rotation. 70 per Cent. Alcohol.
Pure oil •887 59° 25' very insoluble,
1 •897 12° 25' insoluble.
2 •886 3° 40'
3 •887 24° 10'
4 •920 • 10° 25' soluble in 4 parts.
5 •918 10° 55' ,, „ '5 parts,
6 •905 10° insoluble.
SEQUOIA OIL.
Sequoia oil is obtained from the leaves of Sequoia \giganfea\ (Welling -
tonia gigantea, Lindl.), the Californian mammoth* tree. Lunge and
Steinkauler2 obtained the oil from smaller ornamental trees grown in
Zurich. The first portion of the distillate contained a crystalline hydro-
carbon C13 H10, melting at 105°, which these chemists termed sesquoiene.
The later distillate contained a dextro-rotatory terpene boiling at* 155°, and
l 2
Bericht, April, 1898, 14. Ibid., 13 (1880), 1656 ; 14 (1881), 2202.
having a specific gravity 0'852 and optical rotation -f 24°; and an oxy-
genated body, C10H20O3. This body boils at 227° to 230° and has a
specific gravity 1-045 and optical rotation + 6°. It has an odour recall-
ing that of peppermint. These bodies require further investigation, but
as the oil has no commercial importance, it has not attracted much at-
tention so far.
ATHROTAXIS-LEAF OIL.
The leaves of A thro taxis selaginoides, a member of the dense scrub
which abounds in the region of Williamsford, Tasmania, yield about
0-076 per cent, of essential oil, which has been examined by Baker and
Smith,1 who give the following description of it:—
The crude oil is of a light amber colour, is somewhat mobile, and has
a secondary lemon-like odour not well defined. The oil is a terpene one,
and consisted very largely of dextro-rotatory limonene, which had the
very high specfic rotation [a]D = + 112'2°. The oil is somewhat insoluble
in 90°/0 alcohol, but it formed a clear solution with absolute alcohol in
all proportions. Pinene was probably present, but in traces only. A
small amount of an ester was found, but sufficient material was not
available to enable either the alcohol or the acid to be identified.
The oil contained a fair amount of a constituent boiling above 270° C.
—evidently a sesquiterpene or similar body. The reactions for cadinene
were not satisfactorily obtained, although some of the results would seem
to indicate the presence of that sesquiterpene.
The specific gravity of the crude oil at if0 C. = 0-8755; rotation
a D « + 74-8°; the refractive index at 16° C. = 1-4905. The saponifica-
tion number for the esters was 8-6, equal to 3 per cent, of ester as
bornyl-acetate.
Only a small quantity of the oil could be spared for analysis, but this
on redistillation gave a very small amount boiling below 174° C. Be-
tween 174° and 177° C., 47 per cent, distilled ; between 177° and 200°,
23 per cent, distilled; the temperature then quickly rose to 275°, and be-
tween that and 295° C. 12 per cent, distilled.
The specific gravity of the first fraction at if ° C. = 0-8446; of the
second, - 0'8494; of the third, 0'9373. The rotation of the first frac-
tion, a D = + 90-2°; of the second, + 91-8°; of the third, + 29'6°.
On again distilling the first two fractions, 28 per cent, of the total oil
came over between 174° to 175° C., and 18' per cent, between 175° to
176° C. (cor.). The specific gravity of the first fraction at 19° C. =
0-8427 ; and of the second, 0*8425.
The rotation of the first fraction aD = + 91-4^ or specific rotation
[a] = + 108-5°; of the second, -f 94*5°, or specific rotation [a]D _ +
112-2". The refractive index of the first fraction at 20° C. = 1-4783 ; of
the second, 1*4785.
The teti^Jbromide was readily prepared from both fractions, and this
melted at 104° C.
From the above it is evident that the larger portion of the lower boil-
ing constituents of the oil of this tree is dextro-rotatory limonene.
Dipentene does not occur. From the slightly lower rotation and boiling-
point of the first fraction, it is probable that a small amount of pinene
was present, but it can only occur in traces. A trace of the sesquiterpene
1
The Pines of Australia, 303.
CONIFEKÊ 41
•evidently still remained with the fraction, as indicated by the refractive
index, although the results, taken as a whole, are very close to those re-
quired for pure limonene.
IV,. 5.—Athrotaxis selaginoides. King William Pine. Athrotaxis selaginoides.

'The Pine* of Australia.'} Don. Tasmania. [Baker and Smith.
A small amount of a phenolic body was isolated from the higher

'boiling portion of the oil (carvacrol ?)'.
OILS OF ARAUCARIA CUNNINGHAMII.
This Australian tree, known as the Moreton Bay Pine, is found in
New South Wales and Queensland. Its leaves yield a very small quan-
tity of essential oil (O005 per cent.) having the following characters :—
Specific gravity ar, 21° . 0-8974
Refractive index at 21° 1-4U77
Saponification value 4.4
FIGL 6.—Araucaria Cunninghamii. Fasciation at top of a tree under cultivation at

Beecroft, New South Wales. (A rare instance of teratology.)
The Pines of Australia]. [Baker and Smith^
CONIFERS 43
A latex exudes from the tree, which has been examined by Baker and
Smith,1 and is of interest in that it yields an essential oil containing a
pIG. 7_Araucaria Cunninghamii. Cultivated tree at Beecroft, New South Wales.

n
Thehe Pines of Australia.] Fasciation at top. ' [Baker and Smith.
hydrocarbon C10H,0. which as a colourless liquid having a specific gravity

0-7927 at 19°,' refractive index 1-4437 and boiling-point 155°. It has an
1
The Pines of Australia, 334.
odour recalling that of menthene. It is probable that a second hydro-
carbon of the formula C10H18 is also present. The oil itself has the fol-
lowing characters :—
Specific gravity at 22° 0-S058
Kefractive index 1-4670
Optical rotation . +3-2°
CONIFEK.E 45>
OILS OF THE GENUS CALLITRIS.
A large number of essential oils derived from various parts of this
important family of Australian pines, have been examined by Baker and
Smith.1 These authorities summarise a number of interesting points
which their researches on these oils have established as follows :—
The rotation of the terpenes of the oil from the leaves of some species-
of Callitris is in the opposite direction to that obtained from the fruits,
even if collected from the same tree.
The acetic ester of geraniol is more pronounced in the leaf oils than
is that of borneol, and it continues to increase in the several members
of one section, until a maximum of over 60 per cent, is reached in the
oil of Callitris Tasmanica.
An ester of terpineol was found in the leaf oil of Callitris gracilis.
The lirnonenes and dipentene occur in the leaf oils, the dextro-
rotatory form reaching a maximum in Callitris arenosa, and the laevo-
form in Callitris intratropica. In these oils is seen a well-defined
illustration of the formation in nature of the two active forms of
limonene in the same plant, as well as the racemic modification.
The leaf oil of Callitris Macleayana contains a constituent which
has a marked resemblance to menthene, and is apparently a member of
that group of hydrocarbons.
The leaf oil distilled from some species of Callitris is comparable
with the best *' Pine-needle oils " of commerce.
The oil obtained by steam distillation from the timber of the Callitris
generally, contains the sesquiterpene alcohol Guaiol in some quantity;
the corresponding sesquiterpene is also present.
The characteristic odour of Callitris timber is due to a phenol. This
has distinctive colour reactions and is evidently new. It appears to be
the constituent which renders Callitris timber objectionable to white-
ants. The name Callitrol is proposed for it.
The following species have been examined :—
CALLITRIS EOBUSTA.
The leaves of this tree yielded 0*261 per cent, of oil having a specific;
gravity 0*b825, optical rotation + 10*3°, and refractive index 1*4752 at
19\ The saponification value was 49*59, equal to 17*35 per cent, ester
as bornyl and geranyl acetates. In the cold, with three hours' contact,
the saponification number was 22*78, equal to 7*97 per cent, ester. On
redistilling, practically nothing came over below 155° C. ; between 155°
and 160°, 35 per cent, distilled; between 160° and 165°, 17 per cent.;
between i 165° and 200°, 20 percent.; between 200° and 250°, 12 per cent.
The somewhat large percentage of the oil boiling above 250° indicated
the presence of a sesquiterpene or allied body, but it was not isolated.
The specific gravity of the first fraction at 15° C. = 0*8613; of the
second, 0*8616 ; of the third, 0*8651 ; of the fourth, 0*907. The rotation,
of the first fraction aD = + 12*2°; of the second, + 12*7°; of the third,
+ 14*15U. With the fourth fraction the light did not pass well, but it
was more highly dextro-rotatory than the third fraction, thus indicating
the presence of the dextro-rotatory bornyl acetate, common to these
oils. The saponification number for the esters of the fourth fraction
1
A Research on the Pines of Australia. Published by the authority of the
Government of the State of New South Wales.
was 206-33, equal to 72'2 per cent, of ester. In the separated alcohols
both borneol and geraniol were identified. The high percentage of
•ester in this fraction did not leave much room for the sesquiterpene or
similar bodies.
The fruits yielded 0*363 per cent, of oil having a specific gravity
0-877 at 16°, optical rotation - 17'9° and refractive index 1-4774 at 18°.
The esters present were 5*88 per cent, calculated as bornyl acetate.
CALLITRIS VERRUCOSA.
The leaf and fruit oils have the characters tabulated below.
In the leaf oil both forms of limonene are present, dextro-limonene
predominating. About 3 per cent, of free alcohols (borneol ?) is present
in the oil.
OIL FROM THE LEAVES.
Specific Rotation aD Refractive Ester, Yield,
No. Gravity, ° C. Index, ° C. per Cent. per Cent.
1 0-8596 @ 23 + 44-2 1-4809® 20 3-13 0-331
2 0-8591 @ 23 + 47-5 1 -4809 @ 19 3-8 0-26G
OIL FROM THE FRUITS.

Specific Gravity, Rotation Refractive Index, Ester, Yield,
°C. OD. °C. per Cent. per Cent.
0-8608 @ 22 + 0-3 1-4788® 19 1-78 0-44
CALLITRIS PROPINQUA.
The essential oil from the leaves alone (1) and the leaves and fruits
together (2) have the following characters :—
Specific Rotation Refractive Ester, per Ester, per

No. Gravity, ° C. Index, ° C. Cent, by Cent., in the Yield,
a
D. Boiling. Cold. per Cent.
1,
Without 0-8662 @ 19 + 32-4 1-4752 @ 19 12-2 8-84 0-41
Fruits.
2,
With 0-8709® 20 + 20-5 1-4749® 19 11-29 — 0-326
Fruits.
CALLITRIS GLAUCA.
Dextro-pinene, dextro-limonene, and dipentene were identified in
the leaf oil of this species. Free borneol is present, and probably both
borneol and geraniol in the form of esters (acetate and butyrate ?).
CONIFEE^B
Seven samples gave the results set out in Table I, and five of these
samples yielded fractionation results as set out in Table II.
TABLE I.
No. Specific Gravity, Rotation Retractive Index, Ester, Yield,

°C. «D. °C. per Cent. per Cent.
1 0-8729 (CL 18 4- 27-9° 1-4747® 18 16-46 0-562

2 0-8665 18 4- 31-3° 1-4779 16 11-96 0-616
3 0-8631 24 + 30-8° 1-4755 20 12*76 0-610
4 0-8659 17 4- 28-4° 1-4774 19 12-10 0-635
5 0-8657 19 + 31-25° 1-4749 19 13-27 0-569
6 0-8665 24 4- 25-2° 1-4720 24 14-07 0-563
7 0-8782 24 + 22-7° 1-4774 19 14-21 0-532
TABLE II.
Fractious. Specific Gravity and Rotation of

Fractions.
No.
1st. 2nd. 3rd. 4th. 1st. 2nd. 3rd. 4th.
1 156-160° 160-175° 175-200° 200-230° •8562 •8571 •8689 •9415

30°/0 45% 8% 12% 4- 30-4 4- 27-2 + 21-0 4- 32-4
2 156-161° 161-165° 165-200° 200-228° •8545 •8555 •8649 •9434
30°/0 22% 37% 6% + 32-6 + 32 4- 30-7 + 33-5
3 Below 160° 160-165° 165-180° 180-225° •8477 •8494 •8561 •9256
27°/0 37% 16% 12% + 32-4 4- 31-6 + 80-5 + 34-2
4 Below 161° 161-165° 165-200° 200-225° •8550 •8565 •8664 •9416
27% 27% 31% 7% + 30-5 + 29-3 + 27-2 4- 32
5 Below 160° 160-165° 165-200° 200-225° •8529 •8537 •8649 •9322
28% 28% 32% 7°/0 + 32-2 4- 31-7 + 30-6 4- 32-5
CALLITRIS ARENOSA.
The oil from the leaves of this tree resembled ordinary pine-needle
oil in odour, but had a marked suggestion of lemon. The principal con-
stituent was limonene, dextro-limonene preponderating. Two specimens
had the following characters :—
Specific Rotation, Refractive Ester, Yield,

Gravity, ° C. «D. Index, ° C. per Cent. per Cent.
0-8491 @ 23 + 35-8° 1-4760® 23 5-17 0-402
0-8452 ® 26 + 18-9° 1-4764 @ 26 3-57 0-294
CALLITRIS INTRATROPICA.
The leaf oil is practically a terpene oil, the principal constituents
being pinene, dipentene, and laevo-limonene. Bornyl and geranyl esters
are present in very small amount. Two samples gave the following
values :—
Specific Rotation, Refractive Ester, Yield,

Gravity, ° C. «D. Index, ° C. per Cent. per Cent.
0-8481 @ 22 - 21-6 1-4768,® 22 3-81 O'll
0-8563 @ 23 — 1-4755® 19 4-75 —
CALLITRIS GRACILIS.
The leaf oil of this tree contains about 12 per cent, of esters (acetic-
and butyric) of borneol, terpineol, and, probably, geraniol. Pinene is
the principal terpene, and traces of a phenol are present. The oil has
the following characters :•—
Specific gravity . , 0-8683 at J 20°
Rotation + 8-7
Esters 12*1 per cent.
Yield . . 0-723 „
CALLITRIS CALCARATA.
Both forms of limonene are present in the leaf oil as well as dextro-
pinene. The oil contains 46'8 per cent, of esters, both of geraniol and
borneol, the former preponderating. The oil from the fruits is prac-
tically identical with that from the leaves, the samples examined having
OlLS FROM THE LEAVES.
Specific Rotation, Refractive Ester, per Ester, per Yield,

No. Gravity, °C. «D. Index, ° C. Cent, by Cent, in per Cent.
Boiling. Cold.
1 0-8949 @ 17 + 11-7 1-4747® 19 46-58 39-4 0-168
2 0-8861 @ 19 + 14-1 1-4760® 19 41-33 27-08 0-162
3 0-8S03 @ 23 - 4-5 1-4752 @ 19 38-6 ~~ 0-164
OIL FROM THE FRUITS.
Rotation, Refractive Ester, per Ester, per Yield,

Specific Cent, by Cent, in
Gravity, ° C. a
D. Index, D C. Boiling. Cold. per Cent.
0-8797 @ 23 + 2-15 1-47 44® 23 33-37 31-18 0-229
CALLITRIS EHOMBOIDEA.
The esters present in the leaf oil—nearly 30 per cent.—consist almost,
entirely of geranyl acetate, borneol and bornyl acetate being almost en-
CONIFEBJE
tirely absent. The terpenes present appear to be laevo-limonene and
pinene. The oil has the following characters:—
Rotation - 19-2°
Esters (boiling) 30*4 per cent.
„ (cold) 29-8 „
Yield 0-0335 „
This tree has been introduced into India, and a trial distillate of the
leaves gathered in the Nilghiris yielded 0'04 per cent, of essential oil
having the following characters :—
Specific gravity . 0-871 at 16°
Optical rotation . . . . . - 27-6°
Refractive index . . . . . 1-4695 a t 18°
Ester value . 51-1
Acid „ . 1-2
Saponification value (after acetylation) . 59-8
Free alcohols (as geraniol) . . 2-1 per cent-
Total ,, . 17-3 „ „.
Esters as geranyl acetate . . . 17'85 ,, >y
CALLITRIS TASMANICA.
Pinene and limonene are the predominant terpenes in the leaf oil of
this species. Traces of a phenol are present, and about 60 per cent, of
geranyl acetate, which imparts a fine odour to the oil. Two samples
Specific Rotation, Refractive Ester, per Ester, per Yield,

No. Gravity, ° C. Cent, by Cent, in
«D. Index, ° C. Boiling. Cold. Per Cent.
1 0-9036 @ 22 + 1-0 1-4738® 25 59-95 59-91 0-14
2 0-8976 @ 15 - 5-8 1-4739 @ 15 62-75 62-2 0-208
CALLITKIS DBUMMONDII.
In the leaf oil dextro-pinene, dextro-limonene, and dipentene were
present. The fruit oil is practically identical with the leaf oil. They
have the following characters :—
OIL FROM THE LEAVES.
Specific Rotation Refractive Ester, per Yield,
Locality and Dtte. Gravity, ° C. a Index, ° C. Cent. per Cent.
D.
West Australia, 0-8591® 17 + 42-2 1-4739 @ 19 1-85 0-547

26/6/03
OIL FEOM THE FRUITS.
Locality and Date. Specific Rotation, Refractive Ester, per Yield,

Gravity, ° C. «D. Index, ° C. Cent. per Cent.
s
West Australia, 0-8663 @ 15 + 45-1 1-4798 @ 19 2-4 0-3

26/6/03
VOL. I.
50 THE CHEMISTEY OP ESSENTIAL OILS
CALLITBIS MUELLEBI.
The leaf oil resembles turpentine in odour and consists almost en-
tirely of terpenes, amongst which both forms of pinene and limonene
predominate. The oil has the following characters :—
Rotation. - 4-7°
Esters 2-76 per cent.
Yield 0-103
CALLITKIS OBLONGA.
The principal constituent of the leaf oil is pinene, but both forms of
limonene are present in small amount. The esters were principally
geranyl acetate, with traces of bornyl acetate, and a high boiling constitu-
ent, probably a sesquiterpene, was present in small amount. The oil had
the following characters:—
Rotation + 3S'1°
Esters (boiling) 6*05 per cent.
„ (cold) 5-6
Yield 0-054
CALLITRIS MACLEAYANA.
Dextro-pinene, dextro-limonene, dipentene (?), and a hydrocarbon
which is probably menthene were identified in the leaf oil. A sesquiter-
pene, probably cadinene, and traces of esters are present. The oil has
Specific gravity . 0'8484 at 20°
Rotation + 42-5°
Esters (boiling) 3*5 per cent,
,, (cold) . 3-2
Yield . 0-172
OILS OF DACKYDIUM FBANKLINI.

This tree is known as the Huon pine and is found chiefly in Tasmania.
The results of the investigation l of the oil from its leaves, and also
of those of the oil of the timber, are interesting. The principal con-
stituent occurring in the leaf oil is apparently a previously undetected
terpene of the formula C10H16, for which the name Dacrydene is
proposed. This terpene readily forms a nitrosochloride, melting sharply,
and with decomposition at 120° to 121° C. (cor.), which is far away from
the melting-point of any nitrosochloride formed with a previously known
terpene. The boiling-point of dacrydene appears to be 165° to 166° C.
(cor.) ; the specific gravity at 22 D C. = O8524 ; the refractive index at
22° C. = 1*4749 ; and the rotation a D = + 12-3°, or a specific rotation
txJD + 14' 48°. It is a colourless mobile oil, with a turpentine-like odour,
ut slightly more aromatic and less pungent than pinene. It is very
volatile, and quickly and entirely evaporated from a watch glass without
leaving any residue.
As it occurs in this oil together with a small quantity of laevo-rota-
iory pinene and dextro-rotatory limonene, it was, of course, impossible
1
Baker and Smith, The Pines of Australia, 397.
CONIFEEJE 51
to obtain it pure by fractional distillation ; but by continued redistillations
10 per cent, of the oil was obtained, boiling between 165° to 166° C.,
which gave the results recorded above.
The presence of the small amount of dacrydene still remaining with
the pinene fraction, raised the melting-point of the nitrosochloride pre-
9.—" Huon Pine." Dacrydium Franklini, Hook of Tasmania.
pared from that substance several degrees, and no melting-point less than
110° C. was obtained.
Dacrydene forms a liquid bromide, and no crystalline product was
formed when the oil was saturated with dry hydrochloric acid. Scarcely
any colour was produced when concentrated sulphuric acid was added
to a solution of the terpene in acetic anhydride, but when treated with
nitric acid a yellow nitro-compound was obtained. When dissolved in
light petroleum and treated with sodium nitrite and acetic acid, no cry-
stalline product separated, but after some hours, a thick, dark-coloured
mass formed at the junction of the liquids. After two days this was
washed in ether and then dissolved in ether-alcohol, from which solution
on evaporation a yellow-coloured substance separated, and after drying
on a porous plate an ochre-yellow powder was left. This darkened much
at about 130° C. and melted with decomposition at about 150° C. It
readily dissolved in nitrobenzene, but did not become blue on heating.
On further investigation it may become possible, perhaps, to prepare a
nitrosonitrite more definite in character with this terpene.
The higher boiling portion of the leaf oil contained the methyl ether
of eugenol, and veratric acid was prepared from it by oxidation. This
methyl ether is the main constituent of the oil from the timber of this
tree.
The crude oil was of a very light amber colour, and the odour some-
what resembled that given by the oil from the wood, thus indicating the
presence of the methyl ether of eugenol, as the constituents of the wood
oil had previously been determined. The leaf oil was very mobile, and
had a low specific gravity. As it was mostly a terpene oil, it was but
little soluble in alcohol, and it required 1 volume of absolute alcohol to
form a clear solution, but it was soluble in all proportions afterwards.
The constituents identified were d-limonene, Z-pinene, dacrydene, and
the methyl ether of eugenol.
An oil was also obtained, to the extent of 0*56 per cent., from the
timber of this tree. It had a specific gravity 1*035 at 18°, optical rota-
tion + 1*4°, and refractive index 1*5373 at 23°. Its chief' constituent is
the methyl ether of eugenol, with a small amount of a sesquiterpene,
possibly cadinene.
LEAF OIL OF PHEKOSPHÊRA FITZGEKALDI.
This tree grows freely in New South Wales, and its leaf oil has been
investigated by Baker and Smith.1
.The specific gravity of the crude oil at ff ° C. = 0*8705; rotation
aD = + 15*1°; refractive index at 23° C. = 1*4841. The saponification
number is 2'4, equal to 0*84 per cent, of ester as bornyl or geranyl
acetate.
Pinene and cadinene were detected in the oil, and possibly limonene.
LEAF OIL OF PHYLLOCLADUS EHOMBOIDALIS.
This Tasmanian tree is known locally as the Celery Top Pine. Its
essential oil, which has been examined by Baker and Smith,2 is of par-
ticular interest, as it contains the only solid crystalline diterpene so far
identified. The oil contains Z-pinene, probably mixed with d-pinene, the
diterpene referred to, and possibly a sesquiterpene. '
The diterpene was readily prepared in a perfectly pure condition, so
that it was possible to determine satisfactorily its composition and phy-
sical properties. This well-crystallised body is thus one of the very fetv
members of this class of plant substances which can be prepared from
natural sources in a perfectly pure condition. The oil was obtained by
steam distillation, and contained about 3 per cent, of the solid diterpene.
1 2
The Pines of Australia, 412. Ibid., 419.
CONIFEE^ 53
The oil was almost free from compounds containing oxygen, and esters,
alcohols, aldehydes, and similar bodies were practically absent, only ,a
very small amount (about 1 per cent.) of an alcohol being determined by
acetylating the oil. The higher boiling liquid portion showed no ten-
dency to resinify, so that when the semi-solid crystalline mass, which
contained the diterpene, was spread upon porous plates for a few days,
the whole of the liquid portions were absorbed, the diterpene remaining
in a perfectly white, and even at this stage, almost pure condition. It
' was slightly soluble in cold alcohol, but more readily in hot alcohol, and
dissolved easily in chloroform, ether, petroleum ether, and benzene.
The best method for purification, after the first separation from alcohol,
was to dissolve it in chloroform and precipitate by the addition of al-
cohol. If the chloroform was in excess, so that on the addition of
alcohol no precipitate was formed, then, on slow evaporation, crystals
readily separated. These crystals were microscopic needles, but were
not well defined. When "only a small amount of chloroform was used
as solvent, then on addition of the alcohol the solid substance at once
crystallised out. When this was dried it had more of a tabular struc-
ture, was pure white, of a nacreous lustre, and was practically without
odour. It was dextro-rotatory, and the determination of the specific
rotation was made with both benzene and chloroform, the specific rota-
tion, [a]D = -f 16*06°, being identical with both solvents. Its ready
solubility in benzene enabled the molecular weight to be determined by
the cryoscopic method, and this, together with the results of the analy-
ses, showed it to have the formula, C20H32. Its melting-point was 95°
C. (cor.), and it did not matter what the solvent had been. The fused
substance also melted again at the same temperature. This diterpene
has been named phyllocladene.
THE PINE-NEEDLE OILS.

It will be convenient to deal with the oils obtained from the leaves
of various species of Pinus, Larix, Abies, and certain closely allied
plants, under the general description of pine-needle oils. A consider-
able number of these have been examined, but only a few are commer-
cial articles.
1. Oil of Pinus sylvestris.—The oil distilled from the leaves of this
tree varies in character to some extent, according to the locality in
which the tree is grown.
English distilled oil is laevo-rotatory, whilst most other varieties are
dextro-rotatory. It has the following characters :—
Optical rotation - 7° „ - 22°
Esters as bornyl acetate . . . . . . 2'5 to 4 per cent.
1
Umney examined samples distilled in summer and winter, and
found that the two specimens had the following characters:—
Distilled Distilled
in June. in December.
Yield 0-5 per cent. 0*133 per cent.
Specific gravity 15° C 0'885 0'889
Optical rotation (100 mm.) . . . - 19° - 7-75°
Percentage of bornyl acetate . . 3'5 2-9
L
Pharm. Jour., 55 (1895), 161, 542.
THE CHEMISTRY OF ESSENTIAL OILS
On fractionation the two oils gave the following results :—
June Oil. Decemb er Oil.
157° t o!67° 8 per (3ent. 13 per cent.
167° , 177° 27 24
177° , 187° 20 , 9
187° , 197° 3 , 6
197° , 240° 7 7
240° , 252° 6 4
Resid ue . 29 37
The oil contains Z-a-pinene, dipentene, sylvestrene, and a small
amount of bornyl acetate.
German distilled oil, which is obtained to the extent of 0'4 to 0'6 per
cent., has the following characters :—
Esters as bornyl acetate 1 to 4 per cent.
The oil is soluble in 7 to 10 volumes of 90 per cent, alcohol. On
fractional distillation 10 per cent, is obtained between 160° and 170°, and
about 45 per cent, between 170° and 185°. The ester value of the acety-
lated oil is about 15. (Austrian oils are sometimes slightly laevo-rotatory.)
The oil contains a-pinene, principally the dextro-rotatory variety,
d-sylvestrene, cadinene, the acetic ester of either borneol or terpineol and
probably dipentene. A small amount of free alcohol (borneol or ter-
pineol) is also present.
Swedish oil agrees in its characters with the German distillate.
2. Oil of Abies Sibirica.—This oil has of late years come into pro-
minence on account of its high content in bornyl acetate, and its extremely
low price. It is known commercially as Siberian " Pine " oil, although
distilled from the leaves of Abies Sibirica (Abies pichta. Forb.). It is
produced in North-East Russia, principally in the Wjatka district, very
little being distilled in Siberia itself on account of the high cost of trans-
port. The oil has a most fragrant odour and is highly esteemed as a
cheap perfume.
A pure oil has the following characters :—
Optical rotation - 30°,, -43°
Acid value 1» 4
Esters as bornyl acetate 29 to 43 per cent.
It is soluble in 1 volume of 90 per cent, alcohol or in 15 volumes of
80 per cent,1 alcohol.
Umney has examined an apparently authentic sample of this oil,
which had an exceedingly fine odour, and which had characters falling
outside the above-mentioned limits. Its physical and chemical charac-
ters were as follows :—
Optical rotation - 41-2°
Esters . . . . . . . . . . 53*4 p e r cent.
2
This oil contains a hydrocarbon, distilling below 145°, of the formula
C9H4, to the extent of from 3 to 4 per cent., which has been termed
santene. This hydrocarbon boils at 140° and has a specific gravity =
2
ip.and E.O.R., 1912, 289. Aschan, Bericht, 40 (1907), 4918.
CONIFERS 55
0*8698, refractive index 1*4696, and yields a nitrosochloride melting at
109° to 111°. Pinene is present in its various stereo-isomeric forms, as
well as camphene and phellandrene. The chief constituent, from the
odour point of view, is bornyl acetate. The sesquiterpene bisabolene is
present to a small extent in the high boiling fractions of the oil. Esters
of terpineol are also present to a small extent.
3. Oil of Pinus longifolia.—The leaves of the Indian pine tree, Pinus
longifolia—the so-called " Chir" pine—yield an essential oil having the
following characters :—
Acid value 1-03
Ester „ . 14-51
Saponification value 15-54
Iodine value 271-2
Distils from 160° to 165° 23-8 per cent.
„ 165° „ 170° 29-0
„ 170° „ 180° 19-8
„ 180° „ 200° 15-1
„ 200° „ 215° 6-7
Residue above 215° 5-6
These five fractions had the following physical characters :—
Specific
Fraction. Gravity at 20° Rotation
160° to 165° 0-860 - 12° 12'
165° „ 170° 0-861 - 9° 15'
170° „ 180° 0-863 - 6°
180° „ 200° 0-868 - 3°
200° „ 215° 0-909 - 2°
The ester value of this oil is 14*5, which corresponds to about 5 per
cent, of esters calculated as bornyl acetate, which is, of course, to be ex-
pected with an oil with the range of distillation temperatures indicated
above; for bornyl acetate is sought for in essential oils in the fraction
boiling at 220° to 230°, which is practically non-existent in the oil in
question.
4. Oil of Pinus pumilio.—This oil, although usually classed as a pine-
needle oil, is usually distilled from the leaves mixed with small twigs and
woody portions of the branches of Pinus pumilio (Pinus montana Mill.).
It is principally distilled in the Austrian Alps, largely in the Tyrol, and
in several other districts. The yield of oil is, as would be expected, very
variable, as low as 0*25 per cent, being obtained, or as much as 0*75 per
cent. The oil has the following characters :—
Optical rotation - 5° to - 10° (rarely to - 16°)
Esters as bornyl acetate . . . 3 to 10 per cent.
It is soluble in 5 to 10 volumes of 90 per cent, alcohol.
These limits may be exceeded if the distillation material is not fresh,
and oils with a specific gravity up to 0*892 have been recorded. The
following fractions were obtained on distilling an authentic specimen of
the oil:— x
155° to 165°. 2 per cent.
165° „ 180°. 59
180° „ 200°. 21 „
above 200° . 18
1
Umney, Pharm. Jour., 55 (1895), 163.
The oil contains Z-a-pinene, Z-phellandrene, sylvestrene, cadinene, and
bornyl acetate. Bocker and Hahn have recently isolated from the oil an
aldehyde of the formula C^HÔ,1 an oxygenated body of the formula
C15H24O, the nature of which has not yet been determined, and a body
of the formula C8HUO, having the characteristic odour of the oil. This
body is a cyclic compound, and has been named pumilone, having the
general characters of a ketone. It has the following characters :—
Boiling-point 216° to 217°
The principal adulterant of this oil is ordinary turpentine, which, of
course, reduces the ester value, and yields a large amount of distillate
below 165°.
5. Oil of Abies excelsa.—This oil is distilled from the leaves and twigs
of Abies excelsa (Abies pectinata, De Candolle; Abies alba Mill.). It has
Esters as bornyl acetate . . . . . . 4 to 12 per cent.
Ib contains Z-a-pinene, Z-limonene, bornyl acetate, lauric aldehyde,
probably traces of decyl aldehyde, and the hydrocarbon santene, C9H14.2
An oil is also distilled from the young cone's of this tree. It contains
more terpenes than the leaf oil, and has the following characters :—
Specific gravity . . 0-850 to 0-890
Ester value 1 ,, 6
It consists chiefly of Z-pinene and Z-limonene, with a small amount
of bornyl acetate.
6. Douglas fir-needle oil.—This oil is distilled from the leaves of
Pseudotsuga taxifolia, the so-called Douglas pine, a native of North
America. The needles, twigs, and very young wood are used for the dis-
tillation, and the yield is from 0*8 to 1 per cent. The oil has been
examined by Brandel and Sweet and by A. W. Schorger. The oil in-
vestigated by the first-named was distilled in Washington, whilst that
examined by Schorger was distilled in California. The two oils had the
following characters:-
IBrandel and Sweet. Schorger.
Specific gravity 0-868 0-873 to 0-876
Optical rotation - 62-5° - 17° „ - 22°
Refractive index 1-4758 „ 14780
Acid value . 0 0-65 „ 1-1
Ester ,, 86*6 11 „ 25
Bornyl acetate 30-3 per cent. 3-9 per cent.
Free borneol 4-5 to 8-5 per cent.
Whether the difference in locality alone is responsible for the dif-
ference in the oils is not clear. Six hundred grams of the oil were
fractionated by Schorger. *
The following compounds were identified in the oil: (1) Furfural.—
This was isolated by shaking the first fraction distilled with water. (2)
a-Pinene.—By repeated fractionation 151 grms. of oil, boiling at 156° to
l 2
Jour. prakt. Chem., ii. 83 (1911), 489. Aschan, Bericht, 40 (1907), 4919.
CONIFEKÊ 57
160° were obtained. On refractionation 4ihe oil boiled at 156° to 157°, had
a specific gravity 0*8682, and optical rotation - 11*94°. It yielded a
nitrosochloride melting at 103° and a nitrolpiperidine melting at 118°.
Camphene could not be detected. (3) /2-Pinene. —A fraction was obtained
which boiled at 164° to 166°, and had specific gravity 0*872, and optical
rotation - 17*19°. This was easily oxidised by means of alkaline per-
manganate to nopinic acid, which melted at 126°. This fraction was
therefore /3-pinene. (4) Dipentene and Limonene. — Two fractions were
•obtained, having the following characters : —
1. 2.
Weight ...... 2-9 per cent. 2-6 per cent.
Boiling-point ..... 170° to 172° 172'6° to 178-2°
Specific gravity ..... 0-8628 0-8616
Optical rotation ..... - 28'12° - 26-24°
'The former fraction yielded a dihydrochloride, melting sharply at 50°
after several recrystallisations from alcohol. The latter fraction yielded
a tetrabromide, which melted at 117° to 119°, or after further recrystallisa-
tion at 121° to 122°. It is probable that this fraction contains both di-
pentene and laevo-limonene. (5) Borneol. — The oil recovered from the
•saponified ester fraction was distilled. The fraction 208° to 213° had a
rotation of - 19*42°. It was treated with phthalic anhydride for eight
hours. The resulting acid phthalic ester was converted into the sodium
salt and exhausted repeatedly with ether. After saponification the oil
was oxidised with chromic acid, and camphor, melting at 174°, recovered
by steam distillation. This establishes the identity of borneol. (6) .Acetic
Acid. —This acid was found to be the principal acid constituent of the
esters. (7) A green oil having a specific gravity 0*9370 was isolated,
but not identified. The approximate amounts of the above compounds
present are as follows : a-pinene, 25 per cent. ; /3-pinene, 48 per cent. ;
dipentene and limonene, 6 per cent. ; furfural, traces ; esters, 6*1 per
'Cent. ; free borneol, 6*5 per cent., green oil, 3*0 per cent.
Pseudotsuga taxtfolia is also known as P. Douglasii. According to
Henry and Flood l the Douglas fir growing in Oregon is rightly described
under this name, whilst the Colorado or blue Douglas fir is P. glauca.
C. T. Bennet has examined the oils distilled from material grown in
England, of both plants, and reports upon them as follows : —
FROM LEAVES OF THE OREGON DOUGLAS FIR.
" 1. 50 Ibs. of leaves of young trees growing at Avondale, sent in
August, 1919. When distilled less than 0*01 per cent, of an oil with a
very aromatic odour was obtained—a quantity too small for examination.
" 2. 50 Ibs. of leaves of old trees growing at Buckhold, Berks, sent in
November, 1919, when distilled yielded 0*11 per cent, of oil having the
following characters : —
Specific gravity ........ 0-876
Optical rotation . . . . . . . . —7°
Refractive index ........ 1-4835
Esters as bornyl acetate ...... 12*4 per cent.
"The ester content is much lower than that of the Colorado Douglas
fir oil, but the odour is more fragrant. The oil contains dipentene or
limonene, but if pinene is present, the quantity is very small, as prac-
tically nothing distils below 175°.
1
Proc. Roy. Irish Acad., May, 1920.
" 3. A few days later another 60 Ibs. of leaves from the Oregon Douglas-
fir from Buckhold were distilled, and enough oil was then available for
further investigation. On fractionating the oil, an appreciable quantity
of geraniol was separated, and this appears to be the chief odorous con-
stituent. The proportion of total alcohols by acetylation calculated as-
geraniol is 31*5 per cent. The presence of bornyl acetate somewhat
masks the odour in the original oil. There is also a small trace of citral,
but the proportion is too small for determination. Geraniol occurs in
the oils of some species of Callitris in Australia, but has apparently not
been recorded as a constituent of the oils distilled from other conifers.
Geraniol is the chief constituent of Indian palmarosa oil obtained from
the fragrant grass Andropogon Schoenanthus Linn. (Cymbopogon Martini),.
and occurs in citronella oil, otto of roses, lemon oil, etc.
"OlL FROM THE LEAVES OF THE COLORADO DOUGLAS FlR.
"50 Ibs. of leaves of moderate-sized trees growing at East Liss,.
Hants, sent in October, 1919, yielded on distillation 0*31 per cent, of oiL
Optical rotation -46°
Refractive index (20°) 1*4717
Esters as bornyl acetate 34*5 per cent.
" The terpenes consist principally of pinene. The odour is chiefly
due to the bornyl acetate present.
" It would appear from these analyses that the strong odour of
Colorado Douglas fir, which is like that of turpentine mixed with camphor,
is due to the large percentage of pinene and bornyl acetate. •
" In the Oregon Douglas fir, pinene is not present, and the bornyl
acetate is much less in percentage. The peculiar fragrance is chiefly
due to the presence of the highly odoriferous substance geraniol, slightly
modified by the small amount of bornyl acetate present."
7. The leaves and twigs of Pinus Sabiniana, the so-called digger pine,
yield from 0*078 to 0*102 per cent, of essential oil having the following
characters:—
Optical rotation - 20° „ 39°
Refractive index 1*4670 to 1*4671 at 15°
Acid value 1*47 to 2-05
Ester „ 6*77 „ 11-98
,, „ (after acetylation) . . . . 25*86 „ 37'16
Schorger l has identified the following constituents in the oil :—
n-heptane . 3 per cent.
Z-a-pinene . 58 to 59
Mimonene . 18
Bornyl esters 3-5
Borneol 6
8. The oil from the leaves and twigs of Pinus contorta, the lodge-
pole pine, has the following characters :—
Acid value 0*9
Ester 6*02
, (after acetylation) 32-3
1
Jour. Ind. Eng. Chem. (1915), 7, 24.
CONIFEEÊ
The oil contains Z-camphene, Z-/3-pinene, 1-a-pinene, Z-phellandrene,
dipentene, borneol, bornyl acetate, and cadinene.
9. The oil from the leaves and twigs of Abies magnified has the
Acid value 0-75
Ester „ 9-93
„ ,, (after acetylation) 36-22
Traces of furfural were found in the oil, as well as Z-/3-pinene, Z-phel-
landrene, bornyl 1esters and free borneol.
10. Schorger has examined the oil distilled from the leaves and
twigs, and also that from the cones of Pinus ponderosa, the Western
yellow pine, and found them to have the following characters :—
Leaves and Twigs. Cones.
Yield per cent. 0-04 to 0-126 0-063
Specific gravity (15°) . 0-8718 „ 0-8849 0-8757
Optical rotation (20°) . . - 15-73 „ - 19-59 - 11-48
Refractive index (15°) . . . . 1-4789 ,, 1-4838 1-4789
Acid value 0'67 „ 2'36 1-27
Ester „ 3-88 „ 8-10 7*20
„ (afteracetylation). . . 24-11 „ 35'68 22-41
The constituents identified are as follows :—
Leaves and
Twigs. Cones.
Furfural . . . . . . — trace
Z-a-pinene . . . . . . 2 6
Z-camphene . . . . . . — —
Z-0-pinene . . . . . . 7 5 6 0
Dipentene . . . . . . 6 12 to 13
Esters a s bornyl acetate . . . . 2 2-5
Free alcohols (Z-borneol). . . . 7 4
"Green oil" . . . . . 3 3 t o4
Sesquiterpene . . . . . — —
11. The oils from the leaves and twigs, and from the cones of Pinus
Lambertiana have also been examined by Schorger2 with the following,
results :—
Leaves and Twigs. Cones.
Yield p e r cent. . . . . 0-045 t o 0-120 0-32
Specific gravity (15°) . . . 0-8676 „ 0-8738 0-8692
Optical rotation (20°) . . - 11*07 „ - 16-50 - 23-18
Refractive index (15°) . . . 1-4777 ,, 1-4794 1-4771
Acid value . . . . . 0'68 „ 2-38 0-63
Ester „ 2*22 ,, 5-91 3-75
„ „ (after acetylation) . . . 23*25 „ 32-04 17-04
The percentage composition of the oils is as follows:—
Leaves and Cones.
Twigs.
Furfural trace trace
Z-o-pinene 21 22
Z-camphene . 21
Z-j8-pinene . 51 39 to 40
Dipentene . 12 4 „ 5
Esters . 1-5 1-5
Borneol 3-5
" Green oil"
Sesquiterpene
1
Jour. Ind. Eng. Chem. (1914), 6, 893.
THE CHEMISTKY OF ESSENTIAL OILS
, '-12. The leaves and twigs of Abies concolor yield O03 to 0'27 per
-cent, of essential oil which has the following characters :—
Specific gravity . . . 0'872 to 0-878
Acid value 1 „ 1-8
Ester „ 12-5 „ 27'4
The bark of this tree yields an oil having the following characters :—
Acid value . . . 0*87 „ 1-22
Ester „ 6'4 „ 6-9
The approximate composition of these oils is as follows :—
Leaf and Twig Bark Oil.
Oil.
Furfural . trace trace
Z-a-pinene . 12 per cent. 9 per cent.
Z-camphene 8
Z-£-pinene . 42 60 per cent.
Z-phellandrene 15 IDipentene 12 to 13 per cent.
Esters as borny acet ate 6-5 2-5 „
Free borneol 9-5 4-5 „
" Green oil" 3 5
Loss . 1 7
.."
The remaining "pine-needle oils" may be summarised as to their
characters and constituents in the table on page 61, which includes most
of any importance which have been examined.
N. 0, GRAMINE/E.
(THE GRASS OILS.)
The principal oils of this natural order are derived from the family
formerly known as Andropogon. Much confusion had crept into the
nomenclature of these oils which1 has been cleared up finally by the ex-
cellent work of Dr. Otto Stapf. This authority has discarded the old
names and has made the following classification, which has been uni-
versally accepted:—
Cymboppgon genus, with 10 species.
Vetiveria genus, with 1 species.
Andropogon genus, with 1 species.
The following are the salient features of these grasses as classified
by Stapf :—
1. Cymbopogon Scho&nanthus Spreng (Andropogon Schoenanthus L.).
This is known locally as Camel grass. It is a characteristic desert
plant able to exist on the smallest amount of water, and is distributed
over Northern Africa and Arabia, and is also found in the Persian Pro-
vince of Kirman where it grows at altitudes of 6000 ft. and in Afghani-
stan, Beluchistan, and the Punjab.
2. Cymbopogon Iwarancusa Schult. This grass is believed to be the
Nardus Indica of the Ancients. The natives call it Terankus (fever-
healer). The plant is highly aromatic. At great altitudes it becomes
small and narrow-leaved and then represents a transition form towards
Cymbopogon Schoenanthus.
l
Kew Bulletin (1906), 8, 297.
i
Specific Rotation. Refractive Esters as Constituents.
Oil. Gravity. Index. 1 Bornyl Acetate.
Abies balsamea . 0-890 to 0-892 - 30° 17 to 20°/0 Z-pinene ; bornyl acetate.

,, canadensis. 0-907 „ 0-913 - 18° to - 26° 35 „ 40°/0 Z-pinene ; bornyl acetate, cadinene.
,, magnified . 0-8665 - 16-7° —
1-4861 3'5°/0 Z-jS-pinene ; Z-phellandrene ; furfural ;
borneol ; bornyl acetate.
Larix decidua . 0-878 + 0° 22' 8°/ Borneol ; bornyl acetate.
,, pendula . 0-881 — ' 15°/ a-pinene ; bornyl acetate.
Picea canadensis 0-922 — - 25°/° Limonene ; dipentene, bornyl acetate. £
,, excelsa (P. vul- —
garis) . 0-875 to 0-890 - 20° to - 40° — 6 to 10°/0 Z-pinene; dipentene; 1-phellandrene ; p
cadinene ; bornyl acetate.
„ nigra . 0-913 - 23° 50' — 38°/0 Bornyl acetate. Q
„ rubens 0-954 — 8°/0 Borneol; bornyl acetate.
— —
Pinus cembra 0-880 4- 29° Pinene.
„ contorta . 0-869 - 18° . 1*4831 2°/0 Furfural ; Z-piuene ; Z-camphene ; Z-phel-
landrene ; dipentene ; cadinene ;
% bornyl acetate and methyl-chavicol(?). tei
,, cubensis . 0-868 + 9° 40' — fe
,, halapensis 0-880 to 0-896 - 20° to - 25° — 2-5 to 3°/0 Z-pinene ; limonene ; borneol ; bornyl
—
acetate and free fatty acids.
„ heterophylla 0-887 „ 0-889 - 32° „ - 36° 1-4845 to 1-4869 3'5°/0 Furfural; Z-pinene; 1-camphene; dipen-
tene ; borneol ; cadinene ; bornyl
acetate and free fatty acids.
,, laricio 0-865 „ 0-870 + 3° „ + 8° lto3-5°/ 0 Bornyl acetate.
,, palustris . 0-883 „ 0-885 - 26° „ - 31° — 1-4830
1-4810 to 1-5 to 2°/0 Furfural ; Z-pinene ; Z-camphene ; dipen-
tene ; cadinene ; borneol and its
esters.
,, strobus . . 0-901 - 39-7° 1-4827 8-6°/0 Z pinene ; bornyl acetate.
3. Cymbopogon Nardus Eendle (Andropogon Nardus L.), citronella
grass. In this grass also various botanists suspected the Nardus Indica
of the Ancients, and for this reason Linnaeus gave it the name Andro-
pogon Nardus. Grimm, a physician who lived at the end of the seven-
teenth century in Colombo, called the grass Arundo Indica odorata.
He stated that it grows in large quantities in the neighbourhood of
Colombo (probably cultivated), and that an essential oil is distilled
from it.
Citronella grass is only found cultivated; it is grown particularly in
the southern part of Ceylon, and also in the Malacca peninsula and
Java; in most recent times attempts have also been made to cultivate it
in the West Indies. The mother-plant is very probably the wild mana
grass, Cymbopogon confertiflorus Stapf, found in Ceylon.
It is well known that citronella grass is cultivated in two varieties:
" Maha pengiri" (Maha pangiri), and "Lenabatu" (Lana batu). The
first-named is also called "old citronella grass" or "Winter's grass,"
as it was only cultivated by Winter & Son, whilst it is chiefly grown
in the Malacca peninsula and in Java. It has fairly broad leaves, larger
tufts than " Lenabatu," and is characterised by a rapid growth, but it is
soon exhausted and dies after ten to fifteen years. As for this reason it
frequently has to be planted out afresh, it has gradually been replaced
by the Lenabatu variety. It yields an oil of lower specific gravity, readily
soluble, and rich in acetylisable constituents.
The variety known as " Lenabatu " ("new citronella grass"), which
forms the bulk of Ceylon citronella grass, yields an oil of less value,
which differs from the other by a higher specific gravity, lower geraniol-
content, and contains methyl eugenol.
Morphological differences between the two varieties do not exist, as
Stapf proved with two specimens which, however, were not very well
preserved.
4. Cymbopogon confertiflorus Stapf (Andropogon confertiflorus Steud.).
This grass is found in India in the district between the Nilghiris and
Ceylon, and also in Ceylon itself. It grows to a height of 5 ft. and,
more. It is possibly the wild mother-plant of citronella grass, and it
has also the same odour as the latter, but it only gives a small yield of
oil. The Singhalese name for it is " Mana," whilst in the Nilghiris it
is known as " Bambe ".
5. Cymbopogon flexuosus Stapf (Andropogon flexuosus Nees ex Steud.),
Malabar or Cochin grass, is distributed in the Tinnivelli district and in
Travancore. During the last few years large areas have been planted
there with this grass. According to Stapf, the oil, which is known in
commerce as lemon-grass oil, is obtained from two wholly different plants,
the oil coming from the Malabar coast being produced from C. flexuosus
Stapf, whilst the other species of lemon-grass, designated as C. citratus
Stapf, yields an oil which, though very similar, is not identical with the
former.
6. Cymbopogon coloratus Stapf (Andropogon coloratus Nees) is found
from the Tinnivelli district to the Anamalai mountains, and also in the
district Karnatik (Madras Presidency), and belongs to the lemon-grasses
of the Malabar district. It differs from C. flexuosus in that it is much
smaller.
7. Cymbopogon citratus Stapf (Andropogon citratus D. C.) only
occurs in the cultivated state. It is found in most tropical countries,
N. O. GEAMINEJE 63
especially in Ceylon and the Straits Settlements, also in lower Burma
and Canton, Java, Tonquin, Africa, Mexico, Brazil, the West Indies,
Prench Guiana, Mauritius, Madagascar, New Guinea, etc.; in the Malay
peninsula, and especially near Singapore, the grass is cultivated on a
large scale.
The oil obtained from it differs from the Malabar lemon-grass oil by
its lesser solubility in alcohol and the frequently lower citral-content, for
which reason it is usually less valuable than the Malabar oil.
8. Cymbopogon Martini Stapf (C. Martinianus Schult.), Eusa grass,
geranium grass. The vernacular name " rusa," which is largely used
for this grass, is probably derived from the brown-red coloration of the
panicles in autumn.
Eusa grass is found from the Eajmahal mountains (on the bend of
the Ganges) to the Afghan frontier, and from the sub-rtropical zone of
the Himalayas to the twelfth degree latitude, with the exception of the
desert and the steppe region of the Punjab, the external slopes of the
Westghat, and apparently a large part of Northern Karnatik.
A distinction is made between two varieties of the grass: " sofia "
and " motia," but it is for the present undecided whether they are
botanical varieties, or only different conditions of maturity of the same
species.
9. Cymbopogon caesius Stapf (Andropogon caesius, a et ft Nees),
Kamakshi grass.
This grass is very closely allied to C. Martini, but yet distinctly
different; only where the two Species meet, transition-forms occur
which unite the two species completely. C. caesius grows in the greater
part of Karnatik, where it is fairly common. It replaces C. Martini in
South-Eastern India.
In the Administration Eeport of the Government Botanic Gardens
and Parks, the Nilghiris, for 1901, p. 5, an article appears on this oil.
The grass used for the distillation originated from Arni, in the North
Arcot district, Madras Presidency, where it is found in large quantity.
The oil-yield from the grass freshly cut at the end of December was
O431 per cent. Another parcel, distilled at the end of April in an entirely
dry state, yielded 0*711 per cent. oil. With regard to the properties of
the oil no data are available.
10. Cymbopogon polyneuros Stapf (Andropogon polyneuros Steud.) is
a fairly strong grass which has a great tendency to form numerous rami-
fications upwards, so as to form thick clusters. It is found in the South-
western parts of India, especially in the Nilghiris, and here replaces
C. Martini. It is also found in Ceylon, preferably at greater altitudes (up
to 4500 ft.), and further in the island Delft in Adams' Strait, where
it is called " Delft grass " and forms good food for horses. The odour
of the rubbed leaves is said to remind one of fennel or anise. The oil was
distilled in 1902 in Utakamand, and obtained in a yield 0*25 per cent.;
with regard to its properties nothing is known.
11. Vetiveria zizanioides Stapf (Andropogon muricatus Eetz.) is vetiver-
grass, Anglo-Indian " Khas khas," or " cus-cus," a name which is
probably of Hindu origin and means " aromatic root".
Vetiver grass occurs* both in the wild state and cultivated, and is
much esteemed on account of its roots which are used for many pur-
poses. In the wild state it is distributed all over British India and
Ceylon, being chiefly found on the banks of rivers and on rich marshy
soil up to an elevation of 1800 ft. Occasionally it is cultivated, for
example in Eajputana and Chutia-Nagpur. In the Malay districts
vetiver only occurs cultivated or accidently growing wild;—the same
applies to the West Indies, Brazil, and E6union. The best sort of grass
is found in the neighbourhood of Tutikorin, which is still at the present
day the most important shipping port of vetiver root.
The vetiver oil prepared from the root does not appear to be distilled
in India itself or in the other countries of origin with the exception of
K6union. 1
Jowitt, however, does not consider that the so-called Mana grass,
C. confertiflorus, is the true mother-plant of the cultivated citronella
grasses. He states that C. Nardus, the genuine citronella grass, also
grows wild in Ceylon. C. Nardus Rendle, which occurs in a wild state,
is identical with the so-called "old citronella grass" (Winter's grass,
Maha Pengiri) and forms a species distinct from Mana grass. It is pos-
sible that the third variety, known as Lenabatu grass, has resulted
from hybridisation of citronella and Mana grasses. In these circum-
stances Jowitt considers it advisable to designate the Maha Pengiri
variety as a separate species under the name of Cymbopogon Winterianus.
In this case the name C. Nardus Eendle should be applied only to the
Lenabatu grass.
There are numerous intermediate plants between the regular culti-
vated varieties and the wild mother-plants, and the oils from these have
been investigated by Pickles,2 whose results point to the fact that by
continued cultivation the oils become richer, in some cases in geraniol,
in other cases in citronellal, the former approaching Lenabatu oil and
the latter Maha Pengiri oil.
The principal oils belonging to this important family are the
following:—
CEYLON CITRONELLA OIL.
This oil is distilled in Ceylon, from the grasses described above, on a
very large scale. The oil, which is used in cheap perfumery, especially
in soap manufacture, is produced in more or less primitive stills, to the
extent of between 1,500,000 and 2,000,000 Ib. per annum. It is largely
distilled by natives, and is almost universally adulterated.
The grass is cultivated almost entirely in the south of Ceylon.
About 50,000 acres are devoted to it, and but little attention is necessary.
The growth is continuous, and three harvests can be obtained annually
in very favourable years, but usually two are found sufficient—one in
July or August and one in December, January, or February. The yield
of oil is about sixteen to twenty bottles (22 oz.) per acre for the summer
crop, and five to ten for the winter crop. After a lapse of fifteen years
the plants become exhausted, and new plants become necessary. There
are somewhere about 600 stills at work on the island, and the enormous
output of the oil indicates its importance as an article of commerce.
The distilleries are usually situated in small sheds and consist of a steam
boiler with a safety valve and water indicator, resting upon a solid
foundation ; two cylindrical stills 6 to 8 ft. high and 3 to 4 ft. broad, and
a spiral condenser in a tub of cold water. A still will produce from
20 to 30 Ib. of oil a day.
1
Annals Royal Botanic Gardens, Peradeniya, iv. 1908, 4, 185.
*Bull. Imp. Inst., 8 (1910), 144.
N. O. GEAMINEÊ 65
The trade in citronella oil is in a very unsatisfactory condition, as
practically all the oil exported from Ceylon is, by consent, adulterated,
the amount of pure oil sold being almost negligible. This aspect of the
question will be discussed latter.
A pure distillate should have the following characters :—
Specific gravity = 0-898 to 0-920
Optical rotation = _ 7° to - 18° (rarely to - 20°)
Refractive index = 1-4785 to 1-4900
FIG. 10.—Citronella oil still. 1 chimney; 2 steam boiler; 3 still; 4 and 5 con-
denser; 6 underground cellar; 9 receiver.
The total acetylisable constituents, calculated as geraniol should not

fall below 55 per cent., and is often above 57 per cent., rarely reaching
60 per cent. The oil should dissolve to a clear solution in 1 to 2
volumes of 80 per cent, alcohol, and on the addition of more alcohol up
to 10 volumes, no turbidity—or at most a slight opalescence—should be
produced. The principal adulterant of this oil is petroleum, but resin
spirit has also been used, and during the past few years the lighter frac-
tions of petroleum of the petrol type have been employed. The author
and Bennett have examined the effect of adulteration on the characters;
of the first 10 per cent, distilled from the oil, with the results set out*in
the following tables :—
TABLE I.—PURE CITRONELLA OILS.

Characters of first 10 per cent, distilled at 20 to 40 mm. pressure.
Specific Rotation in Refractive
G cavity 100 mm. Index at
at 15-5°. Tube. 190 C.
A 0-861 - 44° 1-4680
B 0-861 - 43° 1-4732
C 0-860 - 35° 1-4692
D 0-P63 - 23° 1-4655
E1 - 6° 1-4590
0-867 - 11° 1-4571
1
E is an oil from the Straits Settlements.
2
F is a Ceylon oil distilled by Winter, and probably prepared by fraction a ti on.
VOL. I. 5
TABLE II.—CITRONELLA OILS MIXED WITH ADULTERANT.
Characters of first 10 per cent, distilled at 20 to 40 mm. pressure.
Gravity 100 mm. Index at
at 15-5° Tube. 19° C.
1 E + 5 per cent, resin spirit 0*855 - 7° 1-4563
2 E + 10 0-848 - 3° 1-4545
3 E + 15 0-841 - 2° 1-4525
4 E + 20 0-833 — 1° 1-4505
5 D + 5 0-854 - 17° 1-4570
6 D + 10 0-845 - 14° 1-4515
7 D + 20 0-835 - 8° 1-4490
8 C + 10 ,, petroleum spirit 0*848 - 24° 1-4514
TABLE III.—ADULTERATED CITRONELLA OILS ON THE MARKET.

Characters of first 10 per cent, distilled at 20 to 40 mm. pressure
Specific "
Rotation in _ - ..
Refractive
at 15-5° Tube. 19° C.
0-822 - 26° 48' 1-4492
0-824 - 23° 50' 1-4504
0-833 - 18° 20' 1-4525
0-820 - 22° 1-44%
0-844 - 17° 30' 1-4540
0-S36 - 29° 1-4495
TABLE IV.—'BESIN AND PETROLEUM SPIRITS.

Characters of first 10 per cent, distilled at 20 to 40 mm. pressure :—
at 15-5° Tube. 19° C.
1 Resin spirit . . . . . 4° 1-4403
2 l
0-802 + 2° 30' 1-4425
3 Petroleum spirit (turpentine substi-
tute) 1° 1-4435
4 Petroleum spirit x (turpentine substi-
tute) 0-801 + 1° 30' 1-4416
The lightest fraction which the author and Bennett obtained from
the adulterated oils had a specific gravity of 0*798, an optical rotation of
- 17°, and commenced to distil at 112° C. In none of the fractions has
any odour of paraffin been observed, nor any fluorescence—hence the
conclusion that resin spirit is the adulterant.
Suggested Standard.—From a consideration of these figures the fol-
lowing standards for pure citronella oil are suggested :—
1. The oil must dissolve either clear, or at most with the slightest
opalescence, in 10 volumes of 80 per cent, alcohol at 20 J C.
2. The first 10 per cent, distilled under reduced pressure (20 to 40
mm.) must have a specific gravity not below 0*858 and a refractive index
at 20° not below 1*4570.
It may be regarded as fairly certain that no adulterated sample will
pass these tests, although the limit for refractive index has been placed
1
The actual source of these turpentine substitutes has not been ascertained, as
the distillers decline to give information. They have a faint odour of paraffin, and a
distinct though slight fluorescence, and probably consist only in part of petroleum
spirit.
N. O. GEAMINEÊ 67
lower than the figures found for normal Ceylon oils, in order to meet the
requirements of other oils, such as those from Java or the Straits Settle-
ments, and, in general, those with low terpene-content. But any Adul-
terated oil which might show a higher refractive index than has been
indicated would fail to pass the specific gravity limit if more than traces
of the adulterant were present.
For many years it was the custom to sell citronella oil " guaranteed
to pass Schimmel's test ". This was merely a solubility test, which re-
quired that the oil should dissolve in 10 volumes of 80 per cent, alcohol
with not more than slight turbidity, without any oil globules separating.
It was soon found that the oil could be adulterated down to the limits of
this test, and a so-called "raised test" was suggested, but never applied
to contracts commercially. This consisted in adding 5 per cent, of
kerosene to the oil in question, which should in this condition pass the
ordinary " Schimmel's test ". To-day, however, the empirical character
of these tests is fully realised, and discriminating buyers insist on valuing
the oil on its acetylisable constituents calculated as geraniol. This de-
termination is carried out in the usual manner for the determination of
free alcohols, the citronellal present being, converted into isopulegol and
then into isopulegyl acetate, so that the result expresses the geraniol to-
gether with the citronellal. If it be desired to determine these two
constituents separately, the process of Dupont and Labaune l may be
employed.
This depends on the fact that citronellal-oxime, produced by shaking
the oil in the cold with a solution of hydroxylamine, is converted, on
heating with acetic anhydride, into the nitrile, which is not affected by
saponification with alcoholic potash.
The difference in the molecular weight of the nitrile formed and that
of citronellal is so small as to be negligible, and the calculation of the per-
centage of geraniol from the saponification is made by the usual formula.
• ; The method of procedure is as follows: 10 grms. of hydroxylamine
hydrochloride are dissolved in 25 c.c. of water ; 10 grms. of carbonate
of potash separately dissolved in 25 c.c. of water are added and the
mixture filtered. With this solution 10 grms. of the oil are thoroughly
shaken for two hours at 15° to 18° C. The oil is then separated, dried
by means of anhydrous sodium sulphate, and acetylated with twrice its
volume of acetic anhydride in the usual way for 1-J hours on a sand
bath under a reflux condenser. ' The oil is washed, dried, and neutral-
ised, and a weighed quantity (about 2 grms.) saponified with alcoholic
potash.
Working on a mixture of citronellal and geraniol, the authors ob-
tained 55*9 per cent, geraniol as against 55 per cent, theoretically
present, and when the heating with potash was prolonged for four
hours the result was not appreciably altered, showing the stability of
the citronellic-nitrile.
A Java oil which showed 83 per cent, of total acetylisable con-
stituents gave 43 per cent, of geraniol and 40 per cent, citronellal,
whilst a Ceylon oil containing 60*2 per cent, of total geraniol and
citronellal was found to contain 43 per cent, of geraniol.
The authors are convinced, by treating considerable quantities of
citronella oil, notably the Java type, that the quantity of geraniol really
1
Roure-Bertrand's Bulletin, April, 1912, 3.
68 THE' CHEMISTEY OF ESSENTIAL OILS
contained in it is lower than that indicated by analysis. This is due to
the presence of a compound, or a mixture of compounds, distilling at a
higher temperature than geraniol and susceptible to acetylation, which
they are further investigating.
Geraniol can also be directly estimated by the following l process :—
Two grms. of the oil are heated with 2 grms. of phthalic anhydride
and 2 c.c. of benzene for two hours on a water-bath. The mixture is
allowed to cool, and shaken for ten minutes with 60 c.c. of semi-normal
aqueous caustic potash, in a stoppered flask. At the end of this time
the anhydride is converted into neutral phthalate, and the acid geranyl
ester into its potassium salt. The excess of alkali is titrated with semi-
normal sulphuric acid. By deducting from the proportion of alkali
absorbed by the quantity of phthalic anhydride used, the quantity of
alkali used up in the experiment, the quantity of alkali absorbed by the
geranyl ester is obtained, and hence the percentage of geraniol can be
calculated. The results of this method applied to the above mixtures-
were as follows:—
I. Geraniol present, 45 per cent. Pound, 47-9 per cent.
II. „ „ 40 „ 41-1
The slightly high results are evidently due to the fact that the
citronellal contained a small proportion of alcohols which react with
the phthalic anhydride.
Schimmel & Co. examined five samples of Ceylon oil by the above
method, and give the following results :—
Citronellal.
| Specific Total
Gravity. Rotation. Acetylisable Geraniol.
Constituents . Kleber's Dupont's
Method. Method.
•
! 0-9012 - 11° 22' 54-1 per cent. 30*7 per cent. 11-4 per cent. 7 '9 per cent.
0-9016 - 11° 28' 57-2 33-2 ll'O 8'0
| 0-9034 - 11° 40' 58-6 30-0 11'6 7'H
0-9039 11° 43' 56-3 29-8 10-8 6-7
0-9033 - 11° 31' 57-6 30-8 11 5 7-9
i
For other methods, which do not appear to be of great practical
value, papers by Kleber 2 and Boulez3 may be consulted*.
Ceylon citronella oil contains about 10 to 15 per cent, of terpenes,
wrhich include camphene, Z-limonene, and dipentene. Geraniol, borneol,
citronellal, methyl-eugenol, methyl-heptenone, isoamyl alcohol, isovaleric
aldehyde, valeric acid esters, a-terpineol, thujone (?), nerol, esters of
citronellal, farnesol, a mixture of at least two sesquiterpenes (one of low
and the other of high specific gravity), and a terpene of very low specific
gravity have all been detected in this oil.4
JAVA ClTKONELLA OlL.
This oil is distilled from Cymbopogon nardus in Java, the grass being
of the Maha Pangiri type. The Singapore distilled oil is of almost
exactly the same character.
1
Schimmel's Report, October, 1912, 43. * American Perfumer, 6 (1912), 284.
4
9
Bull. Soc. Chim., iv. 11 (1912), 915. Schimmel's Report, April, 1912, 44.
N. O. GEAMINE^] 69
It is of a considerably higher value than the ordinary Ceylon oil, and has
a quite different and much finer odour. The principal difference between
it and the Ceylon oil lies in its considerably higher citronellal value, and,
naturally, a much higher content of total acetylisable constituents.
De Jong has carried out a series of experiments on the oil value of
Java citronella grass in various stages of development in order to decide
which is the most favourable time for distilling. As the leaf ages the
oil content decreases; the sheaths of the leaves and the roots contain
much less oil than the leaves themselves. De Jong considers it the best
plan to cut the grass as soon as four or five leaves have developed. As
regards' the properties of oil from different batches of old leaves, the
optical rotation and total geraniol content (geraniol and citronella) show
only insignificant variations. The rotation varies irregularly; values
ranging from - 2° 7' to - 7° 36' being observed in oil from leaves of
various ages. The total geraniol content first increases in an ascending
scale from the newest up to the oldest leaf and afterwards decreases in
a corresponding manner ; the lowest value was 85'5 per cent., the highest
93*3 per cent. The results of this investigation induced de Jong to make
experiments as to the time required for acetylation, the behaviour of the
oil towards acetic anhydride, the amount of acetate of sodium to be added,
and the time required for saponification. As a result of these inquiries
de Jong considers that two hours are needed both for acetylation and for
saponification, and that for every 20 c.c. of oil and acetic anhydride,
2 grms. of sodium acetate are required in order to yield accurate re-
sults. He draws these conclusions because in his experiments on citron-
ella oils he obtained the highest values by using these precautions.
The oils examined by de Jong were soluble in three parts of 80 per
•cent, alcohol; when more than four parts of the solvent were used,
turbidity ensued.
Ultee has carried out a series of experiments on the oil distilled from
plants grown at Salatiga, which is south-east of Buitenzorg where de
Jong's oils were distilled. The former place is situated at a considerably
higher altitude than the latter. Ultee obtained 0'66 per cent, of oil hav-
ing the following characters :—
d29o 0-8721, a D - 3° 15', total geraniol 92'75 per cent., soluble in
1*5 volume and more of 80 per cent, alcohol. The oil was distinguish-
able from the Buitenzorg distillates in the first place by its greater
solubility, for according to de Jong the Buitenzorg oils only gave a clear
solution with 3 volumes of 80 per cent, alcohol, which became cloudy
when diluted to over 4 volumes. As Ultee only obtained an oil yield of
0'66 per cent., whereas in Buitenzorg the yield ranged from 0*5 to 0*9
per cent., experiments were made at Salatiga to ascertain whether the
oil content of the grass could be raised by suitable fertilising. Out of
four experimental fields, three were treated for this purpose with dif-
ferently composed artificial manures. The grass was cut after ten
weeks and equal quantities of it distilled in an exactly similar manner.
The oil yields obtained ranged from 0*60 to 0'65 per cent., showing that
manuring had not affected the oil content of the grass.
Java citronella oil has the following characters :—
Optical rotation - 2° to - 3° (rarely + 2° to - 5°)
Total acetylisable constituents 80 to 94 per cent.
Geraniol . 35 „ 45 „
Citronellal 35 „ 50 ,,
Schimmel & Co. have examined seven samples with especial re-
ferences to their geraniol and citronellal values, and give the following
results :—
Citronellal.
Total
Rotation. Acetylisable Geraniol.
Gravity. Constituents. Kleber's Dupont's
Method. Method.
0-8913 - 2° 15' 85*4 per cent. 35-3 per cent. 36-0 per cent. 36-6 per cent.
0-8859 - 1° 45' 87-6 35-3 40-0 45-2
0-8866 - 1° 35' 88-7 36-4 40-0 46-3
0-8868 - 1° 22' 88*0 33-5 38-8 39-5
0-8883 - 1° 28' 87-5 40-1 38-7 35-4
0-8925 - 2° 11' 84-7 35-9 38-0 37-2
0-8881 - 1° 11' 91-0 37-0 36-8 40-1
Abnormal samples are occasionally met with, which are slightly

dextro-rotatory, or whose specific gravity may rise to 0*900 to 0*905.
In the determination of acetylisable constituents in Java citronella
oil it is l necessary to use considerable excess of acetic anhydride.
Durrans prefers the following quantities and conditions :—
Ten c.c. of the oil with 20 c.c. acetic anhydride (95 to 100 per
cent.) and 3 grms. anhydrous sodium acetate are boiled for two hours
utxder a reflux condenser. The mixture is then cooled, about 50 c.c.
of water added through the condenser, the flask heated on the steam-
bath for fifteen minutes and then cooled, the condenser being connected
to the flask during the whole of these operations. The contents of the
flask are washed in a separatory funnel with cold water (or brine), then
with a 1 per cent. Na2CO3 solution until neutral, and finally with water.
The washed oil is dried with anhydrous sodium sulphate, and from 2*5
to 5 grms. saponified with 50 c.c. normal alcoholic KOH for two hours
under a reflux condenser, the excess being titrated back with acid and
phenolphthalein as usual.
Java citronella oil owes its odour principally to citronellal with
geraniol and some citronellal. Traces of methyl-eugenol, about 1 per
cent, (as against 7 or 8 per cent, in Ceylon oil), are present, and about 0*2
per cent, of citral. A sesquiterpene, isolated by Semmler and Spornitz,2
and termed by them sesquicitronellene, is also present. This body has
Specific gravity at 20° 0*8489
Refractive index . . . . . . . . 1-5325
Boiling-point at 9 mm 138° to 140°
Spornitz3 also detected an oxide in the higher boiling fractions of
the oil, which he named dicitronelloxide, a colourless liquid of the
formula C20H340, and having a specific gravity 0*9199 at 20°, and optical
rotation - 4°.4
Furukawa finds eugenol and probably chavicol, and traces of citronellic
acid in Java citronella oil.
There are a few varieties of citronella oil, distilled in various coun-
1
P. and E.O.R. (1911), 201; (1912), 123. a Bericht, 46 (1913), 4025.
3 4
Ibid., 47 (1914), 2478. Jour. Chem. Ind. Tokyo (1918), 21, 515.
N. O. GBAMINEJE 71
tries, which are, in most cases, obtained from practically the same grass
as that grown in Java. None of them, however, are commercial articles
except, to a very small extent, the Burmese oil.
Burmese oil has characters identical with those of the Java oil, except
that the geraniol is usually present in rather larger amount than the
citronellal. Practical tests with soap appear to show that this oil has
not got so high a perfume value as the Java oil.
Citronella oil distilled in French Guiana (probably from Cymbopogon
citratus) was obtained to the extent of 0*316 per cent. It has the fol-
lowing characters :•—1
Specific gravity 0'8864
Total alcohols as geraniol . . . . . 71*3 ,,
The chief portion of the " alcohols " appears to be citronellal.
Citronella oil from the Comoro Islands has been examined 2 and
found to have a specific gravity 0-892, optical rotation - 0° 52', and to
yield 80 per cent, to a solution of sodium bisulphite.
The oil distilled in German New Guinea does not differ from the
Java oil in any respect, and the same is true of that distilled in the
Malay peninsula. Jamaica oil has been found to have the following
characters:—
Rotation - 4° 16'
Refractive index . . . . . . . 1*4710
Total alcohols, etc. . . . . . . *" . . 86*4 per cent.
Seychelles oil of citronella, distilled from grass derived from Ceylon,
resembles the Ceylon oil in all its characters (Lenabatu oil).
The oil distilled from the wild parent grass (C. Nardus, var. Linnaei
and Confertiflorus) has been examined by Pickles.3 These oils had the
Var. Linnaei. Var. Confertiflorus.
Specific gravity . . 0'894 to 0*926 0'900 to 0'929
Rotation . . . + 4° 54' „ - 6° 32' + 12° 12' „ - 2° 11'
Total " geraniol " . . 43-5 to 64*7 per cent. 39'1 to 64-2 per cent.
Formosan citronella oil has been examined by Furukawa,4 who found
it to have the extraordinary specific gravity 0*960, and to contain 22*15
per cent, of geraniol and 11 per cent, of citronellal. Its odour is poor.
It is not clear whether the grass used is true citronella grass or not.
LEMON-GBASS OIL.
The lemon-grass oil of commerce is almost entirely Bast Indian.
A certain amount was imported a few years ago from the West Indies,
but it was not a successful industry and such oil is not available to-day.
Some few years ago it was regarded as essential to a pure lemon-
grass oil that it should be soluble in 3 volumes of 70 per cent, alcohol.
The West Indian oil was, however, found to be insoluble in 70 per
cent, alcohol (although much of it appears to have been soluble when
freshly distilled, but to have become insoluble during the voyage to this
country). To-day most of the East Indian lemon-grass is not soluble
in 3 volumes of 70 per cent, alcohol. This fact is mentioned now, as
1 2
3
Roure-Bertrand'x Report, April, 1910, 62. Ibid., October, 1909, 42.
Bull. Imp. Instit., 8 (1910), 144. *Jour. Chem. Ind. Tokyo (1918), 21, 515.
leading up to a speculative view as to the actual type of grass used in
the distillation.
Stapf, in the admirable work on the Cymbopogon grasses described
under Citronella Oil (p. 60), has held that the soluble lemon-grass oils
are obtained from Cymbopogon ftexuosus as the parent plant, and that
the insoluble oils are derived from Cymbopogon citratus.
The chemists of the Imperial Institute,1 however, hold the view that
the insolubility of much of the Cochin lemon-grass oils is due to the fact
that the oil is distilled by steam, which has carried over the less volatile
and insoluble fractions, whilst the soluble oils are distilled over a naked
fire in the old-fashioned manner.
The conclusions drawn by the Imperial Institute chemists do not
seem to have any great amount of evidence to support them. The
author observed, some years ago, that West Indian lemon-grass oil de-
creased considerably in citral value by keeping, and also became far less
soluble. The freshly distilled oil from Cymbopogon citratus distilled in
the West Indies was soluble in 3 volumes of 70 per cent, alcohol when
freshly distilled. Since then he has had the opportunity of examining
numerous samples of Cochin oil which had been tested before shipment,
and which on arrival in Europe had lost from 3 to 5 per cent, or even
more of their citral contents. In the author's opinion, there is room
for tha belief that the recently found insolubility of Cochin lemon-grass
oil may be due to differences in the exact type of grass used, and also in
the conditions of cultivation.
The oil-content of tfce individual parts of Cymbopogon citratus in
their various stages of development has been the subject of researches
by A. W. K. de Jong so as to ascertain which period is the most favour-
able one for the harvest and the distillation. According to him, the leaves
contain most of the oil, of which the quantity is always largest in the
leaf of the latest formation, whilst with the increasing age of the leaf,
the oil-content continuously diminishes. The citral-content of the oil
becomes slightly higher as the age of the leaf increases, viz., from 77 to
79 per cent, in the youngest, up to 83 per cent, in the oldest leaves.
The sheaths of the leaves also contain oil, but considerably less than the
leaves themselves. In the roots of" Cymbopogon citratus essential oil is,
according to de Jong, also present—not in the thin, fibrous roots, but
in the thick bulbs, and in the young bulbs more (about 0'5 per cent.)
than in the older ones (about 0*35 per cent.). For this reason de Jong
recommends that the roots should also be included in the distillation,
but unfortunately he gives no information as to the properties of the
root-oil. De Jong concludes from his experiments that it is inadvisable
to wait longer for the cutting of the grass than until four to five leaves
have been formed.
De Jong observed, that although the Java oil immediately after dis-
tillation is soluble in 2 volumes of 70 per cent, alcohol, the solubility
diminishes considerably after a few days, and after a prolonged time
the oil only forms a very cloudy solution from which, if left standing,
part of the oil again separates. The cause of this change is, in de Jong's
opinion, the polymerisation of a terpene; an oxidation process appears
to him out of the question, as the oil becomes insoluble if it is kept with
the air excluded. Various attempts made to prevent the change, re-
1
Bull. Imp. Instit., June, 1914.
N. O. GKAMINEÊ 73
imained unsuccessful; it was found that the change takes place rapidly
when the oil is heated to 100°.
Distillation experiments have also been carried out at one of the
.agriculturo-chemical experimental stations in Cochin China. It was
then found that the content of oil during the dry season is considerably
larger than during the rainy season, and that the portion of the leaf
equal to one-third its length measured from the tip, is much more
aromatic than the other two-thirds.
From well-dried leaves 8 to 8*5 per cent, of oil was obtained, whilst
;from leaves distilled directly after harvesting, 2 per cent, was obtained
in the rainy, and 5*5 per cent, in the dry season.
According to Bacon,1 a variety of grass which, from the character-
istics of the lemon-grass oil it produces, is regarded as Cymbopogon
citratus D.C., is cultivated to a small extent in the Philippines, although
it occurs everywhere throughout the Archipelago, both as a garden-
plant and in the wild state, and grows in special profusion in the high-
lands of the province of Benguet. In the Tagal language this oil-grass
is called by the name given to it in 1635 by the Spanish Jesuit, Juan
Eusebius Niirnberg, who was the first to describe it, viz.: tanglat or,
more accurately, tanglad. Other native names for the plant are salai
and balyoco; its Spanish name is Paja de Meca. A grass five months
old, distilled two days after being cut, produced 0*2 per cent, of an oil
30°
having the following characters: d ^ 0*894, aD3o° + 8*1°, n 30° 1*4857,
.citral-content 79 per cent. The same plants, when cut again four
months later, produced 0*2 per cent, oil with the following characters:
30°
d -jo- 0*8841, aD3o° + 2-1°, nD3Qo 1*4765, citral-content 77 per cent. A
grass S3ven months old from another plantation, distilled immediately
after being cut, produced 0*21 per cent, oil, possessing the following
30°
-characters: d — ^ 0*891, aD30° + 7*76°, 7^D30' 1*4812, and citral value 78
per cent.
Lemon-grass oil is also produced in small quantities in Burma, the
Citral-content
Origin. <H50. «D. (Bisulphite
Method).
Ceylon 2 . 0*9058 - 0°6' 76°/ 0

India, Tyrna' 2 0-9021 - 0° 20' 72-5 %
„ Cochin 2 0-9053 - 0° 39' 84-5 °/0
,, Mariani 0-9140 - 0° 5' 73%
Uganda a 0*870 to 0*894 + 0° 10' to - 0° 24' 64-5to75°/ 0
Bermuda 2 0-8689 - 0° 21' 40%
Montserrat 2 — over 74 %
German New Guinea :j 0-881 —
to 0-892 - 0° 11' to - 1° 15' 65 to 78 %
Mayotte 3 0-893 - 0° 23' 87%
Seychelles 4 0-895 to 0-910 - 0° 15' to - 2° 40' 76 to 81 %
Formosa 5 0-865 „ 0-914 0° to - 0° 8' 54 „ 76%
Celebes 5 0-880 - 0° 15' 69%
1 2
Philippine Journ. fife., 4 (1909), 111. Bull. Imp. Iwtit., 9 (1911), 334.
4
'"SchimmeVs Report, April, 1909, 65. Ibid., April, 1914, 67, 68.
5
Ibid., April, 1913, 72.
Seychelles Islands, Uganda, Bermuda, and various other places. There
is, however, nothing particularly characteristic about these oils, the fore-
going figures illustrating the general characters of a number of them.
Lemon-grass oil has the following characters if distilled in the East.
Indies; it may occasionally fall outside these limits, and, as will be seen
from the above, may vary considerably from them when distilled else-
where :—
Optical rotation + 1° 30' to - 5°
Citral (bisulphite method) . . . . . . 68 to 85 per cent.
The oil is somti'mes soluble in 3 volumes of 70 per cent, alcohol, some-
times insoluble.
Generally speaking, the citral is determined by absorption with sodium
bisulphite, but this determination will include bodies other than citraL
Some chemists prefer to determine it by neutral sodium sulphite, but as
this process gives lower results the method used ought always to be
stated. The sulphite method gives from 3 to 6 per cent, lower results
than the bisulphite method.
According to most chemists who have worked seriously on this oil,
citral is the only aldehyde present in the oil, with the exception of traces
of an isomeric aldehyde, and of decyl aldehyde, and citronellal.
Upon this point Tiemann, Semmler, and Doebner, the three chief
authorities on this oil, are completely agreed. Stiehll has claimed to have
separated the aldehydic constituent into three different bodies. He urges
that the large amount of citral found in the oil usually is due to the
isomerisation of the other aldehydes by means of the bisulphite of sodium
used in separating it, which is generally too acid. If this salt be perfectly
pure he claims that this isomerisation does not take place. These alde-
hydes he terms citral (the aldehyde usually known as such), allolemonal
and citriodoraldehyde, and he gives the following as their properties :—
Citriodoraldehyde. Allolemonal. Citral.
Boiling-point . . . . 228° to 229° 233° to 235° 225° to 227°
Specific gravity at 20° . . . -8883 -9017 -8868
Rotation 0° - 5° 6' 0°
Melting-point of compound with
naphthocinchoninic acid . 204° 235° 197°
Doebner, however, has shown—in the author's opinion conclusively
—that these other aldehydes are merely impure citral. By the term
citral is meant a mixture of the stereoisomeric bodies, a-citral and
/3-citral.
Traces of an isomer of citral, having a specific gravity 0*908, have
been detected, and also traces of decyl aldehyde. Methyl-heptenone is
present, as 2well as geraniol, linalol, dipentene, and limonene. \
Kafaku has identified myrcene, and a new aldehyde in Formosan
lemon-grass oil.
This oil is largely used for the preparation of citral for the manu-
facture of ionone, so that it is usually sold on its citral value.
OIL OF CYMBOPOGON SENNAAKENSIS.
O. D. Eoberts 3 has examined at the Imperial Institute the distillate
from the above grass, which is known in the British Sudan as " ma-
1 2
Jour, prakt. Chem., 1898, 51. Jour. Chem. Ind. Tokyo (1917), 20, 825.
s Jbwr. Chem. Soc., 1915, 1465.
N. O. GEAMINE^ 75
hareb " grass. The material yielded 1*0 per cent, of a pale yellow oil,
possessing a pleasant odour resembling that of pennyroyal herb, but
more fragrant. It had a specific gravity of 0*9383, optical rotation
-f 34° 14', saponification value 14, ester value after acetylation 60*2. A
larger supply of material gave T2 per cent, of oil having a specific
gravity of 0*9422, optical rotation + 29° 38', acid value 4*2, ester value
14*5, ester value after acetylation 62*1 The results of further investi-
gation showed that the oil has the following approximate composi-
tion :—
Per Cent.
Terpenes, including d-limonene and probably pinene . . . 13-0
Ketones, chiefly or entirely ^'-menthenone . . . 45'0
Sesquiterpene alcohol C^HÔ . . . . . . . 25*0
Undetermined alcohol with rose-like odour 3'0
Phenols undetermined (benzoyl derivative melting-point 70°
to 72°) 0-2
Acids, probably acetic, octoic, and decoic, both in free state and
as esters, with palmitic acid as esters . . . . . 2'0
Besidue, probably containing sesquiterpenes . . . .11-8
A'-menthenone was first obtained synthetically by Wallach and
Meister, who prepared it from 1 : 3 : 4 trihydroxyterpane, and its proper-
ties were fully investigated by Schimmel & Co., who isolated it from
Japanese peppermint oil, which appears to be the first record of its-
occurrence in nature. On reduction it yields menthol.
OIL OF VETIVERT.
This oil is distilled from the roots of Vetiveria zizanioides Stapf,
the plant formerly known as Andropogon muricatus Ketz. These roots
are known in Bengal under the name of khas-khas, from which the
name cus-cus is easily traced. The plant is a perennial tufted grass
growing to a good height, and is found all over the country near the
Coromandel coast, Mysore, Bengal, Burma, and the Punjab. In con-
tradistinction to the grasses previously described, the leaves themselves
are practically odourless, whilst the roots have a strong, agreeable odour.
The perfume of the roots is suggestive of myrrh. It appears to be
indigenous to the East Indies; is common in the islands of the Malay
Archipelago, on the Malabar coast, in Bengal, Ceylon, in the islands of
the Indian Ocean, the Antilles, Brazil, Jamaica, New Caledonia, and
many other localities.
The plant requires a warm, damp climate, a mean temperature of
25° C., and a firm, sandy, clayey soil. Propagation is made by means
of fragments of the root nipped off and transplanted. This is generally
done in the rainy season, the fragments being planted in borders along
the roads or on slopes where landslips are feared, as the long roots bind
the soil together.
After one year the vetivert has developed strongly, and as a hedge
to plantations of sugar-cane, rice, vanilla, etc., forms a thick curtain,
effectually protecting the crops against storms of wind and dust. On a,
commercial scale the plants are set in rows about 1-J- metres apart, 65
rows to the hectare, a total of 6500 metres representing about 43,000
roots. Such a plantation from the second year will give from 30,000
to 35,000 kilos, of roughly-shaken roots, which after washing will yield
about 2-£ tons of cleaned product. In other words, a hectare of land
gives 2-J tons of marketable vetivert roots.
On distillation, the first fractions passing over are much more volatile
and lighter than those which come over with difficulty towards the end
•of the distillation. These " light " and "heavy " oils can be separated
by using a steam-jacketed still with steam at a pressure of about 10 lb.,
until no more oil comes over. The heavy oil is then obtained by passing
steam at a higher pressure direct into the retort. The oil distilled in
Europe, however, is usually, if not always, a single distillate, and the
fractionated oils are scarcely commercial articles. Be"union distilled oil
is, however, of much lighter specific gravity than European distillates,
and is usually found to vary from 0*980 to 0'995. The yield of oil is a
matter of much disagreement. According to Piesse, 100 lb. of oil yield
about 9 to 10 oz. of oil, whilst Watts states that only 2 oz. are obtained.
Other,observers give from *4 to *9 per cent. Probably about 1 per cent,
is the usual average.
In order to determine the yield of cus-cus oil from the roots grown
in various localities, Puran Singh examined the following seven samples
.from different localities in India with the following results :—
. +z
0)
.2 +
O
•^P
Locality.
Month of
Collection.
fe
OJ
^
8
°1 as
^Pn e
"c 03
1. Godhra Range, Panch Mahal April, 1913 8-51 2

2-66 0-72
District, Bombay
2. Ajmer, Rajputana March, 1913 10-14 3-10
3 1-13
3. Pilibhic, United Provinces . April, 1913 10-46 4
4-30 0-69
4. Ditto, and inferior sample, July, 1913 9-51 4-71
4 0-37
.thin White Roots
5. Belgaun Forest Division, May, 1913 10-88 3-84
3 0-99
Bombay
6. Yeotmal Forest Division, Aug., 1913 9-45 3-10
3 0-45
Central Provinces
7. Delhi, from the Bazar. The Jan. to Feb., 9-81 2
2-97 1-14
best long Fibres used by 1914
Native Perfumers.
A sample distilled in India by Puran Singh,1 and rectified by steam

distillation, had the following characters :—
Acid value . . . . . . . . . . 10*5
Ester „ 69-6
The resinous matter left in the still had the following characters:—
Optical rotation . + 488°
Acid value 46-9
Ester ,, 64-3
Vetivert oil of commerce, however, is always dextro-rotatory, obvi-
1
Chemist atid Druggist, 85 (1914), 225.
N. O. GEAMINEÊ 77
ously containing the high boiling constituents left behind in the above-
rectification.
Vetivert oil distilled in Europe has the following characters :—
Optical rotation . +25° , + 40°
Refract ive index . 1-5200 1-5230
Acid va lue . 25 , 65
Ester , 10 . 25
, (after acetylation) 130 , 160
On fract ionation the oil yields results as follows : —
Boiling-point at 23 mm. Per Cent. Rotation.
144° to 164° 8 - 4° 10'

164° „ 170° 10 - 3° 20'
170° „ 180° 24 + 2° 5'
180° „ 185° 30 + 31° 40'
185° „ 200° 20 + 47° 5'
Vetivert oil distilled in Reunion, or in the Seychelles, has the following

characters :—
Specific gravity 0-982 to 1-020 (rarely, over 1-050)
Optical rotation . . . . ri- 10° to 38°
Refractive index . . . . 1-5150 „ 1-5285
Acid value . . . . 4 ,, 20
Ester ,, . . . 5 „ 20
,, , t (after acetylation) 103 „ 150
Oil distilled in the Fiji Islands has a specific gravity 1*018 to 1*0298,
acid value about 30, ester value about 17, and ester value after acetylation
about 145. In all other respects it corresponds with European distilled
oil.
Vetivert oil is soluble in 1 to 3 volumes of 80 per cent, alcohol,
usually becoming cloudy on the addition of more alcohol.
A vetivert oil distilled from roots from the Philippines has been ex-
amined by Eouiv-Bertrand Fils l and found to have the following char-
acters :—
Specific gravity . . . . 1-0139
Optical rotation . . . + 30n 8'
Acid value . . . . . 21-5
Ester „ . 6-5
Free alcohols (C15H24Oj . . 7 1 - 5 p e r cent.
Seychelles distilled oil agrees generally with Eeunion oil in charac-
ters. It has, however, a lower optical rotation—usually from 4- 10° to
+ 20°—and a rather lower free alcohol value, the ester value of the acety-
lated oil varying from 100 to 135.
Castor oil and other fatty oils are sometimes used as adulterants.
These oils will raise the ester value, and lower the specific gravity and
refractive index.
The chemistry of vetivert oil is in a somewhat unsettled state,
1
Report, April, 1914.
-each successive investigator differing somewhat in his results from
previous workers. Furfural, diacetyl, and methyl alcohol are present
in the distillation waters of:the oil.
Fritzsche & Co. claimed to have isolated a mixture of ketones which
they termed vetiverone, having the empirical formula C13H22O and a
specific gravity about 0*990. Two alcohols were also found having the
1. 2
Formula C9H14O CnH18O
Boiling-point at 10 mm 150° to 155° 174° to 176°
4 Genvresse and Langlois 2 have isolated a sesquiterpene from the oil,

C15H24, which they term vetivene. It boils at 262° to 263° at 740 mm.,
and has a specific gravity 0*932 and optical rotation + 18° 19'. A ses-
quiterpene alcohol, C15H26O, was also isolated, which the discoverers
term vetivenol. It boils at 169° to 170° at 15 mm., and has a specific
gravity I'Oll at 20° and optical rotation + 53° 43'.
An acid, or mixture of acids of the empirical formula C16H24O4 was
also found, and the authors consider that the characteristic odour of the
oil is principally due to the presence of esters of these acids with
vetivenol. 3
Bacon considers the acid or acids present in this oil to correspond
with the formula C15H24O2. He also found benzoic acid present in the
oil. The4 most recent work on this oil is that of Semmler, Risse, and
Schroter. According to these chemists the formulae given by Genvresse
and Langlois are incorrect, the correct ones being, for vetivenol C15H240
and for the acid C15H22O2. The last-named investigators examined an
oil possessing the following properties : d20°- 1*0239; aD + 31°; n^,^
1*52552. They distilled 400 grms. of this oil, at 12 mm., intD the fol-
lowing four fractions :—•
(A) Boiling-point 129° to 175°, 23 per 390:
(B) ,, ,, 170° ,, 190°, 34
(C) ,, ,, 190° ,, 250°, 8
(D) ,, „ 250° ,, 300°, 30
Fraction (D), when subjected to further distillation, was s^lit up into
two portions, as follows :—
(D, a] BDiling-point 138° to 260° (13 mm.), 28 per cent.
(D, b) „ „ 260° „ 298° (13 mm.), 62
Analysis showed that the portion (D, b) consisted of an ester C30H4402
of the acid C15H22O2 and the alcohol C15H.)4O. The characters of the
free alcohol are as follows : boiling-point 170° to 174° (13 mm.) ;
d.20o 1-0209; aD + 34° 30' ; nD 1-52437; molecular refraction 65*94.
Hence the vetivenol of this fraction can only be a tricyclic, simply un-
saturated alcohol. The acid C15H22O2 boils at 202° to 205° (13 mm.), is
tricyclic and is called vetivenic acid by the authors. Its methyl ester
boils at 170° to 173° (18 mm.) and has the following characters : d00o
1-0372 ; aD + 42° 12'; WD T50573 ; molecular refraction 71-05.
Fractions (A) and (B), when subjected to repeated fractional distilla-
tion in vacuo yielded a fraction boiling between 173° and 180° (13 mm.),
from which vetivenol was obtainable by treatment with phthalic anhy-
1
DM.P., 142415 (1902) - '2 Comptes rcndus, 135 (1902), 1059.
4
'•' Philipp. Jour. Sc., 4 (1909), 118. Bericht, 45 (1912), 2347.
N. 0. GRAMINE^ 79
dride. It therefore appears to be a primary alcohol. Vetivenol (tricyclic)
yields an acetate, boiling-point 180° to 184° (19 mm.) ; d200 1*0218 ; ao +
28° 48'; nn 1-50433; molecular refraction 75-91. Fraction (C), upon
saponification, yielded an oil from which, under repeated distillation,
there was obtained a portion boiling between 178° and 185° (19 mm.) :
d20o 1-0137; aD + 52° 12'; nD + 1-52822; molecular refraction 66-81.
This body, therefore, represents a mixture of bi- and tricyclic vetivenol.
The acid of fraction (C) was identical with vetivenic acid. The frac-
tions (A) and (B) also contained a primary bicyclic vetivenol, which may
possibly be ident cal with that from fraction (C). These portions also
contained tricyclic vetivenol.
Repeated fractionation in vacuo of fraction (A), the last fractionation
being conducted over sodium, yielded two hydrocarbons :—
I. Boiling-point 123° to 130° (16 mm.); d2QO 0*9355; aD + 2° 16';
WD 1*51126 ; molecular refraction 65'32.
II. Boiling-point 137° to 140° (16 mm.); d2QO 0'9321; aD - 10° 12' ;
nv 1*51896 ; molecular refraction 66*42.
The characteristic ester of the European distilled oil is absent from,
or only present in very small amount in, Reunion distilled oil, which is
very low in ester-content.
It has been suggested that vetivert oils with high specific gravities
are superior in odour value to the Reunion oil. This, however, is cer-
tainly not the case when money value is taken into account, these latter
being quite disproportionate from the odour values, which do not differ
very materially.
PALMAROSA AND GINGEK-GKASS OILS.

These oils are distilled in India from the grass Cymbopogon Martini
(Andropogon Schoenanthus Linn.). There are two forms of this grass,
known in India as " Motia " and " Sofia," but their botanical differences
are not yet established.
The " Motia " grass yields the important commercial oil, palmarosa
oil, whflst the " Sofia " grass yields the less valuable and quite different
ginger-grass oil.
The common name in India for this grass is Rosha or Rusa grass
and as for many years the oil found its way into Europe via Constanti-
nople, it was called—and still is to some extent—Turkish geranium oil,
as it is an oil rich in geraniol and having an odour something like that
of geranium oil.
The plant has a wide distribution, being generally found in the drier,
hot localities of India. Watt in his Commercial Products of India
states that there are specimens in the Kew Herbarium from Kashmir,
Punjab Hills, Simla, Alrnora, Garhwal, Singhbhum, the Central Pro-
vinces, Bombay, Rajputana, and Southern India. From a commercial
point of view the more important areas in which Rosha grass is worked
for the oil are the Bombay Presidency, the Central Provinces, and the
Berars and certain native States in Central India.
According to Haines it is found growing from Singhbhum to the
Santal Parganas in valleys near water-courses and on the northern or
shady sides of hills. Blunt states that in the Berars the " Motia "
variety prevails in open forests and the less valuable "Sofia" in dense
forests. Pearson 1 has found " Motia " generally growing on relatively
bare, hot slopes, such as the Taloda and Shahada Satpuras and " Sofia"
on the lower ridges and in shady nullas such as are found in the
Pimpalner and Nandurbar Eanges of the Khandesh District, the Yeola,
1
Indian Forests Records, V, vii. 2.
N. O. GEAMINE^ 81
Sinnar, and Kalwan Eanges of the Nasik District, and in the Dohad and
Jhalod Eanges of the Panch Mahals. >
Dunbar Brander states that "Motia" is found on bare, hot slopes
a
I
e3
O>
CQ
tf
II
CM'
and "Sofia" in denser moist areas. He states that the two forms are
divided by a sharp line and that there must be some factor governing the
occurrence of the two varieties. Donald supports the above statement
VOL. i. 6
and further states that " Sofia" is often found in poorly-drained
areas.
" Motia " grass is rarely, if ever, found growing gregariously over
large tracts of country ; it is generally found in single clumps a foot or
two apart which together form open grass land, while " Sofia " on the
other hand is much more gregarious in its habits and in some cases
covers considerable areas as a dense crop of grass.
Pearson1 gives the following account of the distillation of the oil:—
The local practice, which is at present the only method by which
the oil is extracted from the stems, leaves, and flowers, is that of direct
firing of the still, steam distillation having t>nly been tried as an ex-
periment.
The portion of the plant from which the oil is obtained is the flower
and leaf, while only small quantities of the oil can be obtained from the
stem itself. The flowers and upper third of the stem are collected in
September and October, being tied into bundles or "pulas" of about
£th of a pound each. Donald2 in describing the process of distillation
states that the inflorescences are cut twice, a second flowering occurring
after the first inflorescence has been cut. The grass is either distilled
in a partially green state or the flower heads and portion of stem are
carefully dried in the shade before distillation, during which period they
lose from about 20 to 40 percent, of their weight according to the
degree of dryness which they are allowed to attain before being treated.
The plant used by the local distillers varies little from district to
district in the Central Provirices and Bombay, being in every case of a
very primitive type. The still is in all cases erected within a few feet
of a stream or pond, because considerable quantities of water are
required for the distillation process itself and also for cooling the con-
denser. The still itself is of iron or copper and of cylindrical shape,
having a sufficiently large opening at the top to allow of the charge
being introduced; it is also often fitted with handles for transport pur-
poses. The size of such stills varies in-different localities, varying from
12 to 14 gallons.
The still is either built in and covered with mud up to the neck, or
is simply supporced on stones over a fire-grate by which direct heating
is obtained. The opening at the top of the still is closed either with
an iron or wooden disc in which a 1^ in. to 2 in. hole is drilled in the
centre, the disc being luted to the still with flour paste or mud and
chaff, with the help of a. rag which forpas a wrapper over the joint. In
the hole in the disc is fitted a bamboo^'lS ins. to 2 ft. long, the joint of
which is also made good with flour paste. The upper end of the
bamboo is bevelled to an angle of 60° to take another section of bamboo
about 8 ft. long, the joint being either pegged or made good by wrapping
cloth round it, which is further secured by binding twine over the rag
and the whole covered with paste or mud. In order to form the
bamboo into a pipe the nodes are drilled through with the help of a hot
iron, this being done before the bamboo is fixed to the still. In some
cases the bamboo pipe is covered to within 6 ins. or 8 ins. of the lower
end with a strip of rag or it is bound the whole of its length with twine,
thus preventing the bamboo from splitting. The condenser is generally
made of copper, of bulbous shape with a long neck. Donald, however,
] 2
Loc. cit. Indian Forester, xxxix. 3» 149.
«
p
0
W
00
CO
FIG. 13.—Modern steam distillation of palmarosa oil.

[Indian Forest Records. E. S. Pearson, I.F.S.
84 THE CHEMISTBY OF ESSENTIAL OILS
states that an earthern garrah was in use in the distillery visited by
him. It is placed in "running water or in default of running water into
a pond, with the lower end of the condensing tube leading to it. The
capacity of the condenser varies according to the size of the still and is
capable of holding anything from 8 to 15 gallons.
The still is charged with grass and cold water in proportions of one
to four by weight. The fire is then put under the still and the distillate
commences to come over within three-quarters to one and a half hours,
according to the capacity of the still and the size of the grate.
The yield of oil may be as low as 0*15 per cent, in the case of care-
lessly dried material, or as high as 1 per cent, if the material is care-
fully dried.
Experiments on the steam distillation of the oil carried out by
Messrs. Pheroze & Co. of Bombay resulted in a yield of O87 per cent,
of oil by steam-distilling the entire plant, which consisted of 54 per
cent, of stalks, 28*5 per cent, of leaves, and 17'5 per cent, of flower-
heads. Each portion of the plant when distilled separately gave the
following figures:—
Stalks '04 per cent, of essential oil.
Leaves 1-32
Flower-heads 1*71 ,, ,, „
They remark that the yield might have been much more, say 1 per
cent, to 1*25 per cent., had the distillation been carried out with abso-
lutely fresh grass immediately after it was cut, instead of with grass
which must have lost some of its volatile oil during transit to Bombay.
Pheroze & Co. did not report the percentage of moisture in the grass
at the time of distillation. In the fresh green grass, the moisture is
usually about 60 per cent., so that, assuming the moisture in the grass
distilled by Pheroze & Co. to have been 50 per cent., the yield of oil
calculated on completely dry grass works out to 1'74 per cent, on the
entire plant and 2*94 per cent, of oil on flower-heads and leaves only,
neglecting the traces of oil in the stalks.
Experiments carried out with air-dried " Sofia" grass, obtained
from the Melghat Division of the Central Provinces, and containing
13 per cent, of moisture, gave 0*41 per cent, of oil by steam distillation.
The entire plant consisted of 60 per cent, of flower-heads and leaves and
40 per cent, of stalks, so that, calculated on the completely dried flower-
heads and leaves only, the percentage of oil obtained comes to 0*78 per
cent. The yield of oil on the entire plant of " Motia " grass containing
12*88 per cent, of moisture, was 0'5 per cent. The entire plant con-
sisted of 40 per cent, of flower-heads and leaves and 60 per cent, of
stalks. Leaving out of consideration the stalks, the yield comes to-
1-42 per cent, calculated on the completely dried flower-heads and
leaves only. It may be noted here that the grass distilled was dry and
over-ripe, while most of the flower-heads had been damaged in transit..
The percentage, therefore, cannot be compared with that obtained by
Pheroze & Co. The above results obtained by the distillation of dry
grass have only been mentioned to show that by steam distillation not-
only can the green grass be worked in October and November, but that
the air-dried grass containing about half the amount of oil as compared
with fresh grass can be kept in stock for running the still after the crop
has been reaped.
Palmarosa oil is a pale yellow liquid (sometimes rather dark on ac-
N. O. GRAMINEJE 85
•count of the crude methods of distillation used by the natives, wherein
too little water is used in the stills, with the result that the grass is
burned), but sometimes water-white when rectified. It has a char-
acteristic geranium odour, and is a most popular perfume where an
odour recalling roses and geranium is required at a comparatively low price.
The pure oil has the following characters :—
Optical rotation -3° „ +5°
Acid value . . 0„3
Ester „ 12 „ 50
Total geraniol 78 to 94 per cent.
The oil is soluble in 3 volumes of 70 per cent, alcohol.
Samples distilled in Java have been examined by Schimmel & Co.1
Specific gravity . . . . . 0-8906 t o 0*8920
Optical rotation + 0° 30' „ + 0° 42'
Acid value 1-2 „ 1-8
Ester „ 37-5 „ 51-6
after acetylation 272-7 „ 276-8
Total geraniol 94-3 to 96 per cent.
The oil is soluble in 3 to 3-5 volumes of 60 per cent, alcohol.
Palmarosa oil contains free geraniol as its principal constituent to-
gether with a small but varying amount of esters of the same alcohol,
principally those of acetic and caproic acids. Methyl-heptenone is
present in traces, as well as the terpene dipentene. Flatau and Labbe 2
•claimed to3 have detected citronellal, but this is denied by Schimmel &
Co. Elze states that farnesol is present in the oil.
Ginger grass or " Sofia " grass oil differs in characters entirely from
palmarosa or " Motia " grass oil. It has the following characters :—
Optical rotation -30° „ + 50°
Refractive index 1*4780 „ 1-4950
Acid value 2 „ 6
Ester „ 8 to 40 (rarely to 55)
„ „ (after acetylation) . . . . 120 to 200
The oil is usually soluble in 3 volumes of 70 per cent, alcohol, but
generally becomes cloudy on the addition of more alcohol. Some
samples, however, do not appear to be soluble in 3 volumes, but re-
quire considerably more 70 per cent, alcohol to effect solution.
The known constituents of ginger grass oil are the terpenes, dipen-
tene, d-a-phellandrene and d-limonene, together with geraniol, and an
alcohol which is identical with that obtained by the reduction of perillic
-aldehyde, and which is known as" perillic alcohol.
Walbaum and Hiithig 4 have isolated an aldehyde from the oil, having
ihe formula C10H160, having the following characters :—
Optical rotation . ± 0°
Refractive index . 1-47348
Oxime melting point . 115° to 116°
Semi-carbazone melting-point 169° „ 170°
Phenylhydrazone „ 63°
l
8
Bericht.October, 1914; April, 1915, 37. *Comptes rendus, 126 (1898), 1725.
Chem. Zeit., 34 (1910), 857.
*Bericht, Schimmel & Co., April, 1904, 52; October, 1904, 41; April, 1905, 34.
Carvone is also present in small amount. The principal constituents

of the oil, however, are geraniol and perillic alcohol, C10H16O.
Schimmel & Co.* give the following figures for a number of typical
samples of both oils:—
Place of
No. Production. D «D.
ND Acid Ester Total Solubility in
15°. 20°. No. No. Geraniol. 70 °/0Alc ohol.
i
Palmarosa Oils (Motia Oils).

Per Cent.
1 Chi tar 0-8904 - 0° 6' 1-47225 0-8 39-8 91-5 1-5 vol.
2 Kumbi 0-8911 - 0° 5' 1-47176 1-0 47-3 90-7 1-5
3 Mohana 0-8906 - 0° 20' 1-47264 0-8 34-8 92-0 1-5
4 Naoli 0-8903 - 0° 15' 1-47205 0-5 40-7 93-0 1-5
5 Ragarwal 0-8946 - 1° 20' 1-47382 0-8 38-4 88-2 1-5
6 Udhala 0-8906 - 0° 35' 1-47225 0-8 38-7 92-4 1-5
Ginger-grass Oils (Sofia Oils).
7 Astumber . 0-9396 - 19° 42' 1-48996 6-2 10-2 39-2 2-2 vols. if more
cloudy.
8 Bandhera . 0-9372 - 15° 20' 1-48967 2-0 10-0 42-6 2-1 vols. if more
opalescent.
9 Chanseli . 0-9392 - 38° 47' 1-49082 5-3 8-0 41-1 2*2 vols. if more
cloudy.
10 Rapapur . 0-9533 - 27° 15' 1-49252 4-5 8-8 48-1 1*8 vols. if more
cloudy.
LESSEE-KNOWN CYMBOPOGON OILS.

Fiji distilled oils, probably from Cymbopogon coloratus,'2 have been
found to have the following characters :—
Specific gravity 0-9111 to 0*920
Optical rotation . . . . . . - 7° 43' „ - 10° 42'
Geraniol 15*6 per cent.
Citronellal 45-7 to 49-5 per cent.
Another sample, however, examined at the Imperial Institute had
the following approximate composition :—
Terpenes 7*5 per cent.
Aldehydes, chiefly c i t r a l . . . 40
Geraniol 23
Esters, chiefly geranyl acetate . 10
Acetic acid 0-75
Phenols 0-75
Substances not identified . . 18
Four samples of the oil from Cymbopogon polyneuros from Ceyloiv
were found, on examination at the Imperial Institute 3 to have the
1. 2. 3. 4.
Specific gravity 0-942 0-951 0-936 0*943
Rotation . — + 50° 39' + 53° 15' + 30° 53i
Total alcohols . . , 44 per cent. 44 per cent. 38-7 per cent. 51-8 per cent.
Solubility in 80 per cent
alcohol. 1 in 1 1 in 1 1 in 1 1 inl
Cymbopogon Schoenantlmis yields the so-called " camel grass" oiL
1
Report, April, 1910, 85. '2Bull. Imp. Instit., 10 (1912), 27.
Ubid,
N. O. GEAMINE^ 87
According to Dymock l and Schimmel2 this oil has the following char-
acters :—
Specific gravity 0*905 at 29°
0-915 ,, 15°
Optical rotation - 4° to + 34° 38'
The oil contains phellandrene.
Hofman 3 has investigated the properties of an essential oil distilled
from a species of Cymbopogon, which, in the absence of a more precise
determination, he calls Cymbopogon javanensis. It is a light yellow oil,
with a pleasant sweet smell, resembling more the palmarosa type than
the lemon-grass kind. An analysis of the oil yielded the following
results:—
Acid number 1-25
Saponification number 30-9
Geraniol content . 48-2 per cent.
Free alcohols 33-9
Esters . 14-3
Methyl -isoeugenol . 30-4
Among the aldehydes isolated from the oil methyl-vanillin was found,
which had never previously been found in an essential oil. Citral,
Z-a-pinene, and methyl-isoeugenol are also present in the oil.
OIL OF ANDROPOGON GBYLLUS.
The green portions and root of Andropogon Gryllus (A. Ischaemum)
yield up to 1 per cent, of essential oil, which has been examined by
Schimmel & Co.4 Two samples had the following characters:—
Optical rotation - 10° 52' - 11° 4'
Acid value 1-9 0-9
Ester value . 8-4 16-8
,, „ (after acetylation) 37-3
It has no value as a perfume oil. It contains about 10 per cent, of
an alcoholic body calculated as C10H18O.
OIL OF ELIONUKUS TRIPSACOIDES.
This grass is a native of Central America, extending from Mexico to
the United States of Colombia and Venezuela. It is very abundant in
Bolivia. It belongs to the same tribe of grasses (Andropogonece) as the
ginger-grass, lemon-grass, citronella, and vetivert, but differs from the
genus Andropogon in the spikes of flowers not bearing awns, and ap-
proaches Eottboellia in the slender spikes, differing from it in having
hairs on the rachis of the spikelets, and on the stalks of the flowers,
being, in fact, intermediate between the two genera. The odour of the
root approaches that of vetivert, or cuscus, but is of a somewhat sweeter
and Jess penetrating character.
It is interesting to find that it is not the only aromatic species of the
genus, since in South Africa a species occurs which has a thyme-like
odour, whence its name Elionurus thymiodorus. It occurs in the
1
Pharmacographia Indica, vi., 564. *Bericht, April, 1892,44.
4
b. WeekbL, September 6,1919. Bericht, 1917, 8; 1918,5.
Albany and Uitenhaage and Fort Beaufort Divisions, at an altitude
of 1 to 3000 ft.
Oil from Elionurm tripsacoides has been examined by Umney, the
yield being about 0*1 per cent. It was yellow in colour, and had an
odour somewhat resembling vetivert. It gave a reddish-violet colour
with ferric chloride, but only contained traces of a phenol, probably
eugenol.
The characters of the oil were as follows :—
Specific gravity . . . . . 0*976
Optical rotation - 10
Ester number 10° 5'
Saponification number (after acetylation) 42
The boiling-point of the oil was very high, indicating the presence of
, sesquiterpene as the chief constituent.
The following figures are the result of fractionation :—
Portion distilling below 275° C. . nil.
280° 2 per cent.
290° 14
300° 42
310° 50
320° 56
325° 68
above 325° 32
PALM/E.
OIL OF SAW PALMETTO.
The fruits of the palm, Sabal serrulata, which is found in the
Southern United States, especially in Florida, have been stated to yield
about 1*2 per cent, of essential oil having the following characters :—
Optical rotation 0°
Refractive index. . . . . . . . . 1*4275
The oil is probably not a true essential oil, but the product of reaction
between the free fatty acids of the fruits and the alcohol in which they
had been kept. According to Shermann and Briggs * the oil contains
free caproic, caprylic, lauric, palmitic, and oleic acids, together with
about 37 per cent, of the ethyl esters of these acids.
OIL OF Coco NUT.
A minute quantity of essential oil is obtained by distillation from
crude fatty oil of coco2 nut, Cocos nucifera.
The otf contains methyl- heptyl - carbonyl, CH3. CH(OH)C7H15,
methyl - nonyl - carbinol, CH3 . CH(OH)C9H19, methyl - heptyl - ketone,
methyl-nonyl-ketone, and methyl-undecyl-ketone.
OIL OF ELÎS GUINEENSIS.
Salway 3 has examined the essential oil of palm kernels, the fruit of
Elais guineensis.
The oil has the following characters :—
^Pharm. Arch., 2 (1899), 101.
*Comptesrendus,
3
150(1910), 1013; 151(1910), 697.
Jour. Chem. Soc. (1917), 407.
* N. O. ABOIDEÊ 89
Specific gravity at-|5° 0*842

Acid value . 3 0
Saponification value 15
Iodine value . 93-2
Apparently portions of the fatty oil were present, having.been me-
chanically carried over during the distillation. The only constituent of
the (Volatile oil identified with certainty was methyl-nonyl ketone.
N. 0. AROIDE>£,
CALAMUS OIL.
This oil is distilled from the rhizome of the sweet flag, Acorus cala-
mus. This plant is a member of a family with aquatic tendencies, and
is probably a native of Asia, although now found largely in Europe.
Although the essential oil obtained from the rhizome is known either
as 01. Acori calami or 01. Calami aromatici, the plant must not, as
Pereira points out, be confused with the Calamus aromaticus described
by Eoyle, which is one of the Andropogon family. The banks of Euro-
pean rivers afford a plentiful supply for the markets, and it is also
-cultivated in damp swamps in India. The fragrance of the plant and
its oil appears to increase as the climate in which it is cultivated is
warmer. Commercial rhizome of European origin is obtainable in the
shops, and occurs as somewhat flattened pieces of about 4 ins. long and
about f of an inch thick. Keeping does not improve it, nor does the
process of decorticating it, as is often done for appearance sake. Many
of the essential oil glands occur in the outer layers of the rhizome, so
that the process of peeling naturally lessens the odour value. Dymock
thus describes the Indian rhizome in his Notes on Indian Drugs : " The
root stock occurs in somewhat tortuous, sub-cylindrical or flattened
pieces, a few inches long and from ^ to 1 in. in greatest diameter.
Each piece is obscurely marked on the upper surface with the scars,
•often hairy, of leaves, and on the under with a zig-zag line of little,
elevated dot-like rings, the scars of roots. The root stock is usually
rough and shrunken, varying in colour from dark brown to orange-
brown, breaking easily with a short, corky fracture, and exhibiting a
pale brown spongy interior. The odour is aromatic and agreeable, the
taste bitterish and pungent." The powdered rhizome is used for sachet
and toilet powder. Dried roots yield from 1/5 to 3*5 per cent, of es-
sential oil, whilst the fresh root yields under 1 per cent. Japanese root
which is possibly that of Acorus spurius yields as much as 5 per cent.
The oils do not quite agree in their chemical properties, and that from
the green rhizome has a finer odour than that from the dried. The
chief difference noticeable is that the oil from green root is more soluble
in weak alcohol than that1from the dried.
According to Eussell all parts of the plant contain oil, the roots
having the largest percentage. The oils obtained by steam distillation
from the aerial portions, rhizome, and roots possess varying physical
-and chemical constants. The results of fractionation of these oils indi-
cate that the components of each are present in varying amounts, also
lihat these components vary to some extent. The plants experimented
1
Jour. Amer. Chem. Soc., 37 (1915), 2387.
with were cultivated at Madison, Wis., U.S.A. The oil distilled fron*
the fresh tops of this material was straw-yellow, with a pleasant cam-
phor-like odour and an aromatic bitter taste : specific gravity O9509 at
23° C.; aD + 12-2°; nD23o 1*5035; acid value nil; ester value 12-6;
acetyl value 53*05. The oil from the rhizomes was reddish-brown ;
the odour aromatic and somewhat camphoraceous, the taste acrid and
bitter : specific gravity 0*9547 at 23° C.; aD + 21*7°; nD23o 1*4990; acid
value 0; ester value 15*3 ; acetyl value 38*4. The root oil was golden-
yellow and had a pleasant camphoraceous odour; specific gravity 0*9491
at 23° C.; aD + 18*7°; raD23o 1*5063, and value 0 ; ester value 23*7; acetyl
value 42. The rhizome oil was soluble in all proportions of ethyl
alcohol 90 and 70 per cent. The herb oil was soluble 1: 5 in ethyl
alcohol with turbidity ; and 1:8 in ethyl alcohol 70 per cent. The root
oil was soluble 1: 6 in ethyl alcohol 90 per cent, and 1: 40 in ethyl
alcohol 70 per cent. None of the oils contained phenols : all indicated
the presence of one or more aldehydic constituents.
In the oil from the fresh tops butyric and oenanthylic acids in the
form of esters were found.
A genuine calamus oil has the following characters :—
Specific gravity 0-958 to 0*970 (rarely 0*950)
Optical rotation + 9° to + 35°
Acid value . 0 „ 3
Ester „ 5 „ 20
The oil is easily soluble in 90 per cent, alcohol.
Kurbatow1 was the first chemist to examine this oil. He found about
5 per cent, of a terpene boiling at 158° to 159°, which was probably
pinene, whose presence has since been confirmed by Semmler and
Spornitz.
Thorns and Beckstroem ? isolated n-heptylic acid, palmitic acid, an.
unrecognised unsaturated acid, eugenol, and asarylic aldehyde. There
is also present a body of the formula C15H26O2 melting at 128°, which
was termed calamus camphor by Schimmel & Co., but has been named
calameone by Thorns and Beckstroem. There are present two hydro-
carbons of the formula C15H22 having the following characters :—
1. 2.
Boiling-point . . . 146° at 19 mm. 151° at 22 mm.
Specific gravity . . . 0*933 at 18° 0-9336 at 12°
„ rotation . . . + 34 '83° - 13*38°
A sesquiterpene of specific gravity 0*931 and boiling at 255° to 258°
is present in the oil in small amount. 3
F. W. Semmler and K. E. Spornitz have recently isolated several
new constituents from this oil. The low-boiling portions (boiling-
point 45° to 50°, 9 mm.; <XD + 59°) contained a-pinene, which was
identified by converting it into the nitrosochloride (melting-point 108°).
In addition to pinene, these chemists succeeded in identifying camphene
by conversion into isoborneol (melting-point 212°). Another fraction
contained camphor (melting-point of the oxime 115°). A fraction with
boiling-point 130° to 135° (12 mm.), after being boiled over sodium,
afforded a sesquiterpene C15H24, calamene, which possessed the following,
1 2
Bericht, 6 (1873), 1210. Ibid., 34 (1901), 1021.
* Ibid., 46 (1913), 3700 ; and Schimmel's Report.
N. O. ABOIDEJE 91
properties : boiling-point 123° to 126° (10*5 mm.); d'^-0 0*9224 ; aD + 5°;

WD 1-50572. By treatment with hydrogen in the presence of platinum
black two double bonds were saturated, giving rise to tetrahydrocala-
mene, C15H28, boiling-point 123° to 125° (10 mm.); dg° 0*8951; aD ± 0°;
% 1-48480.
They also obtained a fraction (boiling-point 150° to 160° at 13 mm.;
d28o 0*9611 ; MD 1*5098) of which the analysis pointed to the presence of
a substance C15H24O. This body appears to be a tertiary alcohol which
readily separates water. Water was invariably eliminated from it, when
it was boiled with acetic anhydride, or treated with phthalic anhydride or
with zinc dust in a sealed tube. When boiled for a short time with con-
centrated formic acid the body C15H24O affords a hydrocarbon, cala-
menene, C15H22, boiling-point 136° to 143° (15 mm.); d~°Q 0*9324; aD + 6° ;
WD 1*52317.
As a result of these investigations Semmler and Spornitz regard it
as highly improbable that the hydrocarbon C15H22 described by Thorns
and Beckstroeml is a natural constituent of calamus oil; they consider
it to have been produced by the splitting-off of water from the body
C15H240.
A sesquiterpene alcohol, C15H24O, of specific gravity 0*9688 at 20°,
optical rotation + 8°, and refractive index 1*5126, was also isolated, but
has not yet been named.
Japanese calamus oil is distilled from the rhizome of the same plant
according to Asahina,2 although Holmes3 considers the plant to be
Acorus spurius.
At all events the Japanese oil differs from that distilled in Europe.
It has the following characters :—
Specific gravity . 0'970 to 0-995
Optical rotation . - 12° + 25°
Refractive index . 1-5095 1-5175
Acid value . . 0 2
Ester „ . 1 10
,, „ (after acetylation) . 16 28
It is soluble in an equal volume of 90 per cent, alcohol.
The Japanese oil appears to be free from terpenes, but it contains
methyl-eugenol.
A calamus oil distilled by Dr. Carthaus in Java has been examined
at the Botanical Institute in Buitenzorg. It possessed the following
constants: d26o 1*06 ; aD + 0° 52'; saponification number 9.
Schimmel & Co.4 have examined two calamus oils from the same
source which behaved very similarly. They had a yellow colour and a,
faint calamus odour. The constants of the one were : d}5o 1*0783 ;
aD + 0° 53'; noD200 1-55043 ; ester number 12 ; of the other : d150 1*0771;
aD + 0° 51'; % 20o 1*55065. The oils here referred to differ from ordinary
calamus oil in their greater specific gravity, their much lower rotation,
and their higher index of refraction. In normal calamus oil these
values range within the following limits: d150 0*96 to 0*97 ; <XD 4- 9° to
4- 35°; wD20o about 1*506. Moreover, the Javanese oils are soluble (with
slight separation of paraffin) in 1 to 1*5 volumes of 70 per cent, alcohol,
while ordinary calamus oil is only soluble in 90 per cent, alcohol (in
almost every proportion).
l 2
Bericht,
46(1913), 3700. Apotheker Zeit., 21 (1906), 987.
3 4
Ph. Jour., iii. 10 (1879), 102. Report, April, 1909, 21.
92 THE CHBMISTKY OF ESSENTIAL OILS
N. 0. LIL1ACE/E.
OIL OF GARLIC.
This oil is distilled from the entire fresh plant Allium sativum. The
average yield of oil, according to Schimmel, is about 1 oz. from 1 cwt.
of the plants, although Wertheim obtained 3 to 4 oz. from this quantity.
The oil is a liquid possessing the characteristic unpleasant odour of gar-
lic, optically inactive, of specific gravity 1*045 to 1*060. It was examined
by Wertheim,1 who stated that it contained allyl sulphide and allyl
oxide. The most modern and2 most trustworthy examination of the oil,
however, is due to Semmler. He states that the garlic yielded 0*009
per cent, of oil of specific gravity 1*0525 at 14*5°. A small quantity of
crystals was deposited when the oil was cooled in a freezing mixture.
The oil contains no oxygen, and therefore no allyl oxide. When frac-
tionated under a pressure of 16 mm., four main fractions were obtained.
Fraction 1 (6 per cent.) consisted of allyl-propyl disulphide, C6H12S2, a
bright yellow oil of specific gravity 1*0231 at 15°, and boiling at 66° to
69° at 16 mm. Its odour is that of onions. Fraction 2 (60 per cent.)
consisted of diallyl disulphide, C6H10S2, a light yellow oil of garlic odour,
much resembling the last-named body, boiling at 78° to 80° at 16 mm.,
and decomposing at 150°. Its specific gravity is 1*0237 at 15°. Frac-
tion 3 (20 per cent.), boiling at 112° to 122° at the same pressure, con-
sisted of a body C6H10S3, the exact constitution of which was not
elucidated. Fraction 4 (10*5 per cent.) boiled above 122° at 16 mm.
pressure. It contained still more sulphur, and corresponded to the
empirical formula C6H10S4. Semmler states that allyl sulphide (C3H5)2S,
does not exist in the oil, as originally stated by Wertheim. Wertheim
also attributes to Beckett and Wright the statement that the oil contains
a sesquiterpene, which he (Semmler) also contradicts. In this, however,
Semmler is in error, as Beckett and Wright3 examined the sesquiterpene
from oil of cloves, which was mistranslated into the Jahresbericht4
as Knoblauchol: hence Semmler's mistake, which is reproduced in
Schimmel's report.5
OIL OF ONION.
Oil of Onion is distilled from the bulb and fresh herb Allium cepa.
The average yield of the plant is 0*05 per cent, of an acrid oil of un-
pleasant odour and of dark brown colour. Its specific gravity is about
1*038 and optical rotation - 3° to - 6°. The oil has been examined by
Semmler,6 who states that he obtained 0*05 per cent, of oil, which con-
tains no oxygen; its specific gravity was 1*041 at 9°, and its optical
rotation - 5°. As it decomposes when boiled under ordinary pressure,
it was fractionated at 10 mm. The chief portion of the oil consisted of
a compound C6H12S2, an oil of specific gravity 1*0234 at 12°, boiling at
75° to 83° at 10 mm. From the higher boiling fractions a substance was
obtained, apparently identical with one of the constituents of oil of
asafcetida. No allyl sulphide was found. The employment of this oil,
which is somewhat disagreeable to manufacture, is quite similar to that
of oil of garlic.
Ânnalen
3
51 (1844), 289. *Arch. Pliarm., 230 (1892), 434.
5
Jour. Chem. Soc., 1876, i. 6. * Jahresbericht, 1878, 398.
6
Report, October, 1893- Arch. Pharm., 230 (1892), 443.
N. O. LILIACEÊ 93
OIL OP HYACINTH.
The perfume of the flowers of Hyacinthus orientalis is usually em-
ployed in the form of an extract or pomade, but an \ essential oil is ob-
tainable from them.
By extracting hyacinth flowers with benzene and distilling off the
solvent under reduced pressure, precipitating the fatty matter with dilute
alcohol, and again concentrating, Spalteholtz and Enklarr,1 obtained
0§016 per cent, of crude oil which, until largely diluted, had a somewhat
unpleasant odour. On washing with dilute alkali sulphuretted hydrogen
was detected. After removing the fatty matter by cooling the petroleum
ether solution to - 20°, filtering and removing the solvent, the oil was
fractionated under reduced pressure. The first fraction contained a
very volatile substance, with a disagreeable odour. In the second frac-
tion an unknown oxygenated body was isolated. The third fraction
contained benzyl benzoate, free benzyl alcohol, and a cinnamic ester.
The benzoic acid liberated from an alkaline solution had an odour of
vanillin. A fluorescent body free from nitrogen was also isolated, which
became red with acids and yellow with alkalies. No esters of anthranilic
or methyl-anthranilic acids were detected. The natural wax present
crystallised from alcohol in colourless flakes, which persistently retained
the odour of the flower.
OIL OF ACAEOID EESIN.

The Australian " grass tree gums " Xanthorrh&a hastilis and Xan-
thorrhwa australis yield essential oils of highly aromatic odour. These
oils smell of storax, tolu, or Peru balsam, and have the following char-
acters :—
Xanthorrhcea hastilis Xanthorrhcea australis
(yellow gum). (red gum).
Specific gravity . . ' 0-937 0-963
Optical rotation . - 3° 14' ± 0°
Acid value . . . 4-9 47-6
Ester „ 69-4 37-5
Both oils contain cinnamic acid and the red gum oil contains styrol.
Eennie, Cooke, and Finlayson2 have investigated the essential oils of
several species of Xanthorrhoea resin. They state that little evidence as
to the species has been forthcoming in previous investigations. The red
resin was obtained from either West or South Australia, and its botanical
source is uncertain. A specimen of the leaves was submitted to Professor
Osborne of Adelaide University, who stated that it would require investi-
gation on the spot to determine whether the leaves belonged to Xanthorr-
h<w tateana (the tree which yields the yellow resin from West and
South Australian trees), or to a variety of that species, or to a different
species altogether. The essential oil distilled from this red resin
amounted to about 0-36 per cent, of the weight of the resin, and was
semi-solid at ordinary temperatures. It was found to consist almost
entirely of paeonol, the peculiar acetophenone derivative found in the
essential oil of Paeonia montan.
The essential oil obtained from the yellow resin, derived from Xan-
thorrhoea tateana, was found to contain paeonol, and a hydroxypaeonol,
1 2
Chem. Weekblad, 1 (1910), 1. Jour. Chem. Soc.t 1920, 338.
having the constitution of 2:4:6-trihydroxy-acetophenone, in which
the position of the methoxy group remains to be determined.
The oil obtained from the West Australian red resin from Xanthorr-
hoza preissii was obtained in a yield of over 1 per cent. It was found
to contain paeonol and hydroxypaeonol, and a crystalline compound
melting at 69'5°, of the formula (probably) C13H12O2. The authors con-
sider this compound to be a methoxydiphenyl ether. A small amount
of laevo-citronellol was also found in the oil.
AMARYLLIDACE/E.
OIL OF TUBEROSE.
The flowers of the tuberose Polianthes tuberosa are cultivated to a
considerable extent in the South of France, and are principally used for
the manufacture of concretes, pomades, and similar perfume materials.
Polianthes tuberosa is a bulbous plant originally derived from
Mexico. It is grown in England under glass for the fragrance of its
white flowers, which is most powerful at night. The tuberous bulbs
are imported from Genoa, and also from North America, but even with
artificial heat the flowers do not develop such a powerful perfume as
in the South of France, where the plants are cultivated in the open air.
In the districts round Grasse the tubers are planted 9 to 12 ins. apart
in rows, with a distance of 2 ft. between the rows. A deep, rich soil is
preferable, as the roots penetrate downwards to a considerable depth
in search of moisture. If the soil is dry the plants require well water-
ing and manuring. Under good cultivation each plant will bear 10 to
12 flowers, or even more. These are picked off as soon as they open,
and the harvesting for the pomade factories commences about the first
week in July and lasts until the middle of October. After that time
the flowers are so deficient in perfume that they are no longer of use
to the manufacturer. In November the roots are taken out of the
ground and packed away in dry sand, ready for planting out in the
following March or April.
The essential oil cannot be separated from the flowers by direct dis-
tillation, as apparently it is decomposed in the process, but the extract
prepared by enfleurage yields a small amount of oil on steam distillation.
The oil, according to Hesse/ has the following characters :—
Optical rotation . - 2° 30' ,, - 3° 45'
Acid value . 22 „ 32-7
Ester „ 224 „ 243
Verley2 isolated from the oil a body of the formula C13H20O which
lie considered to be a ketone and which he named tuberone. Hesse
isolated from the oil the methyl esters of benzoic and anthranilic acids,
the latter being present to the extent of 1*13 per cent. Benzyl benzoate
is also present, as well as free benzyl alcohol. Methyl salicylate was
detected in the oil obtained by distilling the enfleurage pomade oil, but
not in that obtained from the petroleum ether extract of the flowers.
1 2
Bericht, 36 (1903), 1459. Bull. Soc. Chem., iii. 21 (1899), 307.
FIG. 14.—Gathering tuberose at Grasse.
[Rouer-Bertrand Fits.
IRIDEÊ.
OIL OF ORRIS ROOT.
Three species of the Iris are used for the preparation of this oiL
These are (a) Iris germanica, common in the districts near Florence,
and also found in Central Europe, Northern India, and Morocco ; (b)>
Iris pallida, found in Istria, Florence, and Lucca; (c) Iris florentina,
occurring on the Macedonian coast, and near the coasts of the Black
Sea, and also in the neighbourhood of Florence and Lucca. The finest
roots are produced in the Tuscany district, and are known as Florentine
orris root, but it must be remembered that Florentine root is not synony-
mous with the root of Iris florentina, but embraces the three varieties,
which grow to the highest degree of perfection in this district. After
the Tuscany root, the Veronese is most valued. The roots, or more
correctly the rhizomes, exported from Morocco and East India are of
very secondary value, and do not arrive in the market in very good
condition. The plant used to be left entirely to itself to grow wild, but
extensive plantations are now cultivated. The plants are grown on hills,
generally on sunny open spaces, or between rows of vines. A dry cal-
careous soil is most suitable. The plants are left undisturbed for two
or three years, when the harvesting commences. Locally the plants
are known as giaggiolo. The fresh rhizome has very little odour, and
must be carefully dried before being sent away. Certain changes ap-
pear then to set in and the odour develops.
The odour of the dried rhizomes resembles the delicate violet per-
fume, and the powdered substance is a usual constituent of violet powder..
The earlier application of this delicate perfume was in the form of an
alcoholic extract, often known as essence of violets. But non-odorous,
substances are also extracted from the root by alcohol, and the odour is
not so delicate as that of the carefully distilled oil. Pure concrete orris
oil melts at about 40° to 50° and has an acid value between 204 and 236.
Its ester value should not exceed 10. The yield of oil is from -1 to -2:
per cent.; but when the rhizome is treated with dilute sulphuric acid,
the starch granules are broken up and liberate more essential oil, but
the odour is much impaired. The essential oil obtained from the plant
is of a buttery consistence, and contains certain non-volatile fatty bodies
which are carried over mechanically by the steam. Fliickiger, who in-
vestigated this substance, showed that it consisted chiefly of myristic
acid with traces of the true volatile oil. Our present1 knowledge of the
oil, however, is chiefly due to Tiemann and Kriiger. These chemists
obtained the oil by extracting the roots with ether, and steam distilling
the residue left on evaporation. The non-volatile portion contains a
little myristic acid, whilst the volatile oil contains a large amount of
myristic acid and its methyl ester, oleic acid, an oleic ester, oleic alde-
hyde, and a body which is responsible for the characteristic odour which
they termed irone. This body was separated in a pure state by con-
verting it into its phenylhydrazone and decomposing this with dilute
sulphuric acid. Irone C13H20O is an oil almost insoluble in water,
readily soluble in alcohol, etc., boiling at 144° at 16 mm., of specific-
gravity *939 at 20°. It is dextro-rotatory. In the pure form the odour
is sharp and unlike violets, but when diluted it somewhat resembles.
1
Bericht, 26 (1893), 2675.
FIG. 15.—Cultivation of orris in the south-east of France.
Mnderne.
the natural violet flowers. Tiemann and Kruger then attempted to
synthesise irone, believing it to be the odorous principle of the violet
flower (of which so small a yield is obtained as to render an exact ex-
amination almost impossible). Whilst they did not succeed in produc-
ing irone, they obtained an isomeric body, pseudo-ionone, by condensing
citral with acetone, which on heating with dilute sulphuric acid is con-
verted into another isomer, which they termed ionone. This body is
the now well-known artificial violet perfume, so extensively used in the
so-called violet scent and soaps.
Schimmel & Co.1 have isolated from the oil furfurol ; a terpene
which was not identified (specific gravity 0*861 ; rotation + 10° 40') ;
decyl aldeyde ; nonyl aldehyde ; naphthalene (a very rare constituent
of essential oils); and a ketone of the formula C10H18O. They do not
agree with Tiemann and Kruger that oleic aldehyde is present in the
oil.
Commercially, the aspect of orris oil is very important. Its unique
delicate odour will prevent it from being replaced by the more intense
but less delicate odour of ionone, and further, it forms an excellent
" fixer " for this artificial perfume, so that a judicious mixture of orris
oil and ionone leaves little to be desired. Its employment in fine per-
fumery is, and has been for many years, very extensive. A quite liquid
oil, from which the inodorous solid constituents have been removed, is
now on the market. According to Stead it has a specific gravity 0*949,
optical rotation — 28°, and congeals at — 5° C. Schimmel & Co., how-
ever, have shown that its characters are, normally, as follows:—
Refractive index at 20° . . . . . . 1-4950
Acid value 1 to 8
Ester „ 20 „ 40
It is soluble in from 1 to 1*5 volumes of 80 per cent, alcohol.
ZINGIBERACE/E.
OIL OF GINGER.
This oil is the product of distillation of the rhizome of Zingiber offi-
cinale, a native of tropical Asia, which is also cultivated in both East
and West Indies, and in Africa, and to a small extent in Australia.
Possibly, also, it is found in China, although the greater part of the
" Chinese ginger " appears to be the product of Alpinia Galanga.
The rhizomes are sometimes imported in the soft juicy condition
known as " green ginger," but the ordinary ginger of commerce consists
of the dried rhizomes which have been picked when the stalks have
withered, and are either washed, dried and scraped (uncoated or white
ginger), or merely washed and dried (coated ginger). Sometimes it is
bleached or limed before sale. The gingers of commerce are of widely
different value, according to their place of origin, and the aroma and
value of the oil naturally depend to some extent upon this. The
Jamaica product is most highly valued. The oil, which is obtained to
the extent of about 2 to 3 per cent., is a pale yellow to dark yellow
liquid of characteristic aromatic odour, but lacking the pungency of the
rhizome.
1
ZINGIBEBACEJE 99
Specific gravity 0-8740 to -886
Optical rotation - 25° - 50°
Eefractive index 1-4885 1-4950
Acid value . . . . . . . . . 0 2
Ester „ 1 15
,, , , (after acetylation) . . . . . . 30 45
l
Abnormal ginger oils are from time to time to be found. Bacon
reports on a sample distilled in the Philippines, having an optical rota-
tion of + 5*9°, and a Japanese oil has been found having a specific
.gravity 0*894 and an optical rotation + 9° 40'. A Java oil has been re-
corded 2 with a rotation of + 13° 9'. Thresh has fractionally distilled a
specimen of this oil prepared in England from the dried root, and ob-
tained the following results :—
Below 150°. 5 per cent.
150° to 200° 10
200° „ 240°
240° „ 265° 60
265° „ 300° 7
Residue 10
These results, however, must be accepted with reserve, as the oil
undergoes decomposition by distillation at ordinary pressure. The
fraction obtained at 155° to 165° is usually dextro-rotatory.
Dextro-camphene and /2-phellandrene constitute the bulk of the ter-
penes present in the oil. Cineol, citral, and borneol have been identified,
with possibly traces of geraniol. Van Soden and Kojahn 3 have isolated
;a sesquiterpene which they have named zingiberene. This body has a
specific gravity 0*872, optical rotation - 69°, and boils at 269° to 270°.
Dodge 4 has isolated a small5 quantity of an aldehyde, which appears
to be decyl aldehyde. Brooks has identified methyl-heptenone, nonyl
aldehyde, linalol, acetic and caprylic esters, a phenol (chavicol ?), and a
•sesquiterpene alcohol having the characteristic odour of the oil. This
body C15H26O, which has been termed zingiberol, boils at 154° to 157° at
14*5 mm. pressure.
OIL OF GALANGAL.
This oil is obtained from the rhizome of Alpinia officinarum, a plant
•cultivated in China and Siam. The oil is obtained by moistening the
ground rhizomes with water, and after some hours distilling them with
steam. The oil is of a greenish-yellow colour, with a sharp taste and
pungent camphoraceous odour. The yield is from *5 to 1*5 per cent.
"The oil has the following characters :—
Refractive index 1-4760 1*4825
Acid value 0 2
Ester ,, 6 15
„ , , (after acetylation) . . . . 40 50
The constituents of galangal oil so far identified, are cineol, d-a-
pinene, cadinene, together with the following compounds described by
1
Philipp. Jour., Sci.t 5 (1910), 259.
iJaarb. dep. Landb. Ned. Ind. Batavia (1912), 57.
zpjiarm. Zeit., 45 (1900), 414. 4 chem. Zeit., 34 (1912), 1217.
5
Jour. Amer. Chem. Sos., 38 (1916), 430.
Fromm and Fluck.1 These chemists isolated a small fraction of from
1 to 2 per cent, boiling at 208° to 210°, which consisted mainly of an
oxygenated compound of the formula C10H16O, the exact nature of which
is undetermined. Two sesquiterpenes were separated, one boiling at
138° to 140° at 12 to 15 mm., and the other yielding a dihydrochloride
identical in melting-point with that of cadinene. But when mixed with
pure cadinene dihydrochloride, a depression of 10° in the melting-point
results, so that the sesquiterpene is not cadinene. From the highest
boiling residues, a sesquiterpene hydrate C15H26O melting at 167° was
separated. Eugenol, which has been stated to be present by Horst,
could not be found.
According to Dragendorff, the oil should not be quite soluble in an
equal volume of 85 to 90 per cent, alcohol. He states that the chief
adulterants are oils of pimento and cloves, which are much more soluble
in alcohol. The ready solubility of samples of oil in all proportions of
80 per cent, alcohol is, therefore, probably indicative of adulteration.
Oil of lemon and turpentine have also been used to sophisticate the pure
oil. These will be indicated by the lowering of the specific gravity and
the alteration in the optical rotation.
A galangal oil has also been distilled from Alpinia Galanga and has
been examined by Ult6e.2 The oil has the following characters :—
Specific gravity . . . . 0-974 t o 0-985
Acid value I to 2
Ester „ 145
It contains about 50 per cent, of methyl cinnamate and 20 to 30 per
cent, of cineol. Pinene is also present.
OIL OF ALPINIA ALBA.
3
Pickles and Earl have made an examination of the essential oil
distilled from the fruit of this plant which is also known as Amomum
medium. They find that the oil resides almost entirely in the seeds.
By distilling the fruits with steam, about 1 per cent, of a pale yellow
oil, having an odour recalling those of lemon and eucalyptus, was ob-
tained. The oil has the following characters :—
The oil was shaken, first with dilute sodium carbonate, next with
sodium hydrogen sulphite solution, then with dilute sodium hydroxide,
and finally with 50 per cent, resorcinol solution to absorb cineol. From
the results of this treatment and the subsequent examination of the
various products, the composition of the oil was found to be approxi-
mately as follows: Cineol, 69 per cent., characterised by the crystal-
line additive product with iodol; aldehydes and ketones, 27*5 per cent.,
consisting mainly of citral, which was characterised by means of the
semi-carbazone and the /J-naphthacinchoninic acid ; phenols, 1'5 per
cent.; acids, 1 per cent. A small quantity of crystalline acid, melting-
point, 46° to 48° was isolated, but not in sufficient quantity for identifi-
cation. The residue, amounting to about 1 per cent., seemed, from its
odour, to consist chiefly of terpenes.
1 2
Annalen, 405 (1914),3 175. Schimmel's Bericht, April, 1911, 19.
Proc. Chem. Soc. (415), 164.
ZINGIBEKACE^S 101
OIL OF ALPINIA GALANGA.
The rhizome and roots of Alpinia galanga yield 0*04 per cent, of
essential oil having the following characters :—
Acid value 1-8
Ester „ 145-6
The oil contains about 50 per cent, of methyl cinnamate, and 20 to
30 per cent, of eucalyptol. Camphor and d-pinene are also present.
OIL OP ALPINIA MALACCENSIS.
The fresh roots of Alpinia malaccensis yield, according to Schimmel
<fc*Co., about 0*25 per cent, of essential oil having the following char-
acters :—
Specific gravity 1-039 to 1-047 at 27°
Optical rotation . + 0° 15' to + 1° 30'
Solidifying-point 25-5°
Saponification value 256 to 278-5
It contains methyl cinnamate.
The leaves also yield an oil which has been examined by van Bom-
burgh,1 who obtained 0*16 per cent, from the fresh leaves. The oil has
Optical rotation , . + 6° 5'
It contains a-pinene, and about 75 per cent, of methyl cinnamate.
OIL OF ALPINIA NUTANS.
The root of this plant yields an essential oil having a specific gravity
0-950 at 29°. It distils principally at a temperature below 230°. The
higher boiling fractions contain an ester of (probably) cinnamic acid.
The oil from the leaves has recently been examined by Kafuku 2 who
obtained 0*053 per cent. It had the following characters :—
Optical rotation + 38*4°
It contains 30 per cent, of d-camphor, 17 per cent, of d-camphene,
cineol, an ester of cinnamic acid, a sesquiterpene, a high boiling
phenol, and probably limonene.
OIL OF CARDAMOMS.
The oils from different kinds of cardamoms, although similar in
general properties, differ to a certain extent chemically. The seeds from
which the oil is distilled are chiefly exported from South-West India
and Ceylon in their pericarps, forming the cardamoms of commerce.
The following description 3 of the principal characters of the more
important varieties of cardamoms is of interest:—
" Mysores.—Divided into rounds and longs. The former are what
1
2
Kon. Akad. Weten. Ammerdam (1898), 550.
3
J. Chem. Ind. Tokyo, 20 (1917),
349.
Chemist and Druggist Diary, 1899, 500.
ZINGIBERACE^ 103
the B.P. calls * ovoid'; they vary in length from £ in. to | in. (the
latter 1 in 10), and have a smooth pericarp of a cream colour, due to
the use of bleaching agents. Their quality is judged by their weight.
Sometimes the seeds are shrivelled (unripe), so that the fruit is husky.
This is not so frequent in the longs, which are simply thinner than the
rounds, and are not so smooth on the surface, nor so pale, as a rule.
The B.P. description, 'longitudinally striated,' might exclude most of
the rounds, as they look smooth until closely examined.
" Malabars.—These are smaller than Mysores, and there is a greater
proportion of seed to pericarp in them. They are fat pods, with a pointed
apex. Generally pale brown or pink and longitudinally striated. Barely
more than £ in. long. They have a full flavour.
" Mangalores.—These are almost globular in shape and not unlike
Malabars. All three are washed or bleached before exportation.
" Seeds.—A goodly proportion of cardamoms come straight into the
market freed from their pericarps. The B.P. excludes these because
they are supposed to lose flavour on keeping. Wholesalers and large
manufacturers use them when fresh ; fine brown seed is as strong as
the kind just freed from the pericarps. Grey seeds are inferior."
It is fairly certain that the plant Elettaria cardamomum produces
most of the ordinary cardamoms, whilst the u Ceylon wilds" are the
product of a variety of this plant, known as variety /3. The majority
of the cardamoms of commerce are imported from Ceylon, and may be
described as Ceylon-Malabars or Ceylon-My sores, according as they fit
in with the above descriptions. The Ceylon wilds are mostly consumed
in the manufacture of a certain cake made in South Germany, and are
not an ordinary article of commerce. Some confusion exists as to the
botanical characters of some of these seeds, and more so as to the es-
sential oils they yield. The oil is usually distilled from Ceylon seeds,
which yield from 3*to 6 per cent, of oil. According to Schimmel, the
oil derived entirely from Malabar cardamoms (Elettaria cardamomum)
is obtained to the extent of from 4 to 8 per cent, of the seeds used. Its
specific gravity was '943 and its optical rotation + 34° 52'. It dissolved
in 4 parts of 70 per cent, alcohol. It was found to require 13*2 per
cent, of potash for saponification, thus indicating a very high ester con-
tent. Haensel gives the specific gravity as 0*933 and the optical rota-
tion as + 26°. Samples of oil distilled from both Malabar and Mysore
(Ceylon) seeds, obtained from authentic sources by the author, showed
that there was practically no difference between the two oils, although
Schimmel states that Ceylon cardamom oil has a specific gravity of
•895 to *910 and a rotation of + 12° to + 13°. It is probable that the
oil from the so-called Ceylon wild cardamoms is here meant.
The Ceylon-Malabar seeds distilled by the author yielded 1*3 per
cent, of oil, and the Ceylon-Mysores 2*6 per cent. Both were bright
yellow liquids, whose odours were scarcely distinguishable. The specific
gravities and optical rotations were as follows :—
Specific Gravity Optical Rotation

at 15-5°. at 16°
(100 mm. Tube).
Oil of Malabar Cardamoms 0-9418 + 40° 41'

Oil of Mysore Cardamoms 0-9418 + 46° 39'
These figures are in fair agreement with those given for Malabar
oil, but in no way resemble those quoted by Schimmel for Ceylon oil,
which are difficult to understand.
The oils were soluble with a slight opacity in 40 to 45 volumes of
60 per cent, alcohol.
Little difference exists between the two oils. On distillation at
ordinary pressure the oil, which is very rich in esters, in both cases
decomposes partially, and a considerable quantity of free acid distils
over. According to Weber (Annalen, 238, 89), formic and acetic acids
are found in the distillate. Acetic acid is undoubtedly the chief acid
constituent of the esters, but the author is unable to confirm the pre-
sence of formic acid. If it is present, it is only in faint traces. On
distillation under reduced pressure the earlier fractions (the boiling-
point rises gradually until 50 per cent, has distilled over) contain
cineol, but only to the extent of 5 to 10 per cent, of the oil. This
figure is the result of an approximate estimation by means of phos-
phoric acid.
The following figures may be taken as covering most pure samples :—
Specific gravity 0'923 to 0'945
Acid value 1 „4
Ester „ 90 „ 150
The oil contains a considerable amount of terpinyl acetate (and
therefore requires at least two hours for complete saponification). The
terpineol was identified as rf-a-terpineol by Schimmel & Co.1 The ter-
pene terpinene has been stated to be present, but this is not confirmed
by the author, nor by Schimmel & Co. Limonene is probably present
in small amount. Free terpineol is also present.
The oil distilled from the Ceylon wild cardamoms, Elettaria carda-
momum /?, has the following characters :—
Acid value 1 „3
Ester , 25 „ 75
This oil contains terpinene, sabinene, terpineol and its esters, and a
solid crystalline substance melting at 60° to 61°.
Siamese cardamom oil is distilled from the seeds of Amomum carda-
momum, which are known on the market as camphor seeds on account
of their camphor-like odour. Schimmel obtained 2*4 percent., which
was semi-solid at the ordinary temperature, and had an odour of cam-
phor and borneol. In order to liquefy the oil it was necessary to warm
it to 42°. Its specific gravity at this temperature was '905, and its
optical rotation + 38° 4'. It required T88 per cent, of KOH to sap-
onify the esters present, and contained alcohols equivalent to 22-5 per
cent, of borneol. It was soluble in 1-2 volumes of 80 per cent, alcohol.
From 800 grms. of the oil 100 grms. of the solid compounds were ob-
tained by centrifugal action. These were examined and found to con-
sist of about equal parts of dextro-borneol and dextro-camphor.
Kameroon cardamom oil is obtained from fruits which are identical
with the Madagascar cardamoms. They are derived from Amomum
1
Bericht, October, 1897, 9.
ZINGIBEBACEÊ 105
-danielli. The yield of oil was 2*33 per cent., its specific gravity was
-907 and its optical rotation - 20° 34'. The oil is soluble in 7 to 8
parts of 80 per cent, alcohol. It contains cineol and possesses an odour
which prevents its being employed as a substitute for the ordinary oil.
Bengal cardamom oil is obtained from Amomum aromaticum, which
yields about 1 to T2 per cent, of oil having a specific gravity 0-920 and
optical rotation - 13°. This oil contains a large quantity of cineol.
The seeds of Amomum Melegueta, one of the Zingiberacese indigenous
to tropical West Africa, yield the so-called "grains of paradise" oil.
which is obtained to the extent of 0*3 to 0'75 per cent. The oil has
«, specific gravity about 0'894 and optical rotation about - 4°. It is
not clearly soluble in 90 per cent, alcohol. Schimmel & Co.1 have dis-
tilled a sample, which was found to have the following characters:—
Its ester value was 41*2, and ester value after acetylation 63'9.
Schimmel & Co. 2 have examined the oil obtained from cardamom
roots from Indo-China. They obtained 0'64 per cent, of oil having the
following characters : îr,o0'9066; ao - 32° 57'; ^020° 1'48151; acid value
3'7; ester value 87'9; ester value after acetylation 96'7. The oil was
soluble in 0'5 volumes of 95 per cent, alcohol; when more alcohol was
added the mixture rapidly turned turbid, and did not .become clear
again until the solvent had been increased to 4 volumes. Fractional dis-
tillation under diminished pressure (5 mm.) gave the following result:—
1. to 35° 5-4 per cent. «D - 0° 10'
2. 35° „ 40° 8-7 «D - 0° 32'
3. 40° ,, 100° 5-4 «D - 17° 5'
4. 100° ,, 110° 10-6 «D - 31° 10'
5. 110° ,, 115° 44-2 «D - 45°
6. 115° „ 145° 6-4 aD - 33° 14'
7. residue 19-3 „ «D - 39° 15'
Fractions 1 and 2 contained cineol, which was identified from the
•double compound it gave with resorcinol. From fractions 4 and 5 a
portion boiling between 117° and 120° (5 mm.) was separated by re-
peated fractionation. Saturated with hydrochloric acid gas in dry
ethereal solution at - 18°, this fraction yielded a hydrogen chloride
•compound which, when recrystallised from methyl alcohol, had melting-
point 79° to 80°. The hydrochloride was inactive; the chlorine-deter-
mination gave the following result:—
0-4306 subst. : 0*5928 g. AgCl
Cl Found Calc. for C15H24, 3HC1.
34*06 per cent. 33'9 per cent.
The probability of this body being bisabolene hydrochloride was
•confirmed by further examination. With sodium acetate and glacial
acetic acid a sesquiterpene was eliminated from it which, when twice
fractionated, was found to possess the following constants : 265° to 267°
(757 mm.); d^ 0-8748 ; aD ± 0°; nm& 1-49063. With hydrochloric acid
this hydrocarbon yielded again the trihydrochloride melting between
79° and 80°.
The residue of distillation of cardamom-root oil solidified at about
l 2
Re1)ortJ October, 1914, 32. I6id., 1911, 105.
15° with separation of paraffin; the last-named body, when recrystal-
lised from alcohol, melted at 62° to 63°.
Korarima cardamom oil is the product of Amomum Korarima, the
yield of oil being from 1 to 2 per cent. It has the following char-
acters :—
Optical rotation - 3° to - 7°
Acid value . . . . . . . . . . 3 „5
Ester ,, 22 „ 50
Oil of Aframomum angitstifolium (Amomum angustifolium) is an
oil obtained from the seed of a species of cardamoms indigenous to-
(German) East Africa from which Schimmel & Co. obtained 4*5 per
cent, of a colourless oil possessing the following characters : d\& 0*9017 ;.
ao — 16° 50'; %D2o° 1*46911; acid value 0*4; ester value 4*2; soluble in
6 volumes of 80 per cent, alcohol. So far as aroma is concerned it
cannot compare with Ceylon cardamom oil, and owing to its high
cineol-content it resembles cajuput oil. Unfortunately, the quantity
of oil was too small to enable its composition to be determined with
any exactitude. Botanical examination of the entire fruit showed that
the seed was derived from Aframomum angustifolium K. Schum., a
plant which occurs also in Madagascar and in the Seychelles Islands.
The wild cardamoms of Indo-China, derived from Amomum globo-
rum, yield about 4 per cent, of essential oil having the following char-
acters :—
Optical rotation . + 43° 54'
Acid value 0-8
Ester „ 128-4
The oil probably contains camphor.
The leaves, roots, and stalks of Amomum Walang (Ackasma Walang)-
yield essential oils, wrhich have been examined.1 They have the fol-
Oil from Leaves. Oil from Oil from

Stalks. Roots.
Specific Gravity at 16° 0-850 0-860 0-856

Optical Rotation . - 0° 34' - 0° 58' - 0° 30'
Acid Value . 10-1 26 18-9
Saponification Value . 70 75-6 70
Sap. Value after Acetylation 285-6 285-6
Aldehyde-content (Sulphite Method) 97 per cent. 96 p. cent. 96 p. cent.
Oil-yield from Green Material 0-25 „ 0*2 0-15 „
OIL OF TURMERIC.
Turmeric oil is distilled from the roots of Curcuma longa, one of the-
Zingiberaceae indigenous to India, and cultivated also in China and
Southern Asia, etc. The oil, which is not of commercial importance,.
is obtained to the extent of about 5 per cent, as a thick yellow oil having
1
Jaarb. dep. Landh. Ned. Ind. Batavia (1911), 45,
ZINGIBEEACE^ 107
Optical rotation - 25° „ + 35°
Acid value . . . . . . . . . 1/5 , , 3*5
Ester „ 8 „ 16
Bacon l has examined an oil distilled in the Philippines and found it
to have a specific gravity 0*930 (at ~); optical rotation + 8*6°; refrac^
tive index 1-5030; and ester value 81.
According to Jackson and Menke 2 it is separable by fractional dis-
tillation under a pressure of 60 mm. into three portions, the first boiling
below 193°, the second from 193° to 198°, and the third forming a semi-
solid residue. The chief ingredient was the fraction 193° to 198° which
consisted of a nearly pure alcohol, a pale yellow oil with an aromatic
smell, of specific gravity 0*956 at ~, and optical activity [O]D = + 24-58°.
At ordinary pressure it boils at 285° to 290°. It appears to be an alcohol
of the formula C18H18O or CUH20O, which has been called turmerol.
Valeric and caproic acids have also been isolated. According to Suida,
the principal ingredient is a body isomeric with carvone, C10HUO, but
this is probably incorrect. The terpene phellandrene has been found in
the oil.
The most recent work on this oil is that of Luksch,3 who isolated
from it a ketone, curcumone C13H18O, probably isomeric with turmerol,
It is a colourless oil of sharp ginger-like taste, having a specific gravity
0*9566 at 20°, optical rotation + 80'55°, and refractive index 1'50526.
It boils at 119° to 122° at 8 to 11 mm. Its oxime boils at 159° and its
phenylhydrazone melts at 92°.
OIL OF ZEDOARY.
The roots of Curcuma Zedoaria yield from 1 to 1*5 per cent, of an
Optical rotation + 8° + 18°
Acid value . 0 2'5
Ester 15 25
(after acetylation) 55
It is soluble in 1-5 to 2 volumes of 80 per cent, alcohol.
Cineol has been identified as a constituent of this oil, and Bacon 4
has isolated a sesquiterpene alcohol, which forms crystals melting at
67°. It is optically inactive and has a specific gravity 1*010 at j^.
OlL OF KÊMPFERIA GALANGA.

The roots of Kcempferia Galanga yield an essential oil having a>
specific gravity about 1-025, optical rotation - 16°, and refractive index
1*5428. It contains the ethyl ester of jp-methoxy-cinnamic acid melting
at 50°, and the ethyl ester of cinnamic acid. It also contains penta-
decane. The roots of Kcempferia rotunda yield 0-2 per cent, of an oil
of specific gravity 0-890 to 0'900, and optical rotation about + 12°. It
contains cineol.
l 2
Philipp. Jour. Sci., 5 (1910), 262. 4
Amer. Chem. Jour., 4 (1882) 368.
*Inaug. Dissert. Basle, 1906. Philipp. Jour. Sci., 5 (1910), 261.
OIL OF K^JMPFEBIA ETHELS.
The oil distilled from the tubers of Kampferia ethela has been
examined by Goulding and Roberts,1 who obtained a total yield of 1'5
per cent., equivalent to 2-0 per cent, on the dry material. The plant
grows in large quantities in the extreme north-east of the Trans-
vaal, and could easily be cultivated. The oil has the following
characters:—
Optical rotation + 19° 47' „ + 30-4°
Acid value . 1-0 „ 2-3
Ester 5 „ 11-5
(after acetylation) 33-6 „ 47-6
The oil is of pale yellowish-brown colour, having a rather pleasant
odour somewhat resembling that of orange flower oil, combined with a
less agreeable smell, recalling that of crushed ivy leaves. On fractional
distillation under low pressure in an atmosphere of carbon dioxide two
fractions were obtained: (1) (42 per cent.) distilling at 160° to 195°;
specific gravity -901; optical rotation - 4° 30'. (2) (25 per cent.) dis-
tilling at 195° to 270°; specific gravity -988; optical rotation + 26° 30'.
The residue (33 per cent.) deposited colourless crystals amounting to
about 8 per cent, of the original oil. The first fraction consisted chiefly
of terpenes and cineol. Dipentene was identified by means of the tetra-
bromide (melting-point 124°), and cineol by its iodol additive compound
(melting-point 112°). An estimation of the cineol by the resorcin
method showed that fraction 1 contained 44 per cent., equivalent to
18'5 per cent, of the original oil. Acetic acid was found to be present,
together with a phenolic body having a creosote-like odour, amounting
to 0*6 per cent, of the'original oil. From the second fraction linalol
was isolated and identified by conversion into citrylidene-cyanoacetic
acid, melting at 120° to 121°. A small quantity of methylanthranilic
acid was also separated, melting at 179°, probably present in the form
of its methyl ester. The crystalline substance separated from the por-
tion boiling above 270°, after repeated crystallisation from alcohol, had
a melting-point of 102° and optical rotation + 198° 20' in chloroform
solution. In dilute alcoholic solution it possesses the characteristic
odour resembling crushed ivy leaves, which was noticed in the oil
itself. It is highly unsaturated, and readily combines with about twice
its weight of bromine. It forms a hydroxylamine-oxime melting atC
184°, an oxime melting at 166°, and a benzoyl derivative melting at 260
with decomposition. The heavy portion of the oil, amounting to 7 per
cent., appeared to consist of a solution of the ketone compound in liquid
constituents of high boiling-point, probably sesquiterpenes. The com-
position of the oil is summarised as follows :—
Per Cent.
Terpenes (dipentenes a n d probably pinene) . . . . . 21'8
Cineol 17'2
Ketonic compound (melting-point 102°) . 13-0
Alcohols (including linalol) 11-2
Esters (chiefly methyl methyl-anthranilate) 1-3
Phenols 0-5
Acids (chiefly or entirely acetic acid) 0*1
ae (probably chiefly sesquiterpe:
Residue sesquiterpene) 34-9
l
Jour. Chem. Soc. (1915), 314.
PIPEEACEÊ 109
PIPERACE/E,
CUBEB OIL.
This oil, which is official in the British Pharmacopoeia, is distilled
from the fruit of Piper cubeba (Cubeba officinalis Miq.). The cubebs
of commerce are the dried unripe fruits, which resemble ordinary black
pepper in appearance, except that they are rather lighter in colour;
they are chiefly imported from Batavia and Singapore.
The berries are coarsely ground and distilled with steam, yielding
from 10 to 18 per cent, of volatile oil. This is of a faint greenish or
greenish-blue colour, and of very characteristic and somewhat aromatic
odour. The colour has been stated to be due to copper, but this is
erroneous, as the higher fractions contain a blue oil in greater or less-
quantity, which determines the tint of the liquid.
The characters of normal cubeb oil are as follows :—
Specific gravity at 15° . 0-912 to 0-930
Optical rotation . - 25° „ - 42°
The solubility in 90 per cent, alcohol is very variable, some samples re-
quiring only 1 to 2 volumes, others up to 10 volumes, to effect solution.
A fractional distillation of the oil yields valuable results, from 65 to
80 per cent, distilling between 250° and 280°. Four pure samples ex-
amined in this manner by Messrs. Oranje l gave the following results :—
i.
Yield, 14 per cent. oil.
Specific gravity (15°), 0*9268 ; optical rotation - 33-70°.
Fractionation of 50 grms. :—
Below 250° . O'O grms. = O'O per cent. Below 250°.
250° to 260° 11-7 „ = 23-4 „ j
260° „ 270° 26-8 „ = 53-6 „ V 250° to 280°
270° „ 280° 4-7 „ = 9*4 „ J
Residue . 6-8 „ = 13'6 „ Residue
50-0 100-0 100-0
2.
Yield, 9-5 per cent. oil.
Specific gravity (15°), 0-9258 ; optical rotation - 27-40°.
Fractionation of 40 grms.:—
Below 250° . O'O grms. = 0-0 per cent. Below 250°. 0*0 per cent.
250°. to 260° 10-9 „ = 27-3
260° „ 270° 15-8 „ = 39'5 250 to 280° . 82-8 „
270° „ 280° 6-4 ., = 16*0
Residue . 6'9 „ = 17'2 Residue 17-2 „
40-0 100-0 100-0
3.
Yield, 15-0 per cent. oil.
Specific gravity (15°), 0-9226; optical rotation - 34-60°
Fractionation of 50 grms.:-
Below 230° 0'Ogrms. =
230° to 240° Below 250°. 18*0 per cent.
240° „ 250° 5-0
250° „ 260° 27-4
260° „ 270° 7-0 250° to 280° 72-2 „
270° ,,280° 1*7
Residue 4*9 Residue 9-8 „
50-0 100-0 100-0
J
P. and E.O.R. (1914), 372.
4.
Yield, 14'0 per cent. oil.
Specific gravity (15°), 0-9233 ; optical rotation - 37'60°.
Fractionation of 50 grms. :—
Below 220° O'O grms. = O'O per cent. ^
220° to 230° 2-3 4-6 [
V Below 250°. 12'8 per cent.
230° „ 240° 1-5 3-0
240° „ 250° 2-6 5-2
•250° „ 260° 20-3 40-6
260° „ 270° 15-5 31-0 250° to 280° . 79-0 „
270° „ 280° 3-7 7'4
Residue 4-1 8-2 Residue. 8-2 „
50-0 lOO'O 100-0

The chemistry of this oil is in need of further elucidation, as it is
<ilear that there are several constituents present which have, so far,
escaped identification. The terpene dipentene is present, and probably
small quantities of pinene or camphene; cadinene is present, as well as
a second sesquiterpene not yet identified. There is also present, es-
pecially in the oil distilled from old fruit, which has doubtless become
partially oxidised, a small amount of the so-called cubeb-camphor.
'This body, C15H25OH, appears to be a crystalline sesquiterpene alcohol
derived from the sesquiterpenes (or one of them) by oxidation. From1
a mixture of ether and alcohol it crystallises in rhombs, melting at 65°
and is laevo-rotatory. It boils at 248°, with decomposition. The nature
of the blue oil found in2 the higher fractions is unknown.
Umney and Potter have reported on some " false cubebs," the fruit
of an unknown species of pepper. These false cubebs may, and ap-
parently do, find their way into commerce, and if distilled with genuine
•cubebs produce a quite abnormal oil. The oil from these false cubebs
has a specific gravity about 0-894 and an optical rotation + 16°. The
following results were obtained on fractional distillation, and are com-
pared with those of a genuine oil under identical conditions :—
FRACTIONATION.
False Cubeb Oil. Pure Cubeb Oil.
1
Below 160° . 12 per cent. _
160° to 170° 8 —
170° 180° 20 —
180° 190° 6
190° 200° 4 Below 200° . . 5 per cent. only.
200° 230° 8 200° to 230° . 11
230° 240° 2 230° „ 240° . 3
240° 250° 4 240° „ 250° . 15
250° 260° 6 250° „ 255° . 31
260° 270° 10 255° „ 257° . 25
The t'ractionation figures, gravity, and optical rotation indicate that

this oil has an entirely different composition from that of normal cubeb
oil. The oil has been further investigated as regards its ester and
alcohol values which are :—
1
Schmidt, Arch, der Pharm., 191 (1870*, 23 ; Schaer and Wyss, Arch, der Pharm.,
206 (1875), 316, give 67°; and Winckler, Annalen, 8 (1833), 203, gives 70°.
2 P. and E.O.B. (1912), 64.
PIPEKACE.E 111
Esters None
Alcohols . . Saponification number after acetylation 56-1
As a result of their observations on these essential oils they come to
the conclusion that certain of the abnormal oils of commerce have been
produced from mixtures of the genuine berries with either this hitherto
unidentified one which has been described, or possibly another variety.
It is perfectly clear that a mixture of one part of the normal cubebs
with one part of this variety would yield an oil having approximately
the characters which have been found in these abnormal oils, namely,
-a rotation of - 15° or - 16° and a specific gravity of about 0*910. It
must not be forgotten that, in taking a mixture in equal parts of the
two fruits, the yield of essential oil of the genuine is practically twice
• as much as that of the substitution fruit.
A sample of false cubeb oil examined in the laboratory of Evans
Sons, Lescher & Webb, Ltd.,1 had the following characters :—
Specific gravity. . . . . . . . . . 0*916
Kefractive index . . . + '4921
On fractionation it behaved as follows (sample a) compared with
two pure oils (b and c) :—
VACUUM-DISTILLED FRACTIONS OF CUBEB OILS.
Fraction. Optical Rotation. Boiling-Point. Refractive Specific

Index. Gravity.
^ , . r + 27° 20' 52° to 59° 1-4675 0-854

5 per
* I 6 I cent J - 31° 5' 57° „ 69° 1-465 0-851
£-5 J|w(a\J -\ * t
f
- 35° 47'
+ 24° 30'
53° „ 109°
to 63°
1-4735
1-469
0-868
1 - 37° „ 86° 1-47 0-855

ce
S. 1 (§ f "t ( - 29° „ 129° 1-485
•^
(a) ^ f +10° ! „ 89° 1-4753
J - 32° 122° 1-49 0-9078
•s
33
(c) J cent
1
c
- 26° 30'
- 20° 20'
133°
119°
1-496
1-4953 0-918
fl
g] 20 per I - 31° 40' 127-5° 1-4957 0-9198
1
(c) J 1 - 25° 40' 139-5° 1-498 0-930
r - 20° 5' 126° 1-5005
0 ' <"> I 10 P^ J - 32° 30' 130° 1-4965 0-927
) / f cent. 1 - 24° 45' 140-5° 1-4993
1 (a) \ 40 per ( - 18° over 126° 1-5041
(6) [- cent, \ - 30° 30' „ 130° 1-498 0-9438
(c) J (residual) 1 - 26° 20' „ 140-5° 1-5012
The following investigation, which was carried out by Dr. J. Dek-

ker,2 Director of the Colonial Museum at Haarlem, throws considerable
light on the question of the abnormalities observed in certain oils of
cubeb.
In a quantity of 500 grms. of cubebs were principally found four
-different kinds of fruit, which have been sorted out and classified as
follows :—
Class 1.—Keal cubebs, i.e. those showing both macroscopically and
microscopically the features of piper-cubebs, producing, if brought into
.touch with concentrated sulphuric acid, the well-known red colouring.
1 2
Evans' Annual Report (1913), 29. P. and E.O.E. (1913), 89.
Class 2.—Much resembling real cubebs, but outwardly shrivelled,,
with longer and broader tail than of real cubebs.
This kind produced, with concentrated sulphuric acid, a yellow
colouring.
Class 3.—Not resembling real cubebs at all—without tail and show-
ing a totally irregular microscopic figure—colouring yellow with con-
centrated sulphuric acid.
Class 4.—Much resembling the real cubebs, but larger and with a
different design of the net-work. With concentrated sulphuric acid
colouring yellow.
In order to check the assortment, 100 fruits of the No. 1 class have
been treated with concentrated sulphuric acid one by one ; it then ap-
peared that 98 gave a red and 2 a yellow colouring. These two proved
to belong to the No. 2 class, and have been taken out, so that at last it
could be accepted that the Class No. 1 consisted of real cubebs exclu-
sively.
The various isolated kinds have then been distilled, and also the
branches and the original (unassorted) sample :—
Original Sample.
Production of oil . 14*44 per cent,
Colour of oil light; green
Refraction 15° 0. . 1-4955
Optical rotation 15° C. - 29-12 (length of tube 10 cm.)
Specific gravity 15° C. . 0-922
2. Branches of Original Sample.
Production of oil. . . 1-67 per cent.
Colour of oil . dark green
Refraction 15° C. . . 1-5011
Specific gravity 15° C. 0-938
3. Assortment of Same Sample.—Class 1.
Production of oil . 17-78 per cent,
Colour of oil. light blue-green
Refraction 15° C. 1-4964
Specific gravity 15° C. 0-924
4. Assortment of Same Sample, Broad-tailed.—Class 2.
Production of oil . . . . 11-56 per cent.
Colour of oil yellow-green
Refraction 15° C 1-4928
Rotation 15° C. . . . . . - 11-24 (length of tube 10 cm.)
Specific gravity 1 5 ° C . . . . 0-912
5. Assortment of Same Sample, Without Tail.—Class 3.
Production of oil . . . . 7*21 per cent.
Colour of oil slight yellow
Optical rotation 15° C. . . . + 14-24 (length of tube 10 cm.)
Specific gravity 15° C. 0'922
6. Assortment of Same Sample, Larger Kind.—Class 4.
Production of oil 13*3 per cent.
Colour of oil slight light green
Optical rotation 15° C - 33'6 (length of tube 10 cm.)
Specific gravity 15° C 0'923
From these figures there results :—
PIPEKACE.E 113
1. That the sample under review did not consist entirely of real
cubebs, and that fruits must have been present that produced an
oil, the physical qualities of which are very different from those of
genuine cubeb oil, even so much that there are fruits among them
which produce instead of the usual laevo-rotation a strong dextro-
rotation.
2. That the reaction with concentrated sulphuric acid may be re-
garded an excellent expedient to recognise different kinds from irregular
cubebs, for all kinds colouring yellow with H2SO4 also show important
irregularities of the physical constants of the oil.
OIL OF MATICO.
This oil is distilled from the leaves and spikes of Piper angustifolium
(Artanthe elongata Miq.), a plant indigenous to tropical America.
Probably other species are sometimes used for distillation, as the im-
ported leaves show considerable variation from time to time, and the.
following species have been recognised in commercial samples :—
Piper angustifolium.
,, camphoricum.
,, lineatum.
,, angustifolium v. Ossanuno.
acutifolium.
,, mollicomum.
,, asperifolium.
The yield of oil is very variable, from less than % per cent, to 6 per
cent. The oil is a liquid of somewhat penetrating odour, and has the
Acid value 0 ,, 4
Ester „ 2 ,, 8
It is usually soluble in 10 parts of 80 per cent, alcohol, but sometimes
25 parts are required. Very little is known of the chemistry of the oil.
There is present a small quantity of " matico camphor," a crystalline
odourless solid of specific gravity 1-080, melting at 94° and having a
specific rotation in chloroform solution - 28'7°. Its formula is C15H26O,
and it has been suggested that it is a derivative of ordinary camphor,
but there is no experimental evidence in favour of this, and it appears
to be a sesquiterpene alcohol. This body seems to be generally absent
from the oil distilled at the present time. Schimmel & Co. state that
they have found asarone C12H16O3 in one sample of the oil, which had
the specific gravity 1*077, and was slightly laevo-rotatory.
An oil has recently been examined by Schimmel which contained
much asarone. A mixture of terpenes and cineol was also identified.
A sesquiterpene alcohol also appeared to be present in this oil, which
is possibly identical with the matico camphor which is now not always
present in normal distillates.
Fromm and v. Emster l have isolated from matico oil a phenol
1
Bericht, 35 (1902), 4347.
VOL. I. 8
ether, which appears to be a methyl-butenyl-dimethoxy-methylene-
dioxy-benzene, but Thorns l considers this ether to be a mixture of
parsley apiol with a little dill apiol. A sample distilled from Peruvian
leaves was found by Thorns 2 to contain limonene, dill apiol, and a ses-
quiterpene having a specific gravity 0*914, refractive index T5125, and
boiling-point 138° to 139° at 17 mm. Traces of palmitic acid were also
present.
The following oils, distilled solely from single species of matico have
been examined:—
Source. Specific Gravity. Rotation. Constituents.
3
Piper campjwrificum . 0-9465 + 19° 21' Camphor, borneol, terpenes,
free acids, phenols, ses-
quiterpene alcohol.
,, lineatum4 . 0-958 + 8° 45'
, , acutifolium 5 1-0965 + 0° 24' Pinene, dill apiol, sesquiter-
pene.
»» M
6
• • 0-9355 + 0° 24' Pinene, dill apiol, sesquiter-
pene, an alcohol C10H16O.
OIL OF BETEL.
Betel oil is distilled from the leaves, either fresh or dried, of Piper
betle (Ghavica betle Miq.). The yield is from *5 to 1 per cent., but if
the leaves are bleached by being kept in a warm shady place, the yield
may reach 4 per cent. The oil varies considerably in characters ac-
cording to the nature of the raw material, and the following results7
have been obtained by various investigators :—
Origin. Specific Gravity. Rotation. Constituents.
Siam 1-024 Betel-phenol and cadinene.

1-020 —
Manila . 1-044 Betel-phenol. —
—
Java 0-958 - 1° 45' Chavicol, betel-phenol, a sesquiterpene.
0-959 + 2° 53'
Bombay 0-940 at 28° —
Manila . 1-0566 — 10'
- 1° —
1-055 + 0° 40' —
Java 1-0325 —
- 1° 55' Betel -phenol, allyl-pyrocatechol, cineol
eugenol methyl ether, caryophyllene.
The refractive index of betel oil exceeds 1-5100, usually about 1*5200.
Eykman investigated the oil some years ago and stated that ifc con-
tained the phenol, chavicol (q.v.), several terpenes, a sesquiterpene, and
possibly cymene and cineol. He described it as a yellowish-green oil,
with a burning taste, and peculiar, pleasant odour. It was stated by
him to be laevo-rotatory. Bertram and Gildemeister, however, in 1890,
distilling the oil from the dried leaves, stated that the oil contained 70
1 2
3
Arch. Pharm., 242 (1904), 328. 4
Ibid., 247 (1909, 591.
5
Thorns, Apotheker Zeit., 24 (1909), 411. Thorns.
6
Ibid, (leaves
7
mixed with some of P. mollicomum and P. asperifolium).
Ibid. Gildemeister and Hoffmann, 1913, ii. 222.
PIPEKACEJE 115
to 75 per cent, of betel-phenol, which was found to be a methoxy-
ohaviool. They identified the sesquiterpene as cadinene. Schimmel
states that the oil distilled from leaves from all sources contained this
betel-phenol, and in addition the oil from Java leaves contained several
terpenes and chavicol, that from dried Siam leaves contained a sesqui-
terpene, andl that from Manila contained betel-phenol, but no chavicol.
Bykman has found a body of peppermint odour in the Java oil
.(menthone or menthol?).
OIL OF PBPPEK.
This oil is distilled from the unripe berries of Piper nigrum. The
yield of oil is from 1 to 2*5 per cent. The oil is often of a greenish
-colour, somewhat resembling oil of cubebs, but with a much more pun-
gent odour. The green colour is due to a high boiling constituent,
possibly identical with that in oil of cubebs.
Pepper oil has the following characters :—
Refractive index . 1*4875 „ 1-500
The oil consists largely of phellandrene, principally the laevo-modi-
fication. Dipentene is also present, and a small quantity of a sesquiter-
pene which is probably caryophyllene. Haensel 2 has isolated from the
.high boiling fractions a body melting at 138°.
Other " pepper oils " of interest are as follows :—
The so-called " long pepper," a mixture of Piper longum and Piper
•officinarumj yields about 1 per cent, of an oil of specific gravity 0*861,
distilling mainly between 250° and 260°.
Piper Lowong, known as a kind of " false cubebs," yields about 12
per cent, of oil having a specific gravity about 0*865. It contains a
•crystalline substance of the formula C10H16, 2H2O, melting at 164°.
OIL OF ASHANTI PEPPER.

According to Schimmel & Co. the fruit of Piper yuineense, or
Ashanti pepper, yields an essential oil which has not previously been ex-
amined. The yields in two cases were 11*5 per cent, and 10*96 per
•cent. The oil was colourless or pale yellow, and had a peppery odour.
The two samples gave the following figures on analysis :—
1. 2.
Specific gravity 0*8733 0*8788
Acid value 0-6 0-9
Ester ,, 5-5 4-2
„ ,, (after acetylation) — 22-1
Solubility in 90 per cent, alcohol 1 in 8 1 in 9
OIL OF PIPER ADUNCUM.

The fruits of Piper Aduncum, known in Java as Daon Sisirihan, yield
1 2
Bericht, 22 (1899), 2736. Pharm. Zeit., 50 (1905), 412.
*Arch. Pharm., 234 (1896), 238.
Optical rotation + 5 ° 40'
Acid value 1*2
Saponification value . . . . . . . . 8'4
CANNABINACEÊ.
OIL OF HOPS.
Oil of hops is distilled from the flowers of the ordinary hop, Hitmu-
lus lupulus, which yield from '3 to 1 per cent. The oil glands are situ-
ated under the scales of the flowers (catkins); these grains or glands
can be separated from the flowers, and are known in commerce as
lupulin. The quality of the oil is, of course, dependent on the state of
the flowers, and when the crops have had to be " sulphured," the oil
obtained from the flowers is less valuable and contains traces of sul-
phur. The pure oil has a pale yellow to faint green tint, but can be
obtained colourless by rectification. It has a penetrating hop odour.
Its characters are as follows :—
Specific gravity . . 0*850 t o 0-893
Optical rotation -2° , +2°
Refractive index 1-4850 , 1-4920
Acid value . . . . . . . . . 1 , 10
Ester ,, 15 , 40
,, ,, (after acetylation) . . . . . . 68 , 80
It is not soluble in 90 per cent, alcohol as a rule, and often not in
95 per cent, alcohol. In 1822 Payen and Chevalier stated that there
were at least two bodies present. Wagner in 1853 obtained a terpene
boiling at 175° and an oxygenated body which yielded valeric acid on
oxidation. Personne claimed to have obtained a dextro-rotatory terpene
of specific gravity '888. The 1 most modern and reliable investigation,
however, is due to Chapman. Four samples of authentic origin gave
the following figures :—
Specific Gravity at 15°. Rotation [«]D.
1 -8802 + 0-41'
2 -8662 + 0-58'
3 -8771 + 0-50'
4 -8743 —
All these samples were free from sulphur and neutral to litmus.
No ketones or aldehydes were detected in the oil. A prolonged series
of fractionations at 60 mm. pressure yielded the following fractions:
(1) 89° to 91°; (2) 145° to 150°; (3) 163° to 168°; (4) 168° to 173°.
The first and fourth were the main fractions, the second and third being
very small. Fraction No. 1 was a colourless oil, practically unacted
upon by sodium. When distilled from this metal, it boiled at 86° to 89°
at the same pressure. Under ordinary pressure it boiled at 166° to 171°
almost entirely, but towards the end, the temperature went up to 250°,
due to polymerisation of the original substance. The specific gravity
at 20° was found to be -799 and the rotation - 0'56'. It is clear that
this body is not a normal terpene, and Chapman's experiments lead
him to consider it as a mixture of tetrahydrocymene, and one of the so.
called " olefenic 'terpenes," bodies as yet but little understood. Frac_.
\Jour. Chem. Soc., 83 (1903), 505; 67 (1895), 54 and 780.
CANNABINACEÊ 117
tion No. 2 was a liquid of specific gravity -885, and may be geraniol.
fraction No. 3 was a mixture of 2 and 4. Fraction No. 4 was found to
be a sesquiterpene, to whicb the name humulene (q*v.) was given. The
same observer has also published figures for hop oils obtained from
different sources as follows :—
Specific Gravity. Rotation.
Bavarian hops, 1894 . . . . 0-8676 + 0 ° 30'
1901 . . . . 0-8403 - 0 ° 08'
Californian „ 1899 . . . . 0-8639 - 0 ° 20'
On distilling one of these oils he again obtained the " olefenic"
terpene above referred to, which is probably myrcene, and linalol,
together with an acid C9H18O2 (probably isononylic acid) in the form of
esters. Dipentene was also detected and probably esters of geraniol.
The sesquiterpene " humulene " and the " olefenic " terpene make up more
than 80 per cent, of the oil. Schimmel & Co. have detected gurjun oil
as an adulterant of this oil.
Deussen,1 however, has since suggested that the sesquiterpene
"humulene" is in fact «-tt-caryophyllene, with a small amount of
/?-caryophyllene.
Eabak 2 has also isolated free formic, valerianic and heptylic acids,
and also formic, acetic, octylic, nonylic, decylic, cenanthylic, and butyric
acids in the form of esters. Myrcenol was also found in the oil.
Babak considers that hop oil contains 15 to 20 per cent, of sesquiter-
penes and 20 to 40 per cent, of esters of myrcenol. This latter figure
must, however, be accepted with reserve, as the ester value is rarely
high enough to account for this quantity of esters.
Kabak gives the following table of characters of a selected number
of samples of hop oil:—
Solubility
Origin. Year. Yield Refractive Acid Ester in 94
per Cent. Rotation. Index. No. No. per Cent.
Alcohol.
California 1907 0-24 0-823 1-4856 2-3 44-4 5-4 Vols.

1908 0-35 0-836 1-4738 1-7 45-5 4
1909 0-38 0-839 1-4730 1-8 46-8 3-6
Oregon . 1907 0-20 0-8343 1-4802 1-6 57-0 4-6
1908 0-32 0-838 1-4730 1-0 50-2 3-3
1909 0-30 0-8433 1-4705 2-8 56-0 3
New York . 1907 0-16 0-862 1-4804 3-6 61-0 3-5
1908 0-14 0-837 1-4756 2-1 47-0 3-5
1909 0-15 0-8777 1-4800 2-5 51-8 3-7
Washington . 1908 0-36 0-850 1-4763 1-0 51-8 3-5
1909 0-38 0-8464 1-4734 1-5 53-8 3-3
Bohemia 1907 0-32 0-855 1-4905 1-5 52-8 4
1903 0-23 0-824 1-4852 1-0 52-8 6
1909 0-24 0-861 1-4829 3-0 55-3 4
OIL OF HEMP.
Hemp Oil.—The flowers of Cannabis sativa, the ordinary hemp,
yield about ^ per cent, of volatile oil of specific gravity about *930.
It is laevo-rotatory to the extent of about - 10° to - 12°. The oil
l
Jour.prakt. Chem., ii. 83 (1911), 483.
2
Jour. Agricult. Eesearcli Dept., Agric., Washington, 2 (1914)? 115.
appears to consist entirely, or nearly entirely, of sesquiterpenes and
terpenes. The principal sesquiterpene present has a specific gravity
0-919 and optical rotation - 10-8°. It boils at 256° to 258° and forma
a solid hydrochloride.
Indian Hemp Oil is obtained by subjecting the flowering twigs of
Cannabis Indica to steam distillation. According to Valenta the re-
sulting oil is of thin consistency, and possesses an agreeable aromatic
odour. It boils between 248° and 268°. Its specific gravity is about
•930, and optical rotation - 10°, and it appears to consist chiefly, of a
sesquiterpene, which has been named cannibene.
Vignolo obtained an oil by distilling the female flowering plant, of
similar boiling-point, and of optical rotation - 18°. Wood, Spivey, and
Easterfield* isolated from the resinous extract an oil of the formula
C18H24O2, which is resinous at ordinary temperatures, and boils at 265°.
Its specific gravity is 1*0424 at 18°. It has been termed cannabinol..
They also found a slightly laevo-rotatory terpene (?), of specific gravity
0-819 and boiling at 160° to 180°. They found that the sesquiterpene
boiled at 258° to 259° and had a specific gravity 0-898 at 18° and optical2
rotation - 8'6°. This body (cannibene) was also isolated by Vignolo,
who found its characters to be practically identical with those described
by Wood, Spivey, and Easterfield.
A substance of the formula C21H290 . OH has been described by
Frenkel and Czerkis 3 under the name of cannabinol, but does not appear
to be the same body as that described above under the same name.
JUGLANDACEjC.
WALNUT-LEAF OIL.
The essential oil of the leaves of Juglans regia has been examined!
by Schimmel & Co.4 Two samples were distilled, one at Miltitz, and
the other at Bar-r&me. The distillates were of an olive-brown colour
and possessed the characteristic odour of walnut leaves. At about 10°
they formed semi-solid, butter-like masses, which melted at about 20°.
From the solutions in 90 per cent, alcohol large quantities of paraffin
separated out, which after repeated recrystallisation from alcohol had
a melting-point 61° to 62°. The constants of the oil are shown in the
table below :•—
Distilled at Yield. *- Acid Ester Ester

after
v.
So- J5 • v. v. Acet
Per Cent.
Miltitz . . . . 0-014 0-9137 ±0° 1-49657 9-3 27-0
Barr6me
83 p. cent. Principal Oil 0-0072 0-9174 - 17° 36' 1-49177 3'7 9-3
17 „ Water Oil . 0-0015 0-9231 - 16° 12' 1-49366 4-7 9-7 —
100 „ Total Oil . 0-0087 0-9185 - 17° 0' 1-49215 —
98-5
— —
l 2
Jour. Chem. Soc. (18%), 543. Gazzetta (1895), HO.
*Annalen, 351 (1907), 467. ^Report, April, 1912, 181.
MYRICACE,E 119
MYRICACE^;.
OIL OF BAYBEREY.
The leaves of the Bayberry, or wax myrtle, Myrica cerifera, yield
about 0*02 to 0*05 per cent, of an essential oil having the following
characters:—l
Acid value * 3*5
Ester „ 21
„ „ (after acetylation) . . . . . . 58
The oil was soluble in 0*5 volume of 90 per cent, alcohol, the solu-
tion becoming turbid upon the addition of 2 volumes or more.
This oil had previously been described as having a specific gravity
of about 0*885 and an optical rotation - 5°. It is doubtful, however,
whether these figures were obtained on a pure sample.
The leaves of the so-called Bog Myrtle, Myrica gale, which (as is
the case with Myrica cerifera) must not be confused with the true
Myrtle (q.v.), also yield an essential oil in small quantity. According
to an early investigation by Eabenhorst,2 the oil had a specific gravity
of 0*876 and was a solid mass at 12*5°. The more recent investigations
of Laloue,3 however, would indicate that, as is true of many of the early
investigations of essential oils, the material investigated was impure.
Laloue obtained about 0*045 per cent, of oil having the following char-
acters :—
Acid value 3*5
Ester value 15'5
„ ,, (after acetylation) 60*2
The oil was soluble in half its volume of 90 per cent, alcohol. On
cooling it becomes turbid at 5°, but does not completely solidify at - 17°.
The oil has also been investigated by Pickles.4 He obtained 0*076
per cent, of oil from a mixture of fresh leaves and twigs, and 0*203 per
cent, from the dried leaves. The oils had the following characters:—
Fresh Dried
Leaves. Leaves.
Specific gravity . . . 0*915 0'912
Acid value 7-0 4-0
Ester „ . 24-7 19*2
(after acetylation 56*4
Enklaar 5 has examined the oil from the flower spikes of Myrica
Gale. He obtained about 0*5 per cent, of oil having a specific gravity
0*899 and optical rotation - 5° 36'. The lowest boiling fractions con-
tained pinene ; but whether a- or /2-pinene, Enklaar was unable to dis-
tinguish. It would appear that the oil contains d-a-phellandrene
J
Babak, Midland Drug and Pharm. Bev , 45 (1911), 484.
2:! Report Pharm., 60 (1837), 214.
Bulletin, Roure-Bertrand Fils, April, 1910^ 54.
4 5
Jour. Chem. Soc.t 99 (1911), 1764. Chem. Weekblad, 9 (1912), 1
(melting-point of the nitrite 112° to 113°).t The presence of cineol was
proved by the preparation of the hydrobromide and the iodol compound.
The highest boiling fractions of the oil contain a sesquiterpene (boiling-
point 150° to 152° [17 mm.]; 263° to 265° [760 mm.]; dlfi0 0'928;
aD - 4° 30'), possibly caryophyllene. The high boiling portions also
contain a solid body which crystallises from alcohol in needles and
possesses the odour of Dutch myrtle.
The oil contains about 0s75 per cent, of paraffin hydrocarbons, of
the empirical formula C29H60 melting at 63° to 64°. Free palmitic acid
was also found, as well as cineol, dipentene, and high boiling sesquiter-
penes and alcohols not yet identified.
Myrica asplenifolia, a North American plant, known as sweet fern,
yields about 0*1 per cent, of an essential oil having a specific gravity
about 0*926, which solidifies on cooling. It probably contains cinnamic
aldehyde.
SALICINEÊ.
OIL OF POPLAK BUDS.
The young buds of the black poplar, Populus nigra, yield from 0*3
to 0'6 per cent, of an essential oil of a pale yellow colour, with an odour
somewhat recalling that of chamomiles. It has the following char-
acters :—
Specific gravity 0*890 to 0*907
Acid value 2 „ 12
Ester value . . . 8 „ 14
,, „ (after acetylation) 18 „ 5H
According to Piccard,1 the principal constituent is a hydrocarbon of
the empirical formula (C5H8)«r, which from a vapour density deter-
mination appears to be2 C20H32.
Fichter and Katz, however, consider that the hydrocarbon is a
sesquiterpene C16H24, which is probably a-caryophyllene. A small
quantity of a mixture of paraffin hydrocarbons melting at 53° to 68° is
also present in the oil.
URTICACEÊ.
OlL OF PlLEA.
An oil distilled in Eeunion from an unnamed species of Pilea has

been examined by Schimmel & Co.3 and found to have the following
characters:—
Optical rotation 33° 53' „ + 58° 20'
Refractive index . . . . . 1-4686 „ 1-4690
Ester value . . . . . 5*1 „ 7-7
„ „ (after acetylation 24-2 „ 34-4
On fractionation the oil behaved as follows : —
^Bericht, 6 (1873),
3
890; 7 (1874), I486. ^ Ibid., 32 (1899), 3183.
Ibid., October, 1906, 84 ; April, 1907, 113.
CHENOPODIACE^ 121
Distilled at
748 mm.
Pressure.
158° to 159° 6 per cent.
159° 160° 35
160° 161° 10
161° 161-5° 10
161-5 163° 10
163° 165° 10
165° 168° 7
168° 174° 2
174° 194° 8
Residue 2
The oil contains a-pinene and sabinene.
CHENOPODIACE/E.
OlL OF WORMSEED.
This oil, known as American wormseed oil, is distilled from the

.herb Ghenopodium ambrosioides, var. anthelminticum, in the United
.States, principally in Maryland. A certain amount of oil is distilled
from the fruit only. Normal oils have the following characters :—
The oil is soluble in 3 to 10 volumes of 70 per cent, alcohol.
No portion of the oil distils below 170°, and any distillate obtained
below that temperature indicates adulteration with turpentine.
The oil has been very exhaustively examined recently by Nelson, to
whom our knowledge of the chemistry of this oil is in the main due.
The lowest boiling fraction consists of _p-cymene; Z-limonen,
;sylvestrene and camphor are also present, but the principal con-
stituent of the oil is the body ascaridol. Nelson * has fully investigated
this body, CJOH16O2, which was originally isolated by Schimmel & Co.
He examined four samples of the oil which had the following charac-
ters : d25o 0-955 to 0-9691; aDi - 5-4 to 8-8°; now 1'4723 to 1-4726; soluble
in from 3 to 7 volumes 70 per cent, alcohol. A fifth sample, at least
one year old, which was used for the purposes of the examination, had
the following characters: d25° 0-9694; aD - 0'35°;ra>2<p1*4780; soluble
in 3 volumes 70 per cent, alcohol; acid value 0; ester value 5*0. As-
oaridol has the following characters :—
Boiling-point at 5 mm. 83°
The results obtained by shaking ascaridol with saturated solution of
ferrous sulphate are, however, of particular interest. At ordinary tem-
perature this peculiar reaction proceeds with such violence as to decom-
pose the ascaridol, the temperature rising considerably with evolution
• of a combustible gas. Jsopropyl alcohol is also formed as a product of
reaction and was isolated from the syrupy product of conversion by
steam-distillation and identified as acetone by oxidising it with chromic
acid. Below 35° the reaction proceeds normally and without decom-
position. In these conditions ascaridol adds the elements of the water and
^ Jour. Amer. Cliem. Soc., 33 (1911), 1405.
is converted into a glycol, C10H18O8, which, when benzoated by Schotten-

Baumann's method, yields a solid benzoate, melting-point 136° to 137°.
According to Schimmel & Co., normal American worm-seed oil contains
from 62 to 65 per cent, of ascaridol, and about 22 per cent, of cymene.
Light oils of inferior quality, due probably to the quality of the material
distilled, having a specific gravity about 0*942, contain from 45 to 50
per cent, of ascaridol and about 38 per cent, of hydrocarbons. II
The oil is used as an anthelmintic.
E. K. Nelson1 has recently investigated the changes taking place in
this oil on keeping. He points out that this oil increases in specific
gravity and decreases in optical rotation after being kept at ordinary
temperatures for a year. If kept in an ice-chest the changes are not so
marked. The following table shows the changes in four samples of the
oil kept for a year at room temperature, and in a refrigerator : —
Fresh.
At 25°. 1. 2. 2. 4.
Specific gravity . . . 0-9691 0-9700 0-9550 0-9584
Rotation ..... - 5-4° - 6-2° - 8*8° - 6*3°
Refractive index . . . 1-4726 1-4723 1-4726 1-4725
Refrigerator.
Specific gravity . . . 0*9700 0*9711 0*9590 0*9595
Rotation ..... - 5-3° - 5*9° - 8'6° - 6'1°
Refractive index . . . 1-4740 1-4740 1-4743 1*4740
Room Temperature.
Specific gravity . . . 0'9703 0-9804 0-9838 0'9600
Rotation ..... - 5'2° - 5-5° - 6*6° - 6'1°
Refractive index . . . 1*4745 1*4750 1-4770 1*4746
Nelson finds that when ascaridol suffers rearrangement, either by
heating or by treatment with ferrous sulphate, there are two other
bodies formed besides the glycol described by Schimmel. One of these
is also a glycol, which he terms /?-glycol, to distinguish it from the
other one. It has the formula C10H18O3, and is decomposed with the
formation of thymol on warming with dilute sulphuric acid. The third
substance is an erythrite melting at 128° to 130°, of the formula C10H20O4,
which when boiled with dilute sulphuric acid yields a ketone with a
strong menthone odour, and a phenolic body melting at 80° to 81°. The
ketone yields a semi-carbazone melting at 182° to 184°. It is probably
an isomeric menthenone, or a mixture of several isomers.2
LAURACEÊ
OF CASSIA
This oil is distilled from the leaves, twigs, and other parts of \the
plant Cinnamomum cassia, which is probably a native of Cochin China,
but which is chiefly cultivated in China proper, the three chief districts
being Taiwu (Lat. 23° 34' N., Long. 110° 18' E.), in the Kwangsi pro-
vince; Lukpo (Lat. 23° 6' N., Long. 112° 24' E.), and Loting (Lat. 22°
52' N., Long. 111° 8' E.), both in the Kwangtung province. Much con-
fusion and mystery existed till recently in regard to the exact botanical
source of the plant and the nature of the oil and the methods of its
distillation, etc., which were largely caused by the shameful adultera-
tion by the Chinese. The following details furnished by actual
1
2
U.S.A. Dept. of Agriculture, Bulletin, No. 109. .
In a still later publication (P. and E. O. R. (1920), from J. Amer. Chem. Soc.)9.
Nelson deals with the distillation of this oil. An abstract of this paper will be found
in the Appendix at the end of this volume.
LAUKACEÊ 123
observers give the most reliable information on much affecting these
questions. In a Report on a Journey to Kwangsi, by H. Schroeter, 1887,
the writer says :—
" The shrubs destined for the production of the Cassia lignea proper
are partly stripped during the summer months of their minor branches
and exceptionally juicy leaves. They are then conveyed in huge bundles
into the valley, where they are boiled in large vessels. From the aro-
matic juice thus obtained the esteemed cassia oil is recovered by means
of a most primitive distilling apparatus. As the Li-kin stations on the
road to Canton levy an excessive duty upon the oil, in addition to that
exacted by the Imperial Customs, the oil is carried in tins across the
hills to Pakhoi and thence transported to Hong-Kong vid Macao, in-
stead of reaching Canton by the waterway intended by nature for its
conveyance."
These statements are in agreement with those contained in a report
presented to the Hong-Kong Government by Mr. Charles Ford, which
will be found reprinted in the Journal of the Linnaan Society, Decem-
ber, 1882, and in which much valuable information is given. More
recently (1895) Messrs. Siemssen & Co. of Hong-Kong, on whose be-
half Herr Schroeter's visit was made, sent a representative, Mr. Struck-
meyer, to the Loting-Chow districts, in company with the German
Consul, Dr. Knappe. The report of these travellers is sufficiently in-
teresting to warrant its reproduction here, as this oil is of great com-
mercial importance, and reliable information as to its production is
very scarce. It read as follows :— i—
" We embarked on the right bank of the West river, opposite Tack-
Hing-Chow, at six a.m. on 15th December, 1895. We left there our large
boat and went to a place with extensive matting factories, located on
the Loting-Chow or Lintau river, arriving there about half-past two
o'clock in the afternoon. Next morning we continued our march to
Loting-Chow, under the guidance of a Chinese, a manager of one of
the largest matting establishments in Lintau. We were attended by a
servant of the Consul, who also served as interpreter, and by several
Chinese coolies. After a brisk march we took up our quarters in a
small Chinese temple, and made strclls through the city, which, although
small, seems to be a busy trading place. Loting-Chow is pre-eminently
a centre for all the products of the cassia tree, and for firewood to be
shipped thence to Canton and Macao.
" The cassia plantations are still further inland, and we had to defer
visiting them until the next day, because they were too far off, accord-
ing to our informants in Loting-Chow. They proposed, however, to
accompany us the following day to cassia plantations as well as to a
distillery. During the afternoon we visited a dealer in cassia oil, the
only one in the place, he pretended. Subsequently, on our return, we
ascertained this statement to be false. At first he was very reticent,
but subsequently yielded to some pressure. He possessed a separating
funnel, a syphon, test-tubes, etc., and pretended to examine all oils offered
to him for sale, because he had been condemned, as he said, to $900
damages for inferior cassia oil sold by him some five years ago. He
assorts the commercial oil into four or five grades, but deals only in the
three best qualities, unadulterated in his opinion. He had in stock but
a small quantity of the best oil, and gave us small specimens of three
kinds of his oil, of which I shall treat more fully further on.
"Although everything was arranged for the next day with our
Chinese guides, we had to face considerable difficulties. During the
evening we were informed that a certain ' Mr. Wong' (who never ap-
peared in person) had arrived from the interior, and reported that a
visit to the cassia plantations would be of no use, and that it would not
be possible to inspect any distillery, because some children had been
instructed by thieves to steal the leaves from the cassia trees, and that
in consequence a brisk contest between the owners and the thieves was
in progress. Besides, it was claimed that only one distillery existed, at
a distance of 20 Lis (about 8£ miles), and that this was not in operation
in consequence of the disturbances. This wondrous story, and the
circumstances under which it was imposed upon us, convinced us that
it was an impudent lie, or, at best, an absurd exaggeration. The more
they tried to dissuade us from continuing our trip, the more we persisted
upon the realisation of our plan. Finally the Lintau Chinaman volun-
teered to accompany us to the plantations, but would not make any
promise in regard to visiting any distillery. The departure was fixed for
six o'clock the next morning. We were in a peculiar position, since our
interpreter also appeared to antagonise our aims ; nor had we 'any time
to lose
11
in order to comply with all other arrangements of our expedition.
The next morning, 17th December, we and our men were ready at
six o'clock, but the two Chinese failed to appear, although we had re-
quested them several times to hurry. We were waiting with our at-
tendants in front of the temple when messengers brought the idle excuse
that the two Chinese had not yet received their breakfast, and that no
carriers for our baggage could be obtained. At a quarter to eight we
sent word that we would start without guides, and when they caught
up with us at ten o'clock we paid no attention to them.
" We finally succeeded in inducing one of the many onlookers to guide
us to one of the distilleries. The march went on very slowly, and the
.actions of our interpreter led us to foresee further intrigues. As on the
previous day, our route passed through a hilly country with numerous
side valleys and little ravines. After having passed a number of hills
covered with young cassia trees, we reached a distillery by ten o'clock,
but found out that it was not in operation. We were again told that
this was the only distillery in the neighbourhood. But as luck would
have it, during our brief stay a small trader appeared upon the scene
and offered some thick cassia bark for sale. By small purchases and
promises we succeeded in inducing the man to lead us to another dis-
tillery, and one in operation.
" We returned the same way by which we had come, and at noon-
time arrived at a distillery in full operation. It was a little off the
road, but was much nearer to our starting-point in the morning than the
distillery to which we had been led at first. We met with a very kind
reception by the owner and his employees, and they readily gave us any
desired information. We ascertained that about twenty distilleries
existed in this immediate neighbourhood, and that most of them at the
time were in full operation. We subsequently found out on our return
to Canton that a few slight disturbances had occurred in the cassia
•district^, but the fact remained that we had been treated to absurd
stories and gross lies, probably at the instigation of some dealers in
Loting-Chow.
" The distillery, like all others, is located in a ravine abounding in
LAUEACEÊ 125
springs which furnish an ample supply of water for coolers. The dis-
tillery with all its arrangements closely resembles the one which some
time ago was described and illustrated in one of the reports of Messrs.
Schimmel & Co.
" An iron pan is securely placed in a brick hearth with a large fire-
place ; upon this pan a large wooden cylinder lined with sheet iron is
placed, upon whose upper rim a large cover of strong sheet iron rests.
The space between the cylinder and the cover, around the rim, is made
tight by strips of moist cloth or rags. Around the lower side of the
cover there runs an outer groove for gathering and drawing off the
water serving for cooling, and a narrow interior groove for collecting
the distillate containing the essential oil. This distillate passes into
tin cans and the oil collects at the bottom.
" At each charge of the cylinder, about 1 picul of leaves and twigs
and 250 catties ( = 2-J piculs) of water are employed; the water used is
mostly from preceding distillates. The distillation lasts about two and
a half hours.
"The yield of one such charge, when consisting of leaves only, is
1£ to 2 taels, and when consisting1 of 70 per cent, of leaves and 30 per
cent, of twigs, 2-J to 3 taels of oil. The oil obtained from leaves alone
is in general the superior one.
" With a still of this capacity, as much as 50 catties of oil are ob-
tained per month, or 3 to 5 piculs per year. The festivities connected
with the Chinese New Year cause an interruption of the distillation for
one or even two months. The quality, of the oil depends upon the
material used for distillation. Both too old and too young trees furnish
leaves less rich in oil; large leaves are better than small young ones ;
this explains the fact that the twigs and leaves gathered in spring and
in winter yield an inferior oil to those gathered in midsummer and in
autumn.
" The distiller who furnishes us this information claims to produce
but one grade of oil, using 70 per cent, of leaves and 30 per cent, of twigs.
A specimen, marked A, was taken by us from the apparatus. The tin
can contained but a small amount of oil resting under the water, and
the sample, collected in a rather primitive way, contained some water.
On standing, some drops of water separated at the top of the slightly
yel'ow oil. It was subsequently examined by Mr. JJ. Neidhardt in
Hong-Kong, with the following result:—
"Specimen A (1895). A turbid liquid which on standing separated
into two layers, the upper one water, the lower one cassia oil of a light
Bhine wine colour.
Consistency : very limpid.
Odour: the true oil of cassia, somewhat smoky.
Taste : the same.
Specific gravity : 1*059.
Residue of distillation: 3'75 per cent.; resinous, sticky.
Cinnamic aldehyde: 86 per cent.
Solubility in alcohol 80 per cent. : complete.
Solubility in solution of sodium salicyiate : complete.
Reaction with lead subacetate: no turbidity.
" The result of this investigation indicates that a rather large pro-
portion of twigs seems to be required to materially reduce the quality
1
16 taels = 1 catty = 605 grms.; 1 picul = 60 kilos 500 grms.
of the oil. Perhaps twigs\ too oli and too thick have a detrimental
effect upon the quality of the distillate.
" The oily water, as collected during the process of distillation, is

milky. Specimen B represents this water as separated from the oil
and mixed with Specimen A.
LAUKACEÊ 127
" Specimen C represents the ready oil as our distiller sends it to
Loting-Chow for sale. The specimen was taken from a tin can by
•ourselves.
"For these samples we were charged in proportion to the regular
price of $600 per picul.
" The distillers generally purchase the leaves and twigs and carry
•on the distillation on their own account; occasionally they rent their
stills to the owners of the raw material, mostly planters, or they run
their stills on the latter's account in return for a compensation.
" In Loting-Chow we obtained two more samples of commercial oil.
Specimen D was said to be a good oil of prime quality obtained from
-old leaves and commanding a price of $600 per picul. It did not
-change when brought into contact with water, but separated into
smaller or larger globular masses, showing a few oil drops on the sur-
face. It was of a light colour.
" Specimen E, said to be distilled from young leaves; price $580
per picul. It showed in water a more compact mass, with a thin,
transparent surface, and more oil drops on top of the water.
" Specimen F was said to have been obtained from old and young
leaves and to have been adulterated with kerosene, and therefore to be
•of no use to the dealer; price $550. When brought into water, this oil
formed a compact mass with a thick surface, partly of a whitish and
•striped appearance. Colour rather dark. The dealer stated that he
had showed us this oil only as a specimen of adulterated oil, that he
kept it only as a sample, and that he had only a small amount of it.
Consequently he could only sell us such a small sample.
" The adulteration is charged by every one to somebody else. We
found no suspicious material in the distilleries; there is an abundance
-of pine leaves growing in the region, but their admixture with the cassia
leaves was peremptorily denied; nor did we find any such admixture
in the contents of the still examined by us. Although a few distillers
may be guilty of dishonest practices, there is no reason to assume that
the majority resort to deliberate adulteration by the admixture of
foreign matter with the cassia leaves and twigs. On the other hand, we
may conclude from the existence of adulterated oil in Loting-Chow,
and from our examination made there, that flie sophistication ought
not to be imputed exclusively to the Chinese of Macao and Hong-Kong,
if at all. The fact is, before the oil is sold to the foreign exporters, it
•comes from an extensive district and passes through so many hands
that it is impossible to determine where and how it is actually adul-
terated. In Loting-Chow it was alleged that most adulterations are
committed in the province of Kwangsi, where ten or even more
qualities of cassia oil can be had.
" The question may here be raised whether the present methods of
examination suffice to detect the most artful and subtle adulterations,
as also whether the Chinese really possess the requisite knowledge and
skill for such refined forms of sophistication.
" Sample A bears sufficient evidence that excellent oil can be, and
is, produced. This detailed account, however, may indicate what diffi-
culties the foreigner has to meet with when trying to get at the bottom
of facts.
"Incidentally it may be added that the residue of the leaves and
rtwigs, after having been dried, is used as burning material. The
remaining ashes are subsequently extracted by hot water, and a kind of
potash called Kamalni is obtained therefrom.
" Consul Dr. Knappe has forwarded a collection of the samples A,
B, C, D, E, and F and an elaborate report to the Foreign Office in
Berlin. Sample A is the only one which we had examined in Hong-
Kong."
Schimmel & Co. have obtained specimens of raw materials of various
parts of the plant and examined the oils yielded by them. The results
of their investigations are summarised as follows :—
" Cassia Budsticks.—Small, thin stalks, about 1 mm. thick and
5 mm. long, which possess a strong and pure cinnamon taste. Six
hundred and fourteen kilos distilled by us yielded 10 kilos 120 grms.,
or 1*64 per cent., of a beautifully bright oil with excellent sweet taste,
indicating a high percentage of aldehyde.
" We determined the specific gravity to be 1*0463, the aldehydic
contents 92 per cent.
" Cassia Leaves.—The dried, leather-like leaves of the cassia plant
with the strong petioles and small twigs. On mastication of leaves
and petioles separately, both communicated a faint but pure taste of
cinnamon, whilst the twigs exhibited strong cinnamon taste.
" In order to obtain exact results we caused a certain quantity of the
material to be sorted into leaves and stalks. One hundred kilos material
yielded—
Leaves 85 kilos.
Small twigs 15 ,,
" On distillation the leaves yielded a beautiful, sweet-tasting oil,
with specific gravity 1-056 at 15~ C. The aldehydic contents were de-
termined as 93 per cent.
" The thin twigs showed a less percentage of essential oil than the
leaves, but this possessed a similar sweet taste to the oil from the leaves.
The specific gravity was 1*045 at 15° C. The aldehyde amounted to
90 per cent.
" The following parts of the cassia plant have been distilled by us
with the appended results :—
1. The Cassia bark (iê Cassia lignea of commerce).
Yield of essential oil: 1-5 per cent.
Aldehyde in oil: 88'9 per cent. Specific gravity 1*035.
2. The Cassia buds (the Ftores cassiae of commerce).
Yield of essential oil: . '550 per cent.
Aldehyde in oil: 80'4 per cent. Specific gravity 1*026.
3. Cassia budsticks.
Yield of essential oil: 1-64 per cent.
Aldehyde in oil: 92 per cent. Specific gravity 1*046.
4. Cassia leaves, leaf-stalks and young twigs mixed.
Yield of essential oil: 0*77 per cent.
Aldehyde in oil: 9-3 per cent. Specific gravity 1-055.
" Nos. 1 and 2 are completely excluded as raw materials for the pre-
paration of cassia oil on account of the price.
" No. 3 is also out of the question, because the value, about $4 per
picul, is still higher than that of broken cassia and because the yield
would not be sufficient.
"It can, therefore, be assumed with safety, that the cassia oil of
commerce is distilled in China from the leaves, leaf-stalks, and young
twigs of the cassia plant, probably together with various refuse pro-
ducts worthless for other purposes."
LAUEACEÊ 129-
Some interesting information has been published recently by the
United States Consul at Swatow l on recent developments in the cassia-
producing industry.
He states that in 1910 Huang Hsi-ch'uan, a member of the
Chinese provincial assembly, instituted a series of experiments in
cassia-culture at Kaying, in the course of which it was found that the
soil and climate there were very suitable for the growth of this plant.
Huang Hsi-ch'uan had previously carefully studied the corresponding:
conditions at Wuchow, on the West river, where there are large cassia
forests, and accordingly he started a model plantation, not only, it is
said, with a view of making money from the undertaking, but especially
in order to promote industrial enterprise and to counteract the tide of
emigration among the people of the region. Two species of cassia are
grown in the new plantations, one large and the other small. The
former flowers when ten years old, but it is only cut down at the age
of twenty years for the purpose of harvesting the bark. Between the
ages of ten and twenty years only the seed, of which the value is small.,
is harvested. The smaller variety yields leaves for the manufacture of
oil at three to four years of age, and its bark is only harvested at the
age of six or seven years. As soon as the trees (and this applies to-
both varieties) are cut down, new shoots immediately spring up around
the stumps, so that such a plantation, once started, lasts practically in-
definitely. The wood is used for fuel, the wood-ashes and the small
twigs are employed for medicinal purposes, the bark yields the " cassia "
of commerce, and from the leaves oil is distilled.
Cassia oil is imported, principally from Hong-Kong, in leaden ves-
sels holding about 16£ Ib. It is always sold as of a definite content of
cinnamic aldehyde, the lowest commercial quality being 70 to 75 per
cent., and followed by 75 to 80 per cent., 80 to 85 per cent., and 85 to
90 per cent. The lower grades are usually adulterated, the usual
adulterant being common rosin, and if a 'really pure oil is required,
one containing 85 to 90 per cent, of cinnamic aldehyde should be in-
sisted upon.
A pure cassia oil should have the following characters:—
Specific gravity 1-055 to 1-072.
Refractive index 1-6000 „ 1-6060:
Optical rotation - 1° ,, + 6°.
Acid value 6 to 16 (rarely to 20),
Cinnamic aldehyde rarely below 85 per cent.
The pure oil is completely soluble in 2 volumes of 80 per cent, alco-
hol, and usually in 3 to 4 volumes of 70 per cent, alcohol. The solu-
bility is impaired by most adulterants, such as colophony, heavy
petroleum oil or gurjun oil.
Colophony is indicated by a high acid value, and may be detected
and approximately determined by the lead acetate test. If to a solution
of 1 c.c. of the oil in 3 c.c. of 70 per cent, alcohol, there be added, drop
by drop, half a c.c. of a saturated solution of lead acetate in 70 per cent,
alcohol, no precipitate should be produced in the absence of colophony.
A precipitate indicates this adulterant. For an approximately quanti-
tative determination 5 grms. of the oil are dissolved in 20 c.c. of 70 per
cent, alcohol, and sufficient lead acetate solution as above added for com-
plete precipitation, 10 c.c. being the average quantity. Tlê precipitate
1
Daily Consular and Trade Reports, 3 July, 1911.
VOL. I. 9
is collected on an ignited asbestos filter, washed with 70 per cent,
alcohol, and dried at 100°. The weight of the precipitate is approxi-
mately equal to that of the colophony present.
The following rough method gives an approximate estimate of the
amount of adulteration, if this is colophony, heavy petroleum oil, or a
fixed oil. Weigh 50 grms. of the oil into a small Wurtz flask, and con-
nect in the usual way to a condenser, and gradually heat with a naked
flame. The oil commences to boil at about 210°, and the bulk distils
over between 240° and 260°. When the thermometer rises to 280° and
white vapours rise the distillation is stopped.
On cooling the flask (whose weight is known) its contents are
weighed ; the residue should not exceed 10 per cent.—it is seldom more
than 8 per cent.—and should not solidify. Over 10 per cent, residue
indicates adulteration, and if this residue solidifies colophony is present.
The most important method of examination, however, is the deter-
mination of the percentage of cinnamic aldehyde, and upon this per-
centage commercial oils are always sold on the market. In this process
the following details should be observed. Ten c.c. of the oil are run
into a Hirschsohn flask (capacity about 100 to 150 c.c., with a neck
about 5 ins. long and ^ in. in diameter, graduated in TVth c-c.). The
flask is then filled about three-quarters full with a 30 per cent, solution
of sodium bisulphite, and the whole well shaken. The flask is then
placed in the water-bath for several hours with occasional shaking,
until the precipitated compound of the aldehyde and bisulphite is
completely dissolved, and only a clear oil floats on the surface. Bisul-
phite solution is then carefully poured in until the oil is driven up into
the neck, and when it has attained the temperature at which the oil was
measured, the amount is read off. This gives the percentage of non-
.aldehydic constituents, the difference being returned as cinnamic alde-
ihyde. Pure oils should not give much less than 85 per cent, of
:aldehyde, the best oils yielding 85 to 90 per cent., or occasionally even
-higher. Strictly speaking,, these percentages are by volume, but the
errors of reading the result, and those due to solubility of the non-
.aldehydes in the aqueous liquid render any correction for* the specific
gravity of the constituents unnecessary in practice. Care must be
taken that every particle of the aldehyde compound is dissolved, as
•otherwise the reading of the oily layer will be obscured, and a serious
•error may be introduced. If the precipitate does not dissolve after
standing three hours in the water-bath with repeated shaking, the pre-
sence of solid resin may be inferred, and the estimation of the aldehyde
in this way, with accuracy, is then impossible. Hirschsohn recom-
mends shaking the oil in a graduated tube with three times its volume
of light petroleum ether. A diminution in volume of the oil indicates
petroleum, resin or fatty oils (except castor oil). An increase in
volume of the oil indicates castor oil. The petroleum layer is then
shaken with copper hydroxide. A blue solution indicates copaiba or
resin.
Hanus1 publishes a new method for the determination of cinnamic
aldehyde in cassia and cinnamon oils depending on the combination of
the aldehyde with semioxamazide. Ten grms. of finely powdered hy-
idrazine sulphate are dissolved in a solution of 9 grms. of caustic soda
l
Pharm. Central, 1904, 37.
LAUKACE^l 131
in 100 c.c. of water, and the alkaline sulphate produced is precipitated
by the addition of 100 c.c. of alcohol. After filtration the solution is
warmed, 9 grms. of oxamaethane are added in small portions, the whole
warmed for half an hour and allowed to cool. The azide separates in
crystalline tables, and these are separated and recrystallised. To esti-
mate the aldehyde by means of this reagent, a small quantity, not more
than 0*2 grm., of the oil is well shaken in 85 c.c. of water, and about
0*35 grm. of semioxamazide in 15 c.c. of hot water is added and the
whole well shaken. After five or ten minutes the compound begins to
be precipitated, and after standing twenty-four hours can be collected
on a Gooch filter, washed with cold water, and dried for a few minutes
at 105°. The amount of the precipitate is multiplied by 0*6083 to obtain
the amount of aldehyde. The constitution of the semioxamazone of
cinnamic aldehyde is NH 2 . CO . CO . NH . N : CH . CH: CH . C6H6.
The main constituent to which the odour of this oil, and of oil of
cinnamon, is chiefly due, is cinnamic aldehyde. Small quantities of
cinnamic acid, its oxidation product, are naturally found in the oil, the
amount varying according to its age. A terpene, and the acetic esters of
cinnamyl and phenyl-propyl alcohols, also exist in very small quanti-
ties. A stearoptene was also found in this oil in 1850 by Kochleder.
According to this chemist its formula1 is C28H29O5. But a recent in-
vestigation by Bertram and Kursten shows that it is ortho-methyl-
coumaric aldehyde C6H4(OCH3)(CH :CH . COH).
Dodge and Sherndal2 have recently shown that cassia oil yields at
least 0*5 per cent, of constituents removable by shaking out with 2 per
cent, sodium hydroxide solution. The oily liquid obtained by liberating
these alkali-soluble constituents in the usual manner was found to con-
sist of approximately 25 per cent, of salicylic aldehyde; 60 per cent, of
coumarin; from 8 to 10 per cent, of cinnamic acid; with small amounts
of salicylic and ben zoic acids, and of a liquid acid not yet identified.
Although the amounts of salicylic aldehyde and of coumarin are small,
they are sufficient to contribute to the composite aroma of the oil. In
fact, the presence of salicylic aldehyde may be detected, by odour alone
in the first fractions of the redistilled oil. It is to this constituent that
the purple colour reaction is due, which is obtained when cassia oil is
shaken with dilute alkali and the acidified aqueous portion is treated
with ferric chloride.
The same chemists have since3 shown that very small amounts of
benzaldehyde and methyl-salicylic aldehyde are also present in the oil.
Cassia oil, being packed in lead containers, usually contains traces of
lead, and in some quarters a demand has arisen for a lead-free cassia oil.
For the determination of the lead the method proposed by Lubetti4 yields
useful results.
5 c.c. of the cassia oil to be tested is diluted to 20 c.c. with 90 per
cent, alcohol; *5 or 2*5 c.c. of this solution is taken according as the lead
content is more or less than 0*025 per cent., which will be determined by
a preliminary test. This amount is pipetted into a 50 c.c. Nessler glass
of small bore (2*5 cm.) and diluted to about 20 c.c. with 90 per cent,
alcohol. A blank from lead-free cassia oil, obtained by distilling the
commercial oil, is prepared in a similar way; 1 c.c. of ammonium sul-
phide solution is added to both glasses and standard lead solution (1
l 2
3
Jour.Prdkt. Chem., ii., 51 (1895), 316. Jour. Eng. Ind. Chem. (1915), 1055.
Jour. hid. Eng. Chem. (1918), 10, 12, 1005. *Jour. Soc. Chem. Ind., 1920, 35.
c.c. =0*0001 grm. Pb.) added to the blank until the brown coloration
produced matches the sample under examination, the liquid being stirred
three times after each addition of standard lead solution by means of a
piston-shaped glass rod.
The results are calculated by means of the formula x = n x 0'04
-i-.m, where x is the percentage of lead sought, n the number of c.c. of
standard lead solution required, and m the amount of original solution
taken. The tint of the solutions can be compared by looking through
the Nessler glasses resting on a white tile. But better results are
obtained by using a Duboscq colorimeter. The values for lead found by
this method are slightly high, the average excess found being 0*00018
grm. This correction may be applied if strictly accurate results are
required. The following were the results obtained on five oils in compari-
son with the results by gravimetric analysis :—
°/0 found by °/0 found by
Oil Gravimetric Colorimetric Difference.
Method. Method.
1 . . 0-0566 . . 0-0536 . . + 0'0030
2 . . 0-0524 . . 0-0520 . . + 0'0004
3 . . 0-0494 . . 0-0512 . . - 0-0018
4 . . 0-0546 . . 0-0520 . . + 0-0026
5 . . 0-0611 . . 0-0592 . . + 0-0019
Experiments were made on the lead-dissolving power of cassia oiL
10 c.c. of the lead-free cassia oil was introduced into each of 22 test
tubes, together with a strip of bright lead about 1 cm. broad and 6 cm.
long. The tubes were then closed with clean corks, shaken at intervals,
and tested at intervals. The amount of lead absorbed increased with the
time, and reached a maximum of 0'074: per cent, after one month, and
then seemed to remain constant. It is noteworthy that after that
period the lead content exceeds the percentage found in commercial
samples, which is, as a rule, from 0*04 to 0*06 per cent.
OIL OF CINNAMON.
The cinnamon oil (i.e. the bark oil) of commerce is understood to be
the product of distillation of the bark of Cinnamomum zeylaniciim, the
Ceylon cinnamon, a native of that island. The leaves and root bark
also yield essential oils, the former of which is of considerable impor-
tance commercially. The cinnamon tree is a small evergreen tree with
shining leaves and panicles of greenish flowers, of somewhat unpleasant
odour. It is extensively cultivated in Ceylon, from which nearly all
the bark of commerce is obtained. It is also grown in India, Mauritius,
the Seychelles and Jamaica, but Ceylon is responsible for practically
the whole of the cinnamon used. Several varieties are cultivated, but
whether they are merely the same plant slightly modified by the in-
fluence of soil, etc., or not, is uncertain. The Colombo, Negumbo, and
Matura districts in the south-west of the island produce the majority of
the bark, and the famous " cinnamon gardens" of Colombo, which oc-
cupy a considerable space, form one of the great attractions of the
island. The age of the tree, the care devoted to its cultivation, and the
time at which the bark is gathered largely determine the value of the
product. The appearance and size of the " quills," together with their
odour and flavour, determine their value on the market. The small
fragments or chips and the bark of inferior quality are used in Ceylon
LAUEACE^ 133
for distillation, and also form the chief material from which the oil is
distilled in England. The oil distilled in Ceylon is usually obtained by
macerating the fragments of bark in sea-water or strong brine for two
or three days and then subjecting them to distillation. The yield is
from *5 to 1 per cent. The majority of that exported, however, is not
genuine. Either the leaves are added to the bark when distilled, or
cinnamon leaf oil is added to the oil after distillation. The important
difference between the two oils is that the bark oil owes its characteristic
odour to the cinnamic aldehyde it contains, whilst the leaf oil contains
only traces of that body; the chief constituent of the latter oil is eugenol,
the characteristic phenol of the oils of cloves and pimento.
The more delicate odour of cinnamon oil causes it to be preferred
to cassia oil in England, whilst the stronger and coarser odour of the
latter, together with its much lower price, gains for it preference in
many parts of the continent.
In ancient literature there appear many references to cinnamon,
but as these do not appear to mean the cinnamon bark as we know it
to-day, and the latter is so largely a British product, the following in-
teresting details, due to E. M. Holmes,1 may be quoted :—
" Some kind of spice, bearing the name of cinnamon, appears to have
been known from the earliest times, but it was apparently not the Ceylon
cinnamon of the present day, since, according to Tennent (Ceylon,
1859, p. 575) 'in the pages of no author from the earliest ages to the
close of the thirteenth century is there the remotest allusion to cinna-
mon as an indigenous production or even as an article of commerce in
Ceylon'. Hanbury (Pharmacographia, second edition, p. 521) re-
gards the cinnamon of the ancients as the bark now known as Chinese
cassia, and the cassia of the ancients as perhaps one of the thicker and
less aromatic barks of the same group, such as are still found in com-
merce.
" Although cinnamon seems to have been the first spice sought after
in all the Oriental voyages in ancient times, and although both cinnamon
and cassia are mentioned by Theophrastus, Herodotus, Galen, Dios-
corides, Pliny, Strabo, and many other ancient writers on plant products,
it is evident that the barks distinguished by those names were extremely
analogous, since Galen remarks that the finest cassia differs so little
from the lowest quality of cinnamon that the first may be substituted
for the second provided a double weight of it be used. That there was
a distinct difference in flavour of the barks called cinnamon and cassia
recognised by ancient writers is quite clear.
".In 1511 Barbose distinguished the fine cinnamon of Ceylon from
the inferior Canella trista of Malabar (' Canella' being the Portuguese
name for cinnamon). About fifty years later Garcia D'Orta stated that
Ceylon cinnamon was forty times as dear as that of Malabar, and in
1571 he saw branches of the tree at Bristol, in Holland. Cinnamon
was then cut from trees growing wild in the forests in the interior of
Ceylon, the bark being exacted as tribute from the Kings of Ceylon by
the Portuguese. The bark appears to have been collected by the Chalias,
a peculiar caste, who are said to have emigrated from India to Ceylon
in the twelfth century, and who possibly brought the knowledge of the
value of the tree with them from the Malabar coast; in aftertimes they
ip.andE.O.R. (1916), 41.

became the regular cinnamon peelers. The bark previous to shipment
was examined by special officers to guard against frauds on the part of
the Chalias. The cinnamon trade fell into the hands of the Dutch in
1636, but it was not until 1770 that the idea of De Koke of attempting
the cultivation of the tree was carried out, and with such success that
the Dutch were able, independently of the kingdom of Kandy, to obtain
400,000 Ib. of cinnamon annually, and supply the whole of Europe,,
and so ruled the trade that they would even burn the cinnamon in
Holland lest an excessive supply should reduce the price.
" In 1796, when Ceylon was taken from the Dutch by the English,
the cinnamon trade became a monopoly of the East India Company,
and when the kingdom of Kandy fell under British control in 1815, the
wild cinnamon produced there was added to the cultivated kind, but
the annual export did not usually exceed 500,000 Ib. The monopoly
granted to the company was abolished in 1833, and the merchants of
Galle and Colombo were allowed a share in the trade. But a heavy
export duty of one-third or one-half its value, and the competition of
cinnamon grown in Java, and of cassia from China and other countries,
decreased the cultivation in Ceylon. This duty was not removed until
A.D. 1853.
" The Cinnamomum zeylanicum is a very variable tree, and, as al-
ready pointed out, it is difficult to classify the varieties that occur, some
botanists regarding them as distinct species. Dr. Beddome, who was
Conservator of Forests in Madras, states that there are seven or eight
well-marked varieties of Cinnamomum zeylanicum in the moist forests
of South-Western India, which might easily be regarded as so many
distinct species, but for the fact that they are so connected by inter-
mediate forms that it is impossible to find constant characters worthy
of specific distinction. He was, therefore, inclined to regard them as
forms of Cinnamomum zeylanicum, especially since they grew from the
sea level up to the highest elevation, and might owe their differences
to their local environment. They are, perhaps, better regarded from a
horticultural and commercial point of view as deserving a distinct
varietal name, in so far as their products possess a different odour, or a
different chemical composition. There can be little doubt that special
strains might be obtained by careful selection and cultivation, yielding
barks richer in oil, or oil of better quality than others.
" According to Thwaites the best cinnamon is produced from a culti-
vated form (var. a), having large leaves varying somewhat in breadth
and length on the same tree. But the shape of the foliage does not
afford any guide to the quality of the bark, so far as uncultivated trees
are concerned, so that the collectors usually taste the bark before com-
mencing to peel the wild trees. Thus the var. b. multiftorum and
y. ovalifolium yield a very inferior bark, which is only collected for pur-
poses of adulteration.
" In the Herbarium of the Pharmaceutical Society four varietes of
the wild Ceylon Cinnamon tree are represented, collected near Pera-
deniya, which were presented by the late Dr. H. Trimen, at one time
director of the Botanical Gardens in Ceylon. The first variety has
oblong-lanceolate leaves, tapering above, and has a cinnamon taste with
a slight flavour resembling that of Calamus aromaticus. This is the
best kind of the collector, but, of course, not equal to the cultivated
plant.
LAUKACEÊ 135
44
The second variety has rather broad and obtuse leaves, and, in ad-
dition to the cinnamon taste, a slight flavour resembling 'that of pepper.
"The third variety has smaller, rather ovate-lanceolate leaves, and
the fourth kind narrow elongate-lanceolate leaves only half the diameter
of those of the first variety. The extent to which the bark of these
varieties enters into commerce is difficult to estimate, but, as a rule, the
most slender and longest quills are obtained from the finest varieties,
so that the size of the quill may be taken as some guide, but the final
judgment must always be determined by the sense of taste. The con-
ditions under which the best variety of cinnamon is grown are a very
sandy clay soil, or fine white quartz with a good subsoil, and free ex-
posure to sun and rain on an elevation up to 1500 ft.
"The seeds are sown in seed beds and planted out 4 to 6 ft. apart,
and when about 2 or 3 ins. high the tops are cut off, so as to induce
them to form stools, on which four or five shoots are allowed to grow
for about two years, or until the bark turns brown by the formation of
a corky layer. They are not all cut at the same time, but only as they
arrive at the proper stage of development of the bark; they are
then about 6 to 10 ft. high and •£ to 2 ins. thick. The bark is most
easily separated in May and June, and again in November and Decem-
ber, after the heavy rains have caused an increased flow of sap, so that
there are two harvests, one in the spring and another in the latter part
of the year. A long sickle-shaped hook called a ' catty' is used to cut
off the shoots and strip off the leaves, and the shoots are then slightly
trimmed with a knife, the slender parts thus removed being kept separ-
ate and sold as 'cinnamon chips'. The bark is then cut transversely
at distances of about a foot and slit lengthwise, and is taken off the
shoots by insertion of a peculiar knife called a 'mama,' the separation
being assisted, if necessary, by strongly rubbing the bark with the
handle. The quills thus obtained are carefully put one into the other,
and the compound sticks thus formed are firmly bound together into
bundles, and are left for twenty-four hours, during which a heating or
fermenting process goes on, which facilitates the subsequent removal of
the corky layer. This is done by placing each quill on a stick of wood
of suitable thickness and carefully scraping off the outer and middle
cortical layers with a knife. After a few hours the operator places the
smaller quills within the larger, also inserting the small pieces so as to
make up an almost solid stick about 40 ins. in length. These sticks are
kept one day in the shade and then placed on wicker trays in the sun
to dry. When dry the sticks are arranged in bundles of about 30 Ib.
each.
"The cinnamon that comes into commerce from Ceylon occurs in
three forms, viz.: (1) The quills above described; (2) the trimmings or
'cinnamon chips,' which are very aromatic; and (3) coarse bark as
much as an inch thick, the pieces of which are slightly curved longi-
tudinally, and are very deficient in aroma. This bark is derived from
old stools, when they are rooted up, and occurs only in small quantity.
The chips or trimmings, which have only been exported since 1867,
sometimes form nearly a third of the export of bark, and are used for
distilling oil of cinnamon, and are also probably powdered for use in
mixed spice.
" There are other commercial varieties of the bark, such as the .Tel-
licherry cinnamon, which is almost as good as the Ceylon product, and
Malabar or Tinnevelly cinnamon, which is also a product of Southern
India.
" Cinnamon has also been cultivated in Java since 1825, the variety
•cultivated having large leaves often 8 ins. long by 5 ins. broad. It is also
.grown in Brazil, and French Guiana and the Seychelles.
*'But the cinnamon of all these countries is appreciably different
from Ceylon cinnamon, partly, perhaps, from want of careful cultiva-
tion, and the absence of the acquired skill of the regular cinnamon
peeler, and partly from the age of the shoots or branches used, and
partly also from climatic differences, or the altitude at which the tree
is cultivated. Cinnamon bark in powder, especially in the cheaper
•qualities, requires careful examination. Bark that has been exhausted
by distillation is apparently sometimes used; in other cases powdered
cassia is sometimes substituted for it.
" The oil of cinnamon imported from Ceylon usually contains 10 to
"20 or even 50 per cent, of leaf oil, possibly due to the distillation of the
leaves along with the bark trimmings or chips. The oil distilled in this
country from the imported cinnamon chips, which are not mixed with
the leaves, would naturally be free from leaf oil. The presence of leaf
oil in oil of cinnamon bark can be detected easily by dissolving one drop
•of the suspected oil in five of alcohol and adding ferric chloride,
which will produce a pale green colour with the pure bark oil, whereas
leaf oil, or bark oil adulterated with leaf oil, produces a deep blue
colour."
There is some difference of opinion as to the limit values in specific
gravity and cinnamic aldehyde-content in pure cinnamon bark oils,
and it is also certain that the characters of the oil will differ materially
according to the origin of the bark.
The oil distilled on the continent usually has a higher specific
gravity and aldehyde-content than English distilled oil. Much of the
•so-called cinnamon oil of continental origin is undoubtedly adulterated
with artificial cinnamic aldehyde, which would explain these characters,
but oils, probably genuine, with these high figures, appear to owe them
to a different method of distillation from that practised in England.
With these reservations, the characters of pure cinnamon bark oil may
be taken as follows :—
English Distilled. Continental Distilled. Seychelles Oil.
Specific gravity . . 0'995 to 1-040 1'020 to T040 0-943 to 0'975
Optical rotation . . 0° „ - 1° 0° „ - 1° - 1° „ - 3°
Refractive index. . 1-5700 „ 1*5850 1-5850 „ 1-5910 1*5280 „ 1-5335
Aldehydes (bisulphite
method) . . . 53 to 70 per cent. 63 to 76 per cent. 25 to 36 per cent.
Phenols . . . 5 „ 10 „ 4 „ 10 6 „ 16 „
The oil is usually soluble in 3 volumes of 70 per cent, alcohol, ex-
cept in the case of Seychelles oil, which requires up to 10 volumes.
Umney and Bennett, in a paper read before the British Pharma-
ceutical Conference in 1910,1 give the following figures for a series of
cinnamon oils, calling attention to the absence of light fractions in the
oils distilled on the Continent:—
No. 1.—Very fragrant, very sweet, but not a normal oil, imported
•direct from Ceylon :—
.O.R. (1910), 169.

LAURACEÊ 137
Specific Refractive
Gravity. Index at 25C.
Original o i l . . . . •944 1-5178
Fraction 1. 20 per cent. . •867 1-4790
2. 20 . •883 1-4880
3. 20 . •936 1-5115
4. 20 . . 1-008 1-5564
Residue 5. 20 „ . 1-005 1-5748
'No. 2.—Distilled in England , from broken quills :-
Specific Refractive
Gravity. Index at 25°.
Original o i l . . . . 1-016 1-5760
2. 20 . •994 1-5568
3. 20 „ . . 1-032 1-5864
4. 20 . . 1-048 1-5928
Residue 5. 20 . 1-051 1-5746
No. 3.—Distilled in England , from Ceylon " chips "•: —
Specific Refractive
Gravity. Index.
Original o i l . . . . •996 1-5602
2. 20 . •984 1-5442
3. 20 . . 1-027 1-5750
4. 20 . . 1-046 1-5912
Residue 5. 20 ,, 1-051 1-5736
No. 4. —Distilled in England : —
Specific Refractive
Gravity. Index.
Original o i l . . . . . 1-004 1-5615
2. 20 . •993 1-5565
3. 20 . 1-029 1-5826
4. 20 . 1-048 1-5934
Residue 5. 20 . 1-052 1-5729
The following two samples were of Continental distillation, guar-
•.anteed pure : —
No. 5.—
Specific Refractive
Gravity. Index.
Original o i l . . . . 1-021 1-5840
2. 20 . . 1-024 1-5878
3. 20 . 1-042 1-6033
4. 20 ' ,, 1-048 1-6078
Residue 5. 20 . 1-053 1-5955
No. 6.—
Specific Refractive
Gravity. Index.
Original o i l . . . . 1-030 1-5920
2. 20 . . 1-026 1-5883
3. 20 . . 1-040 1-6002
4. 20 . 1-050 1-6068
Residue 5. 20 1-058 1-6070
Three samples of cinnamon oil from bark grown in the Gold Coast
'have: been examined recently at the Imperial Institute.1 The characters
•of these oils, together with those of one previously examined, were as
(follows:—
1
Bulletin, 1919, 17, 189.
Sample No. 1 Sample No. 2 Sample No. 3 Previous

from from from Sample
Assuantsi. Coornassie. Aburi. from
Tarquah.
Specific giavity at 15° . . 1-038 1-042 1-041 1-042

Refractive index . 1-594 1-605 1-603 1-603
Aldehydes, per cent. 74 (approx.) 88 (approx.) 86 (approx.) 86 (approx.)
Soluble in 70 per cent, alcohol Soluble in Soluble in Soluble in Soluble in
2-5 vols. 2-4 vols. 2-4 vols. 2-4 vols.
Adulteration with cinnamon leaf oil is indicated by a higher per-

centage of eugenol, and the deep blue colour yielded with ferric chloride
solution. Artificial cinnamic aldehyde is frequently used as an adul-
terant. The oil should be tested for traces of chlorine as described
under oil of almonds, which, if present, is due to the artificial aldehyde.
If this adulterant, free from chlorine, has been used, it will 'be indicated
by a high specific gravity, refractive index, and aldehyde-content.
Ceylon cinnamon bark oil contains, as its principal constituent, cin-
namic aldehyde; it also contains eugenol as well as the following bodies
which were isolated by Schimmel & Co.,2 who have published the fol-
lowing details in reference to them :—
Methyl-n-amyl ketone : CH3 . CO . CH2 . CH2 . CH, . CH2 . CH3.
The first three fractions, distilling from 32° to 163°, were treated
with bisulphite, and from the crystalline double compound a ketone
was isolated, which was recggnised as methyl-n-amyl ketone. Its.
semi-carbazone melts at 122° to 123°. Two combustions of this body
gave figures corresponding to the formula C8H17ON3:—
Furfurol: C4H3O . CHO.
The mixture of methyl-amyl ketone and benzaldehyde isolated from
the first fractions distilled in the following three fractions :—
1. 54° to 95°. 2. 95° to 165°. 3. 165° to 180°.
Of these No. 2 and 3 gave an intense furfurol reaction with a solu-
tion of aniline hydrochloride in aniline.
Pinene : C10H16.
Fraction 160° to 165° had a pronounced terpene odour. Specific
gravity 0*8695 at 15°; optical rotation aD = - 15° 10'. The nitroso-
chloride of the melting-point 102° to 103°, and the nitrol benzylamine
melting at 122° to 123°, obtained from the former, proved the presence
of pinene.
Phellandrene: C10H16.
Fraction 170° to 174° (42° to 43° at 4 to 5 mm. pressure) had the
specific gravity 0*8614 at 15°; the optical rotation aD was - 5° 4'.
The presence of phellandrene was proved by the nitrite, whose
melting-point 102°, after recrystallisation from acetic ether and cold!
methyl alcohol, rose to 103° to 104°. (aD) = + 11° 39' in chloroform
solution.
Analysis gave the following values :—
1
LAUKACEÊ 139
0-1517 grm. of the substance yielded 0-1019 grm. H2O and 0-3154 grm. C(X.
0-1445 „ „ ,, ,, 17-4 cc. N at 19°, at 750 mm. pressure."
Calculated for C10H16N2O3 :— Found :—
C 56-60 per cent. 56*70 per cent.
H 7-55 „ 7-51
N 13-21 „ 13-65 „
Cymene : C10HU.
For the identification of this body, a fraction boiling at 48°, at 4 to
5 mm. pressure, was first oxidised in the cold with dilute permanganate
solution, for the purpose of decomposing terpenes present, and the- oil
driven over with water vapour was boiled for some time with sodium
in order to remove possible oxygenated bodies. The oil, thus purifiedt
boiling at 175° to 177°, yielded on oxidation with 1 to 2 per cent, per-
manganate solution, with the application of heat, an acid of the melting-
point 154° to 156°, p-oxyisopropyl ben zoic acid, whose mother liquors,
heated with concentrated hydrochloric acid, yielded propenyl benzoic
acid of the melting-point 161° to 162°, which dissolves with difficulty
in water. There was further obtained terephthalic acid, which also
occurs in the oxidation of cymene.
Benzaldehyde : C6H5. CHO.
Some of the oil boiling at 168° to 171° (45° at 4 to 5 mm. pressure)
was treated with bisulphite. The aldehyde regenerated from the bi-
sulphite compound distilled at 174° to 179°, and was found to be heavier
than water. The body was identified as benzaldehyde by the phenyl-
hydrazone melting at 156°, and the semi-carbazone of the melting-point
213° to 214°.
Nonylic aldehyde: C9H18O.
In the fractions boiling above 180° (62° to 92° at 6 to 7 mm. pres-
sure), nonylic aldehyde was detected, in addition to benzaldehyde, cin-
namic aldehyde, and the aldehydes mentioned below. This body,
recently isolated from rose oil, was identified by the nonylic acid
(pelargonic acid), obtained by oxidation of the aldehyde with moist
silver oxide. Three analyses of its silver salt gave the following
figures :—
1. 0-3129 grm. of the substance left 0-1271 grm. Ag.
2. 0-3990 „ „ „ „ 0-1613 „ „
3. 0-2524 „ „ „ „ 0-1040 „ ,,
Calculated for Found :—
C9H1702 Ag:- , - ,
1. 2. 3.
Ag 40-75 per cent. 40-62 per cent.; 40-53 per cent.; 41*20 per cent.
Hydrocinnamic aldehyde : C6H5 . CH 2 . CH2 . CHO.
The semi-carbazone melting at 116° to 118° gave the following values
on analysis :—
1. 0-1501 grm. of the substance yielded 0*0956 grm. H20 and 0-3438 grm. C02.
2. 0-1572 „ ,, „ „ 0-0954 „ „ 0'3617 ,,
Calculated for C10H13ON3 :— Found :—
1. 2.
C 62-83 per cent. 62-56 per cent. ; 62-75 per cent.
H 6-81 „ 7*06 „ 6-74
Eepeated recrystallisation from hot ether raised the melting-point
to 126°. The semi-carbazone prepared for comparison from synthetic
hydrocinnamic aldehyde melted at 130° to 131°. Paucity of material
rendered a definite proof of the identity of the two products impossible.
The semi-carbazone of the melting-point 126°, heated with dilute sul-
phuric acid, gave the characteristic odour of hydrocirinamic aldehyde.
Cumic aldehyde : C10H12O.
From the bisulphite liquors from which the double compounds of
the aldehydes mentioned above had separated as solid products, a
small quantity of an aldehyde was obtained which had the odour of
cumic aldehyde. Its semi-carbazone melted at 201° to 202°, and
yielded on combustion values corresponding to those calculated for
the semi-carbazone of cumic aldehyde.
1. 0-1481 grm. of the substance yielded 0-1002 grm. H20 and 0-3494 grm. C03.
2. 0-1475 „ „ „ „ 0-0991 „ „ 0-3457 „
Calculated for CnH15ON3 :— Pound :—
1. 2.
C 64-39 per cent. 64-35 per cent.; 63-93 per cent.
H 7-32 „ 7-52 „ 7'47 „
• -"The semi-carbazone obtained from cuminol had the same melting-
point ; the mixture of the two products also melted at 201° to 202°.
On oxidation of the aldehyde with moist silver oxide, cumic acid of
the melting-point 114° to 116° was obtained ; a mixture of this acid
with pure cumic acid melted at the same temperature.
Linalol: C10H18O.
The fractions of the boiling-point 80° to 92° (at 6 to 7 mm. pressure),
freed from aldehydes by bisulphite solution, were rectified in vacuo, and<
the portions distilling at ordinary pressure at 195° to 205°, which had a
distinct linalol-like odour, were oxidised in the cold with chromic acid
mixture. The specific gravity of this fraction was 0*8772, the optical
rotation - 8° 32'. The resulting aldehyde purified by the bisulphite
•compound had the odour of citral; when heated with pyruvic acid and
/?-naphthylamine, it yielded citryl-/2-naphthocinchoninic acid of the
melting-point 197°.
Linalyl isobutyrate : C10H17. OCOC3H7.
Linalyl isobutyrate appears also to be present. When saponifying
the fractions boiling between 80° and 111° (at 6 to 7 mm. pressure) and
which had been treated with bisulphite, which on the average gave the
saponification number 20*4, there was isolated, in addition to an acid
with a pungent odour (possibly formic acid), another acid with a dis-
tinct odour like St. John's bread. The silver content of its silver salt
did not, however, agree with the value calculated for silver isobutyrate,
which may have been caused by the presence of formate or acetate.
Eugenol: C10H12O2.
In order to detect eugenol, " heavy Ceylon cinnamon oil" was
shaken with 2 to 3 per cent, potash solution; the oil separated from
the alkaline solution by acid gave the blue eugenol reaction with ferric
chloride, and yielded with benzoyl chloride and soda solution, benzoyl
eugenol of the melting-point 69° to 70°.
Caryophyllene : C15H24.
This sesquiterpene could be detected in one of the last fractions,
boiling at 104° (at 5 mm. pressure).
:—' The specific gravity of the portion distilling at 260° to 261° was
0-9047, the rotatory power aD = - T 20'.
Two analyses gave the following values :—
LAUEACEÊ 141
1. 0-1904 grm.'of the substance yielded 0-2012 grm. H2O and 0-6133 grm. CO,.
2. 0-1240 ,, „ „ „ 0-1284 „ „ 0 3984 „
Calculated for C15H24 :— Found :—
1. 2.
C 88*23 per cent. 87*85 per cent. ; 87*63 per cent.
H 11*76 „ 11*74 „ 11*51
For further identification caryophyllenic alcohol was produced from
it, of which the melting-point was found at 95°. Two combustions
yielded values corresponding with those calculated for an alcohol
C16H,60:-
1. 0*2277 grm. of the substance yielded 0*2366 grm. H2O and 0-6727 grm. CO,,.
2. 01819 „ „ „ „ 0-1923 „ „ 0*5399 „
Calculated for C15H95OH :— Found :—
1. 2.
C 81-08 per cent. 80-57 per cent. ; 80*95 per cent.
H 11-71 „ 11-55 „ 11-75 „
Seychelles cinnamon bark oil l contains cinnamic aldehyde, eugenol,
caryophyllene, phellandrene, cymene, camphor, camphene, /2-pinene,
/-limonene, benzaldehyde, linalol, and nonylic aldehyde (?).
Cinnamon leaf oil differs from the bark oil in consisting principally
of eugenol. The oil has the following characters :—
Specific, gravity 1*043 to 1*066
Optical rotation - 0° 10' „ + 2° 35'
Refractive index 1*5300 ,, 1-5400
Eugenol . . . . . . 70 to 95 per cent, (rarely lower)
Aldehydes 0 to 3 per cent.
It is soluble in 2 to 3 volumes of 70 per cent, alcohol, becoming
turbid on the addition of more alcohol. %; ~^
This oil contains eugenol, cinnamic aldehyde, safrol, benzaldehyde,.
linalol, terpenes, and traces of benzoic acid.
The oil distilled from the bark of the root, according to Pilgrim,
has a specific gravity 0*994 and optical rotation + 50°. It contains
pinene, dipentene, phellandrene, cineol, camphor, eugenol, safrol,
borneol, and caryophyllene.
A Japanese cinnamon oil is obtained from various parts of the plant,
Cinnamomum Loureirii, known locally as Nikkei. The oil from the
leaves of young shoots has the following characters :—
Acid value 3
Ester „ 18-6
Aldehydes . . . . . . . . . . 2 7 p e r cent.
It contains cinnamic aldehyde, citral cineol, and linalol. Oil from
the trunk wood contains cinnamic aldehyde and eugenol, and oil from
the root bark contains cinnamic aldehyde, camphene, linalol, and cineol,
Other cinnamon oils of less importance are as follows:—
The oil from the leaves of Cinnamomum glanduliferum (a Nepal
species) has been examined and found to have the following charac-
ters :—2
Optical rotation - 24° 57' „ - 26° 12'
Acid value 0*34 ,, 0*9
Ester „ 8*8 „ 18-4
„ „ (after acetylation) . . . . 46*9 „ 55*3
1
2
Schimmel's Report, November, 1908, 41; April, 1913, 42.
Schimmel's Bericht, April (1905), 84.
The so-called Culilavan oil is obtained from the bark of Cinna-
mortmm Culilawan, which yields about 4 per cent, of oil. This has a
specific gravity T050 to 1*055. It contains about 60 per cent, of
eugenol, together with some methyl-eugenol and terpineol. It is
soluble in 3 volumes of 70 per cent, alcohol.
The bark of Cinnamomum Kiamis yields about 0*5 per cent, of a
deep golden essential oil having an odour resembling, but less delicate
than, ordinary cinnamon bark oil. It has the following characters :—
Specific gravity . . . . . 1-0198
Optical rotation . . . . . — 1 ° 50'
Aldehydes . . . . . . 8 0 p e r cent, (bisulphite method)
It is soluble in 1 volume of 80 per cent, alcohol. It contains about
11 per cent, of phenols (eugenol).
The bark of Cinnamomum oliveri, the so-called Brisbane " White
Sassafras " tree, yields from 1 per cent,1 to 2*4 per cent, of essential oil.
This has been examined by Hargreaves.
The plant is a handsome tree with grey rough bark, growing in the
scrubs on the North Coast Eailway, Queensland. When distilled in a
current of steam the bark yielded approximately 2*4 per cent, of oil,
having a specific gravity of 1*030 and refractive index 1-5165 at 23°.
On fractionation it was found to contain pinene (12 to 15 per cent.),
^-camphor (18 to 20 per cent.), safrol (25 to 27 per cent.), and eugenyl
methyl ether (40 to 45 per cent.). The oil from the leaves contained
about 25 per cent, of a mixture of terpenes, one of which was identified
as pinene, and the other, which formed a nitrosite melting at 103°, was
probably phellandrene. The leaf oil contained about 60 per cent, of
5-camphor and 15 per cent, of phenols and other substances. The
phenol gave a green coloration with ferric chloride in alcohol, and had
"the formula C10H15O2. No safrol was present, and the author could
not detect the presence of eugenol, cinnamic aldehyde nor cineol,
which had been previously suspected by Baker and Smith.
It contains cineol, eugenol, and cinnamic aldehyde, but the principal
constituent is probably safrol.
The bark of Cinnamomum peditinervium, a tree indigenous to the
Fiji Islands, yields about 1 per cent, of oil, having the following char-
acters :—
Optical rotation . . - 5°
Saponification value . . . . . . 44
„ „ (after acetylation) 115'8
The principal constituent is safrol, but linalol, eugenol, and eugenol-
methyl ether are also present in the oil.
The leaves of Cinnamomum Tamala, a South-Asiatic tree, yield an
•essential oil having the following characters :—
Phenols 78 per cent.
It is soluble in 1 to 2 volumes of 70 per cent, alcohol. The oil con-
sists chiefly of eugenol, together with phellandrene and a little camphor.
1
Jour. Client. Soc., 1916, 751.
LAUBACEÊ 143
The wood of Cinnamomum Parthenoxylum, a Javanese tree, yields

.•about 0*8 per cent, of oil, having the following characters :—
Optical rotation . .' + 1° 22'
It is soluble in 2*5 to 3 volumes of 90 per cent, alcohol. Its principal
•constituent is safrol.
rj; Schimmel & Co.1 have examined the oil'from the Japanese bark known
as Yama-nikkei, a wild so-called cinnamon tree. The oil was of a pale
yellow colour, with an odour reminding one of camphor and of ginger.
It had the following characters :—
Refractive index . . . . . . . 1-47779
Acid value . . . 0-6
Ester ,, 14-8
It contains camphor, terpenes, and, probably, cymene.
.The bark of the Japanese Cinnamomum pedunculatum yields an oil
having the following values :—
Acid value 0
Ester ,, 0
,, , , (after acetylation) . . . . 84-6
The oil contains eugenol, methyl-eugenol, phellandrene, and prob-
ably linalol.
The leaves of this tree, which is known as the Yabunikkei tree, yield
1*4 per cent, of a slightly laevorotatory oil having a specific gravity
1*0665. It contains eucalyptol, eugenol, safrol, and terpenes.2
i The so-called Nepal sassafras, or Nepal camphor tree, is probably
Cinnamomum Ceciodaphne. The essential oil from the wood of this
tree has been examined by Pickles.3
The material used for distillation consisted of billets of heart wood,
free from bark. Its odour was rather that of safrol than camphor.
The yield was 2*95 per cent, on the original wood, or 4'16 per cent, on
the wood after grinding. The oil was of a pale yellow colour, and had
Saponification value 2*8
„ ,, (after acetylation) 7
The oil consists almost entirely of ethers, the well-defined ones being
•safrol, myristicin, and elemicin.
No fraction was obtained below 230°, so that terpenes were clearly
absent. No aldehydes were present. A methoxyl determination showed
the presence of 16*16 per cent, of CH3O. As safrol contains no methoxyl
it is obvious that other ethers are present. A complete fractionation
resolved the oil into the following fractions :—
(1) First fraction from which a crystalline body separated, (2) 233°
to 238° = 7'4 per cent., (3) 238° to 243° = 11 per cent., (4) 243° to 248°
- 5-8 per cent., (5) 248° to 253° = 4 per cent., (6) 253° to 258° = 3-6
per cent., (7) 132° to 137° at 12 mm. = 3'2 per cent., (8) 137° to 142° at
1 2
Report, October, 1914, 54. Jour. Chem. Ind. Jap., 18 (1915), 913.
3
Jour. Chem. Soc. (1912), L4b3.
12 mm. = 4-4 per cent., (9) 142° to 147° at 12 mm. = 5 per cent., (10)
147° to 152° at 12 mm. = 11*4 per cent., (11) 152° to 157° at 12 mm.
= 17-8 per cent., (12) 157° to 162° at 12 mm. = 11-4 percent., (13) 162°
to 172° at 12 mm. = 2'2 per cent.: residue, 1*4 per cent.
The first fraction had the following characters: Specific gravity
1*1059; optical activity 0°. Combustion figures agreed with the formula
C10H10Oi{, and the solidified oil melted at 9°. This was practically pure
safrol. It was definitely identified by preparing from it specimens of
piperonal and safrol-a-nitrosite. The piperonal melted sharply at 37°,
and the nitrosite at 130° to 131°. Fractions 2 and 3 consisted chiefly of
safrol also.
Myristicin was identified in the higher boiling fractions by dissolving
a small quantity in petroleum ether and adding bromine, also dissolved
in petroleum ether to slight excess. A heavy oily layer separated, which
afterwards solidified. By recrystallisation from methyl alcohol, crystals
were obtained of the formula C11H10O3Br4, and melting at 128°. This
agrees with the characters of dibromomyristicin dibromide, and this was
confirmed by converting it into dibromomyristicin. This was achieved
by dissolving it in glacial acetic acid and adding zinc dust. After wash-
ing away the acetic acid, the residue was extracted with ether, and the
ethereal solution evaporated. The residue solidified, and was recrystal-
lised from methyl alcohol, when it was found to melt at 52°. It was,
therefore, proved that myristicin was present in the oil. Further proof
was obtained by oxidising this fraction of the oil, when myristinic alde-
hyde and myristinic acid were obtained.
Myristicin, however, only contains one methoxyl group, whilst the
methoxyl determination showed that more methoxyl was present than
is indicated by the amount of myristicin found. A trimethoxy com-
pound was suspected to be present, but, unfortunately, could not be
isolated in a sufficiently pure state for identification. Trimethyl-gallic
acid was found in the oxidation products, which agreed with the pres-
ence of iso-elemicin in the oil, which had first been treated with alcoholic
potash. Therefore, elemicin was probably present in the original oil.
This was confirmed by preparing the crystalline dibromide of iso-
elemicin, which melted sharply at 88° to 89°. Elemicin, which was
isolated from oil of elemi by Semmler, has the formula C6H2(OCHS)«
(CH2 . CH : CH2).
OIL OF SASSAFKAS.
Oil of sassafras is distilled from the root of Sassafras officinale
(Laurus sassafras of Linnaeus), a native of North America. The tree
is one of the most widely distributed in the continent, being found in
Canada, in all the States east of the prairies beyond the Mississippi, and
in Mexico. In Canada it seldom exceeds 30 ft. in height, but in the
south, especially in Virginia and the Carolinas, it reaches nearly 100 ft.
in height. The root bark (except the outer layers) is the most aromatic
portion of the plant, and from this, as well as the wood, the essential oil
is distilled. The roots may be dug out at any season, but those dug
when the sap is not rising yield the highest percentage of oil. Some of
the large roots weigh nearly half a ton, but the smaller roots are most
valued on account of their higher yield of oil, The typical distilleries in
the neighbourhood of Baltimore use wooden tanks as stills. These are
LAUEACBÊ 145
made of kiln-dried pine and consist of wooden boxes built up of staves,
with a pierced false bottom. The head is provided with a trap-door for
filling by, and a large door is fitted to the bottom of the tank, for the
purposes of emptying. To the upper part of the tank is fitted a copper
head, leading to a condensing coil immersed in cold water. Steam at
from 40 to 60 Ib. pressure is admitted between the true and false bottoms.
The stream of condensed products issuing from the pipe is caught in a
copper funnel with a very long spout which reaches nearly to the bottom
of a 20-gallon copper vessel. The oil being heavier than water collects
at the bottom, leaving the water to flow away at the top of the vessel.
A charge of 10 tons requires about two days to exhaust, and yields about
10 gallons of oil. In parts of Pennsylvania and New Jersey a number
of small isolated distillers, often coloured men, carry on a remunerative
business in this oil. A most primitive still is used^ consisting merely
of a barrel with its head luted on, and its bottom pierced and standing
on a steam generator. A natural elbow-shaped branch, perforated
throughout, serves to carry the distillation products to a metal tube
placed in a trough of running water. The condensed products are
then separated in the usual way. Although the yield of oil is much
lower that when distillation is effected in modern apparatus, the process
is a payable one, as the capital necessary for such primitive distilleries
is very small. Properly treated, about 1 per cent, of oil can be obtained
from the root wood, the bark yielding from 5 to 9 per cent.
Pure sassafras oil has the following characters :—
Optical rotation + 1° 30' to + 4a
Refractive index 1*5280 to 1-5310
Acid value 0
Ester „ 1 to 2
It is soluble in 2 volumes of 90 per cent, alcohol.
A sample fractionated by Schimmel & Co.1 gave the following
results:—
Specific Gravity. Botation.
208° to 216° 1-0066 + 5° 40'
216° 221° 1-0546 + 4° 36'
221° 2^5° 1-0764 + 3° 55'
225° 225° 1*0830 + 2° 57'
2_'5° 226° 1-0877 + 2° 5'
226° 227° 1-0916 + 1° 30'
227° 228° 1-0930 + 0° 45'
228° 229° 1-0942 + 0° 12'
229° 234° 1-0905 - 0° 19'
Residue 1*0770 —
The principal constituent of sassafras oil is safrol, which is also
an important constituent of camphor oil. Safrol is obtained in large
^ quantities from the latter oil, and is sold in a more or less pure state,
usually mixed with the lower boiling fractions of camphor oil as " arti-
ficial sassafras oil ".
The earliest chemical investigation of the oil was by Grimaux,2 who
stated that it consisted of 90 per cent, safrol (q.v.) and 10 per cent, of a
terpene which he termed safrene, with traces of a phenol, which was
afterwards identified as eugenol. A recent investigation by Power and
Kleber8 has shown that "safrene" is a mixture of the terpenes pinene
J 2
Schimmel's Bericht, April, 1906, 62. Comptes Rendus (1869), 928.
3
P harm. Review, 14 (1896), 101.
VOL. I. 10
and phellandrene; dextro-camphor was also found, and a body which
was probably cadinene. The average composition of the oil is :—
Safrol . . 80 per cent.
Pinene .
Phellandreue
Dextro-camphor 7
Eugenol 0-5
Cadinene (?) . 2-5
This oil is used on an enormous scale for soap perfumery. Its
strong odour and low price enable it to be used for the very cheapest
of soaps, not only to give them an actual perfume, but also to cover up
the bad odour of poor quality fats. But its use has been very largely
diminished by the discovery that its active constituent exists in notable
quantity in crude camphor oil. By means of fractional distillation and
freezing (safrol melts at about 8°), this body can be extracted in a state
of almost absolute purity as a water-white liquid of specific gravity over
1-100. In this form it is, in the author's opinion, preferable iri every
way for cheap perfumery to the natural oil of sassafras, and its manu-
facture is now an enormous industry. There are on the market, how-
ever, many samples of so-called "artificial sassafras oil" which are
merely fractionated camphor oil, of specific gravity about 1*070. It
should be renumbered that these are often of low specific gravity and
contain not more than 50 per cent, of safrol, and are far less valuable
than the pure safrol. This body can, of course, be frozen out from
ordinary sassafras oil, but it is much cheaper to obtain it from camphor
oil. Safrol, which is identical with " shikimol" from oil of Hicium
religiosum, also finds an extensive use in the manufacture of heliotro-
pine (piperonal), which is one of its oxidation products.
Sassafras leaves also yield a small quantity (*03 per cent.) of an
essential oil, differing entirely from the oil from the wood. This has
also been investigated by Power and Kleber.1 The oil obtained from
8000 Ib. of leaves was only about 2£ lb., and was of a light yellow colour
and agreeable lemon odour. Its specific gravity was *872, and its optical
rotation 4- 6° 25'. The constituents identified were citral, pinene, phel-
landrene, a hydrocarbon of the paraffin series, a hydrocarbon also found
in oil of bay and called by the discoverers myrcene, and the acetic and
valerianic (isovalerianic ?) esters of linalol and probably of geraniol, and,
possibly, cadinene. No safrol could be detected.
OIL OP LIN ALOE (CAYENNE).

Cayenne linaloe oil, also known as oil of " Bois de Hose Femelle,"
and sometimes as oil of Azelia, is distilled in French Guiana.
The botanical origin of this oil has been a matter of considerable
uncertainty. The following account of the question is due to E. M.
Holmes2 :—
" The fragrant wood from which this oil is derived was apparently
known in Europe in the early part of the last century, although it was
evidently confused with other woods. It has been named by various
writers as Bois de Citron, Bois de Kose male, Bois de Eose femelle,
Boia de Cedre jaune, Bois de Citron da Cayenne, etc. The older
authors, however, distinguished between the woods bearing these names.
a
iPharm. Review, 14 (1896), 101. P. and E.O.R. (1910), 32.
LAUEACE^] 147
Guibort;has*pointed out that the name Bois de Citron has been applied
to three distinct woods.
" 1. The Bois de Citron of Domingo, which was also called Hispanille,
and which he doubtfully identified as that of Amyris balsamifera, Linn.
It occurred in commerce in large blocks 6 to 12 ft. long, 12 to 18 ins.
wide, and 6 to 8 ins. thick. This he believed to have been sold in
Pomet's time as Bois de Santal Citron. (This is the tree that now
yields the West Indian Oil of Sandalwood.)
" 2. A wood in smaller pieces, 4 to 7 ins. in thickness, harder, heavier,
and of a deeper yellow colour, with a weak odour which disappeared on
exposure to the air.
" 3. The Bois de Citron de Cayenne, which he had also seen sold
under the name of Sassaffras. This appears to have been the * Bois
FIQ. 18.—Bois de Rose. Preparation of the wood.

[Roure Bertrand Fih.
de Eose ' of Aublet, and the one which now yields the Cayenne Linaloe
Oil. Planchon states that he has seen the last-mentioned wood sold in
France under the name of Bois jaune de Cayenne, and Bois de Citron
del Cayenne, but prefers to retain Aublet's name of Bois de Eose de
Cayenne, or Bois de Licari, to prevent confusion (Licari kanali being
the native Indian name of the tree in French Guiana). He states,
however, that there are two woods known in Cayenne under the name
of Bois de Eose, the one called by the French inhabitants Bois de Eose
male, and the other Bois de Eose femelle. The former he identifies with
the Licari kanali of Aublet. He describes it as hard and heavy, formed
of interlacing woody layers, as having the flavour and odour of roses,
and a bitter taste. He remarks that in fissures and exposed surfaces,
the wood shows an efflorescence of fine white needle-shaped crystals.
It has a yellow tint darkening with age. The other wood, Bois de Eose
femelle, he identifies with Bois de Cedre blanc, which according to Aublet
is derived from Idea, altissima, now called Protium altissimum, March.
This wood is soft and very light, white or greenish when fresh, but
becomes yellowish on exposure. It possesses quite a different odour, re-
sembling that of citron or bergamot, so that it would be better distinguished
by the name of Bois de Citron.
" The only definite information concerning the botanical sources of the
Cayenne linaloe wood is that given by Aublet in the Plantes de Guiane
Francaise, page 313. —
" He names the tree Licaria guianensis, and gives an illustration of a
leafy twig of the natural size, a portion of which is reproduced. But he
had not seen either flowers or fruit, although he had met with the tree in
different districts, and in consequence, for many years, botanists were
FIG. 19.—Bois de Rose Stills at Cayenne.

[Rmtre- fiertrand Fils.
unable to identify it. He does not apply the name male or female to the
tree, but simply states that it is called Licari kanali by the Galibi Indians,
and Bois de Eose by the French inhabitants. He described it as a large
tree 50 or 60 ft. high, with a trunk 3 ft. or more in diameter, having a
cracked and wrinkled bark of a reddish hue, with a yellowish wood a
little dense (pen compacts).
"This tree, the Licaria guianensis of Aublet, or Cayenne Linaloe,
remained unidentified until 1889 when it was referred by Berlin botanists
in the Jahrbuch des Konigl. Bot. Gard. und des Bot. Museum zu Berlin,
1889, page 378, to Ocotea caudata Mez., a Lauraceous tree of which the
female flowers are still unknown, the plant being dioecious. The wood
of the Cayenne Linaloe, as met with_in commerce in Europe, was sub-
LAUEACE^ 149
mitted to histological examination by Dr. Josef Moeller in 1898. He
describes the wood as beavy, bard, and easily split, tbe fresh surface
yellowish, but redder when older, with the vessels and medullary rays
visible to the unaided eye, but with the annual rings of wood not percep-
tible. The odour is that of rose and citron. Under the microscope the
flinuous medullary rays are seen to consist of one or two rows of cells.
The wood consists of strongly thickened woody fibres in which the vessels
occur in groups of 1 to 3, often surrounded by tracheids. The chambered
parenchymatous fibres are here and there widened out into oil cavities,
containing lemon yellow drops of oil. The cells of the medullary rays
are mostly filled with violet-coloured amorphous masses, but in some
there are yellowish or greenish globules which are soluble in alcohol, and
probably contain essential oil. A characteristic feature of the wood is
that the vessels often have internal cells or tyloses with unusually thick
solerotised walls. The wood resembles that of the Mexican lignaloes in
the grouping and form of the vessels, and in the scattered parenchyma
containing volatile oil, but in the structure of the bark, the character of
the cork cells, the form and distribution of the bast fibres, and the occur-
rence of the oil cells and raphides, it is that of the Lauracece.
" Dr. Moeller examined the wood of several genera of the Lauracece
and found that it came nearest to that of the Ocotea.
" It thus appears from the researches made by the German botanists,
and Dr. J. Moeller, that there can be little doubt that the Licari kanali
tree is the Ocotea caudata, Mez. It should be noted, however, that
Moeller is in error in using the name Bois de Eose femelle for Ocotea
caitdata, and that it should be Bois de Eose male according to Guibourt;
the Bois de Eose femelle being that of Protium altissimum, March."
The average yield of oil from the wood is 1 per cent., and the pure
oil has the following characters :—
Refractive index 1-4610 „ 1'4635
Acid value 0 „ 1*5
Ester „ 3„7
On acetylation for the prolonged period of 4 to 6 hours in three to
four times its volume of xylene (since linalol decomposes by acetylation
without such dilution), the oil shows a total linalol value of 60 to 90 per
cent, or over. It is soluble in 2 volumes of 70 per cent, alcohol.
The principal constituent of the oil is Z-linalol, which was originally
described under the name licareol.
Schimmel & Co.1 have shown that geraniol and J-terpineol are present
in the oil as well as small quantities of cineol, dipentene, furfurol, and
(probably) isovaleric aldehyde, and Eoure-Bertrand Fils 2 have isolated
methyl-heptenone and nerol from it. The last-named give the following
as the composition of the oil:—
Methyl-heptenone traces
Minalol 90*5 per cent.
d-terpineol 5*3 ,,
Goraniol 2-4 „
- Nerol 1-2
On fractionation the oil behaves as follows :—
1 2
Report, April, 1909, 68. Bulletin, October, 1909, 40.
Per Cent. Specific Rotation.

Gravity.
To 100° 0-5
194° to 195° 38-0 0-8625 - 15° 48'
195° „ 196° 39-0 0-8638 - 16" 20'
196° „ 200° 16-0 0-8660 - 14° 32'
200° „ 206° 4-0 - 11° 50'
Residue 2-5 —
— —
A sample having the following characters has been fractionated by

J. C. Umney l :—
Esters 2-6 per cent-
Total alcohols 53-7 ,,
The fractionation results were as follows :—
No. Per Cent. Specific Rotation. Refractive

Gravity. Index.
1 10 0-869 - 15° 1-4615

2 10 0-870 - 15° 30' 1-4620
3 10 0-870 - 15° 30' 1'4624
4 20 0-870 - 16° 1-4630
5 20 0-870 - 15° 1-4632
6 20 0-870 - 14° 30' 1-4642
7 Residue 0-873 — 1-4726
OIL OF MASSOI BABK.

This oil is distilled from the bark of Massoia aromatica, a tree found
in New Guinea, in which it occurs to the extent of 6 to 8 per cent.
Woy,2 who investigated the oil, states that it contains a considerable
quantity of eugenol, with some safrol, a body resembling creosote, and
traces of free acetic acid. It is however, doubtful, whether the so-called
massoi bark of commerce ever consists of one kind of bark only. It is
possible that the principal compound of the commercial bark is that of
a species of cinnamon. He also claimed that it contains3 a terpene not
identical with any already known hydrocarbon. Wallach has, however,
shown that this body is a mixture of the terpenes pinene and limonene,
with perhaps, some dipentene. The oil is a clear yellow liquid of clove-
like odour of specific gravity 1'040 to 1*065, and refractive index about
1-5400.
Schimmel & Co.4 obtained 8*2 per cent, of oil from the bark having the
Optical rotation -f- 1° 45'
2
!P. and E.O.R. (1910), 33. Arch, der Pharm., 223 (1890), 22, 687.
3 4
Annalen, 258 (1890), 340. Bericht, 1917, 33.
5
This is the figure given in Messrs. Schimmel & Oo.'s Bericht, but it appears
incompatible with the presence of 85 per cent, of eugenol, and is possibly a misprint
for 1-0469.
LAUBACE.ZE 151
It contained 85 per cent, of eugenol, the non-phenolic portion of the oil
having a specific gravity 0-9343. Safrol could not be detected.
The essential oil distilled from a bark shipped from the Dutch East
Indies, and known there as "Lawang" bark, has been examined by
B. W. Mann. According to Holmes the bark is one of those passing
under the name of massoi bark, and is] derived , from Cinnamomum
Litrea or an allied genus.
The oil has the following characters : —
Specific gravity .......... 1-0104
Rotation at 20° .......... - 6-97°
Refractive index at 20° ........ 1*5095
Acid value ........... 1*15
Saponification value ......... 43*02
Ester value .......... 41*87
Saponification value of acetylated oil ..... 121*91
A portion of the oil was distilled under reduced pressure (35 mm.),
three fractions being collected : —
Specific
Fraction (i) below 180° 35*5 per cent. . . . 0-9335 1-4828

(ii) 180° to 220° 37'0 „ . . . 1*0103 1-5118
„ (iii) 220° „ 228° 21*0 „ . . . 1-0934 1-5402
A crystalline acid, melting-point 51° to 52°. was separated.
OIL OF KUROMOJI,
The leaves and young twigs of Lindera sericea, one of the Japanese
Lauracea, yield the oil known in commerce under this name. It is a
dark yellow oil with a strong aromatic and balsamic odour, of specific
gravity from *890 to *915, usually about *900, and faintly laevo-rotary.
It has been examined by Kwasnik,1 who states that it contains dextro-
limonene, dipentene, inactive terpineol, and laevo-carvone. The oil, on
account of its comparatively low price, has recently come into some
favour as an aromatic.
Schimmel & Co. have examined a sample distilled by themselves and
found it to contain 9*5 per cent, of esters calculated as geranyl acetate.
Distilled at 4 mm. pressure, it yielded the following fractions : —
Temperature. Rotation.
35° to 40° - 22° 26'
40° 45° - 15° 44'
45°. 50° - 9° 38'
55° 66° - 1°56'
66° 70° + 1°
70° 78° - 3° 56'
78° 81° - 12° 37'
Residues - 6° 10'
Linalol was detected in the oil, as well as geranyl acetate.
According to Shinohara 2 this oil contains 11*41 per cent, of esters;
20'21 per cent, of free alcohols ; 7*71 per cent, of cineol; 50*98 per cent,
of terpenes, with traces of a phenolic substance and free acids; and
aldehydes and ketones 9*17 per cent. The alcohols consisted chiefly of
linalol 11*43 per cent, and geraniol 7*16 per cent.
Schimmel & Co.3 have examined samples of Kuromoji oil distilled
l 2
Arch. der3 Pharm., 230 (1892), 265. Chem. Ind. Japan (1915), 18, 417.
Schimmel's Bericht, April, 1904, 98; and (1907), 67.
from other parts of the plant than the leaves and found them to have
Optical rotation - 14° 29' ,, - 22° 26'
Ester value 27-3 „ 29*9
They found present in the oil cineol, linalol, geraniol, and geranyl
esters.
OILS OP PERSEA.
Per sea gratissima is a tree indigenous to tropical America. The
bark yields about 3*5 per cent, of essential oil having the following
characters :—
Specific gravity . 0'969
It contains anethol and methyl-chavicol (hence its original descrip-
tion as " anise bark " oil).
The leaves yield an oil of tarragon-like odour having the following
characters :—
Specific gravity 0*955 to 0 961
Optical rotation + 1° 50' „ -f 2° 30'
Acid value 0
Ester „ 2 to 4
„ „ (after acetylation) . . . . . 18 ,, 22
The principal constituent is methyl-chavicol, with a little pinene
. and a smalll amount of a solid paraffin.
Babak has examined the essential oil distilled from the leaves of
the so-called " swamp bay," Persea pubescens, a North American tree.
He obtained 0*2 per cent, of oil of the following characters :—
Specific gravity . . 0-9272 at 25°
Acid value. 2-8
Ester 14-5
He found it to contain butyric acid in the free state, and butyric,
valerianic, and oenanthylic acids as esters. Camphor, cineol, and pro-
bably borneol are also present, as well as traces of formaldehyde.
OIL OF PICHURIM.
The cotyledons of Nectandra Puchury major- and Nectandra Puck-
ury minor, two species of Lauracea indigenous to Brazil, and commonly
known as the Para nutmeg, yield about -5 to 1 per cent, of a yellowish-
green oil. According to Muller, the oil contains several oxygenated
constituents not completely identified. Esters of lauric and valerianic
acids are probably present. It distils between 180° and 270° and contains
a terpene and probably a little safrol. The fraction boiling at 256° has
a deep blue colour.
Eoure-Bertrand Fils2 have examined the oil distilled from the
Puchury-major bean alone, which they obtained in a yield of 2*3 per
cent. It has a characteristic odour of sassafras, with a suggestion of
nutmeg and cloves. Its characters are as follows:—
1
U.S. Dept. of Agriculture, Bureau of Plant Industry, 235 (1912), 29.
^Bulletin, April (1920), 4, 1, 35.
LAUKACEÊ 153
'Specific gravity at 17° . 1-0396
Optical rotation . -4° 54'
Acid value . . . . i2-8
Ester value 0
Ester value after acetylation 35-5
It contains isoeugenol, safrol, and possibly cineol.
OIL OF CAPABBAPI.
This oil is yielded by the so-called " canelo ' tree of Colombia,
Jfectandra caparrapi. It varies in colour from pale yellow to dark
brownish-red, and is known in commerce under the names of " white "
-and "black". It is a thick liquid of specific gravity about -915 to
*935, and rotary power - 3°. On exposure to prolonged cold, crystals
of an acid are deposited. The black oil probably owes its colour to
overheating. From a sample of the white oil, Tapia1 has extracted
.an acid of the formula C15H26O3, which crystallises in -white needles,
.melts at 84*5°, and has a rotary power [a\d = + 3°. In addition to this
body the oil contains a sesquiterpene alcohol, C15H26O, which the same
chemist terms caparrapiol. It has a specific gravity '9146, and a rotary
power [a]d = - 18*6°, and boils at 260° at atmospheric pressure. By
abstracting water by means of dehydrating agents, a sesquiterpene
C16H24 is formed, termed caparrapene. This is described as a colour-
less liquid, boiling at 240° to 250°, and of specific gravity -9019 and a
rotary power [a]d = - 2*2°. These compounds require further ex-
amination before they can be regarded as new compounds. The oil is
.used for the same purposes as balsam of copaiba.
OIL OF SPICEWOOD.
The various parts of the plant Laurus benzoin (Benzoin odoriferum),
•commonly known as spice wood or wild allspice, yield aromatic volatile
oils. The plant is a North American shrub, inhabiting damp, shady
woods in localities extending from Canada to Florida. Schimmel &
•Co. state that all parts of the shrub possess pleasant aromatic odours,
which, however, are very different from one another. They obtained:
*(1) From the bark, -43 per cent, of an oil smelling like wintergreen.
Its specific gravity was *923, and its constituents boiled between 170°
And 300°; (2) from the berries, 5 per cent, of an oil of a spicy aromatic
•odour, of specific gravity -855, with constituents boiling between 160°
and 270°; (3) from the twigs, -3 per cent, of an oil smelling like
•camphor and calamus, specific gravity *925; (4) from the leaves, -3 per
xsent. of an oil of pleasant lavender odour, specific gravity '888.
The oil from the bark appears to consist largely of hydrocarbons,
with about 10 per cent, of methyl salicylate. It also probably contains
emnamic compounds.
OILS OF TETRANTHBBA.
Most parts of the plant Tetranthera polyantha v. citrata, a plant
found in Northern India, the Indian Archipelago and Java, yield an
essential oil. The fruit yields from 4 to 5 per cent, of an oil of the
i Bull. Soc. Chem. (1898), 638.
Optical rotation . . . + 6° „ +13°
Aldehydes . . . . 79 to 86 per cent, (bisulphite method).
The principal constituent is citral, with some geraniol, geranyU
esters, and a terpene.
The leaves yield about 5 per cent, of oil having the following
characters :—
It contains from 20 to 35 per cent, of cineol, citral, and an alcohol
which is probably geraniol.
The bark yields from 0*1 to 0*8 per cent, of oil of the following
characters :—
Ester value after acetylation 230° „ 252°
The oil contains, according to Charabot and Laloue, 8 per cent, of
citrol, 10 per cent, of citronellal, 56*5 per cent, of alcohols (geraniol ?)
and 2*4 per cent, of esters.
OIL OF MBSPILODAPHNE PBETIOSA.

This tree is one of the Brazilian Lauracea (also known as Ocotea
pretiosa), and all parts of the plant appear to yield an essential oil.
Laloue l has examined the oil obtained from the twigs and from the
wood. From 1*600 grm. of the dry twigs he obtained 7*9 grms. of oil
(0*5 per cent.), having a pronounced odour of linalol. From 25 kilos
of the wood he obtained 173*2 grms. of oil (0*693 per cent.), which
had an odour recalling that of rosewood and cinnamic alcohol. The
oil (4) was easily separated into a light (2) and a heavy (3) oil. The
benzoic esters of linalol and geraniol were found present. The follow-
ing are the general characters of the oils, No. 1 being the twig oil:—
1. 2. 3. 4.
Specific gravity 0-891 0-954 1-055 0-981

Rotation . + 7° 20' + 8° 48' + 3° 8' + 7° 12'
Refractive index 1-469 1-501 1-545 1-519
Acid value 1-4 0-8 3-5 2-1
Saponification value 13-3 100-7 203-7 128-1
Esters as linalyl acetate ±'6°/o 35-3 — —
Acetyl ester value . 165 205 248 220
Alcohols as linalol . 51-8 66-6 — —
The oil from the bark has been examined by Schimmel & Co.2
The bark yielded 0*83 per cent, of a brown oil of cinnamon-like odour.
Its specific gravity was 1-1200 (15°) and its refractive index 1*52712 (20°);
owing to the dark colour it was not possible to determine the rotation.
It was soluble in 6*5 volumes of 80 per cent, alcohol. It is probable
that its constituents do not include esters, but lactone-like compounds,
for when 1-5 grm. of the oil was saponified, 5 c.c. seminormal potash
1 2
Bull. Soc. Chem., H, 602. Report, April, 1913, 76.
LAUEACE2E 155
solution was first used up, but after neutralisation a fresh \separation of
alkali immediately took place and in the end the saponification value
0 was obtained. Acetylation could not be carried out, as with acetic
anhydride a violent reaction ensued, gas being given off and carbonisa-
tion taking place. The presence of lactones and perhaps also of phenols
is furthermore indicated by the fact that the oil is partly absorbed by
caustic soda, about 65 per cent, of the oil going into solution when
shaken with 5 per cent, solution. Judging by its odour, the portion of
the oil which did not react with sodium hydroxide contains caryo-
phyllene.
OlL OF OCOTEA USAMBARENSIS.
Ocotea Usambarensis, an East African tree known as the Ibean
camphor tree, yields an essential. oil varying according to the part of
the tree from which it has been obtained. The oils have been examined
at the Imperial Institute,1 and found to have the following characters :—•
Oil from
Sapwood. Twigs. Branches.
Yield . . . 0 - 4 per cent. 0-52 per cent. 0-14 per cent.
Specific gravity . 0-9641 0-9681 0-9327
Optical rotation . - 7° 30' - 7° 30' - 0° 28'
Saponification value 30-1 30-1 13-3
The oils from the sapwood and the twigs contained a considerable
amount of cineol. Schmidt and Weilinger2 have examined an oil,
from the bark of the tree, which had the following characters :—
Optical rotation - li° 12'
Refractive index . . 1-4760
Acid value 1-2
Ester value 12-5
He found present in the oil myristic aldehyde, Z-terpineol, and a
sesquiterpene.
OIL OF LITSEA ODOBIFEKA.
The leaves of this plant, which are known in Java as Trawas leaves,
yield an essential oil, which has been examined by Eomburgh. The
Optical rotation - 0° 10' to - 7°
The oil contains nonylene-methyl-ketone, methyl-nonyl-carbinol, and
undecenol.
OIL OF CAMPHOR.
Ordinary camphor oil is a by-product in the manufacture of the
ordinary or " Japan " camphor. The tree yielding this is perhaps best
known as Cinnamomum camphor a, but it has been known under
several other names, such as Camphor*, officinalis and Laurus cam-
phora. The tree is distributed throughout the eastern provinces of
Central China, on the Island of Hainan, and to a very great extent in
Formosa, which is the principal seat of the industry. The Japanese
islands Kinshft and Shikokti. also produce it very abundantly. Accord-
ing to Yoshida, the older trees contain more camphor than the young.
1
Bull Imp. Inst., 9 (1911), 340. *Bericht, 39 (1908), 652.
ones, and those over a hundred years of age are exceedingly rich. The
importance of a regular supply of both camphor and camphor oil is
enormous, and the utter neglect which the Chinese gatherers have
shown to the cultivation of the tree is very surprising. They have
largely succeeded in exterminating it along the seaboard of Formosa,
and are continually making fresh inroads into the inland forests, with-
out any serious attempt to replace the trees destroyed. Attempts, more
or less successful, to cultivate the camphor tree have been made in
many parts of the world, such as Ceylon, the Malay States, Further
India, East Africa, North America, and Italy, but as the world's supply
of camphor and camphor oil practically come from Japan, these at-
tempts have little interest from the essential oil point of view. Chinese
camphor and camphor oil are found in the market to a small extent,
but this trade is steadily declining.
The following details, which give in summarised form a number of
experimental results, are from a report by B. J. Eaton 1 published at
the instance of the Government of the Federated Malay States :—
The first experiments in the cultivation of the camphor tree in the
Malay States were made in 1904 at Batu-Tiga, Selangor, seed having
been obtained from Yokohama for the purpose. The plants flourished
excellently and in 1909 the first camphor was distilled. The raw
material consisted of shoots from five-year-old trees and the result of
the experiment is shown below:—
Material. Yield per cent.
Out leaves 1-17 to 1-22
Small stems 0-06 „ 0-45
Mouldy leaves 1-25 „ 1-47
Leaves and stems . 1-25 „ 1-58
Air-dried leaves 1*10 „ 1-16
,, mouldy leaves 1-54
In each case the distillate consisted of camphor with very little oil.
These experiments were repeated upon a large scale with a larger
distilling apparatus. The raw material consisted of the parts of an en-
tire five-year-old tree.
Material. Yield per cent.
Leaves 1-00
Stems under J in. diameter 0'22
Woody stems over j in. diameter 0*61
Boots 1-10
The distillates consisted principally of camphor; the roots .alone
yielded an oil, which possessed an odour reminiscent at the same time of
camphor and of lemons. Afterwards numerous experiments were
carried out with various distilling apparatus which had been partly
modified.
Finally, the author gives a review of similar experiments in other
countries, the results of which are shown in the table on opposite page.
The crude method of preparing camphor from the trees is as follows.
The tree is felled and the young branches and twigs are chopped up
and packed in perforated jars, and heated over a crude steam-bath.
The steam enters the jars, saturates the chips, and causes the crude
camphor to sublime and condense in earthenware pots placed over the
jars. The crude camphor is sent to the port, and a certain amount of
1
Dept. of Agriculture, Bull. No. 15, February, 1912.
LAUBACEÊ
oil exudes from it which is collected and is known as oil of camphor.
The majority of the oil is, however, produced by distilling the chips
with water in crude stills. The crude product amounts to about 3 per
Distilled Yield Properties of

per Cent. Material. the Distillate.
in by
Ceylon . Willis & Bamber . 1 Leaves and small

Stems —
1 Contained
India . Hooper 1 1 from 10 to
— j 75 per Cent.
J Camphor
German ) rO-06 to 0-1 Branches and thin

E. Africa J Lommel
X 0-22
Twigs
Young shoots } Camphor
Oil
and
Jamaica Duncan 0-61 Wood

0-05
2-37
2*52
1-39
Twigs
Green Leaves
Dried
Dead
„ ( Crude
Camphor
West Indies . Watts & Tempany 0-5 Wood

0-5
0-7
Leaves and Twigs
» >i »
} Camphor and
Oil
Italy . Giglioli 1-2 to 1-5 Green Leaves

2-4 „ 3-0 Dry „ j- Camphor
0-02 „ 0-25 Twigs
America Hood & True 2 Shed Leaves
0-7
2-77
Trees from Shady
places
Trees from sterile,
shady places
) Camphor and
Oil
cent, of the wood used. The oil is drained from the crystalline cam-
phor, of which it retains a considerable amount in solution. This is
transferred to a still, and about two-thirds is distilled off, leaving the
bulk of the camphor in the residue, which is cooled and pressed to
separate more camphor. This process is repeated so long as it pays,
and the residue forms the camphor oil of commerce. From a scientific
point of view, one must regard the whole of the products of distillation
of the wood as camphor oil. This, however, contains so much solid
camphor, or stearoptene, that it is commercially regarded as a separate
product, and the liquid portion of the oil is thus known as oil of cam-
phor. Hence the great variability in its properties and composition.
The crude camphor arrives in England in various states of purity,
and is refined by sublimation, generally with quicklime and charcoal..
Formerly camphor oil was regarded as having no value. To-day, how-
ever, it is used to an enormous extent in the preparation of safrol,
which is used as a cheap perfume, for the manufacture of artificial oil
of sassafras, and for the synthesis of heliotropin.
Camphor oil appears on the market in various forms, and as it is a
by-product, varying in characters according to the substances which.
have been removed from it, and the degree of fractionation which it
has undergone, it is obvious that scientific standards for it cannot be
set up. It is frequently sold on the basis of a guaranteed specific
gravity, which gives a good indication of its general quality. The fol-
lowing may be regarded as the general types of oil to be found in com-
merce :—
LAUEACE.3E 159
1. Crude camphor oil, from which the crystallisable camphor has
been removed as completely as practicable at the distillery, This is a
•deep yellow to brownish oil or\ specific gravity from about 0'950 to
0-998.
2. Heavy camphor oil, black camphor oil, or brown camphor oil is
understood to be the highest boiling portion of the oil, rich in safroP
and containing sesquiterpenes and a small amount of phenols. Its speci-
fic gravity usually lies between I'OOO and 1-040.
3. Light camphor oil is the lowest boiling portion of the oil, and con-
sists principally of terpenes. Its specific gravity usually lies between
0-870 and 0*885, rarely up to 0'910. It is water white and resembles,
turpentine in general characters.
4. The very high boiling fractions, rendered nearly colourless by re-
distillation, of specific gravity from 1*060 to 1*075, are sold as " artificial
sassafras oil". I buu
These details show that camphor oil must be bought for what it is-
worth. No definite standards can be laid down, and only a complete
analysis will show the value of a given sample.
The following figures, however, will be of assistance to the analyst..
The oil is always dextro-rotary, varying from 4- 12° in high gravity
samples to + 20° to + 32° in lighter oils. Light camphor oil, of speci-
fic gravity 0*870 to 0*910, will usually yield the following fractions on
distillation :•—
175° to 180° . . . . . about 25 per cent, to 35 per cent.
180° „ 185* 30 „ ,, 45
185° „ 190° 10 „ „ 15 „
Camphor oil has an exceedingly complex composition. The earliest
scientific investigation of this oil was by Beckett and Wright,1 but the
only conclusions they came to were that it was a complex mixture prob-
ably containing a hydrocarbon of the terpene series, a body having the
composition C10H18O, a liquid containing less hydrogen than camphor,
and much ordinary camphor. Oishi2 described it as a crude oil, of
specific gravity *959, which yielded about 25 per cent, of camphor.
The rectified oil was a colourless liquid of specific gravity '895. He
concluded that the oil was a mixture of terpenes, camphors, and some
of the oxidised hydrocarbons. Yoshida3 separated the oil into four
chief portions, which appeared to be (1) laevo-a-pinene boiling at 150°;
(2) a terpene (limonene) boiling at 172°; (3) camphor; (4) an oxygen-
ated body which he termed camphorogenol. A sample examined by
Trimble and Schroeter4 was separated into ten fractions, each of which
the authors claimed to- be pure compounds, but which were clearly
mixtures in several cases. No fewer than five terpenes were given, and
five oxygenated bodies. Bertram and Walbaum 5 and Schimmel & Co/
have examined the oil since, and to them is due the discovery of the
presence of safrol, which is now manufactured on an enormous scale.
They also showed that Yoshida's camphorogenol had no existence.
The result of their researches shows that the following bodies are
present in the oil: /3-pinene, phellandrene, camphene, dipentene, dextro-
fenchene, dextro-limonene, and bisabolene, cineol, camphor, safrol,
eugenol, terpineol, citronellol, cumic alcohol, borneol, a-terpineol, and
cadinene, with traces of carvacrol, aldehydes and acids, including cap-
rylic acid, and one of the oleic series, with the formula C9H16O2, has
been isolated.
The latest investigation of camphor oil is that of Semmler and Kosen-
l
Jour. Chem. Soc. (1876), 7. *Chem. News, L, 275.
*Jour.
5
Chem. Soc. (1885), 782. -Pharm. Jour., xx., 145.
6
Jour, prakt. Chem., ii., 49 (1894), 19. Reports, passim.
LAUEACEÊ 161
berg1 who have isolated a fraction boiling at 130° to 150° at 10 mm.,,
which contained a new sesquiterpene which the authors have termed
sesquicamphene and which has the following characters:—
Optical rotation . . . . . . . . +3°
It is a bicyclic compound.
They also isolated a sesquiterpene alcohol from the fraction boiling
at 150° to 170° at 10 mm., which on dehydration yielded a hydrocarbon
of specific gravity 0-9138 at 20°, optical rotation 4- 50° and refractive
index 1*50895. This alcohol has been named sesquicamphenol.
The highest-boiling fractions of the oil, after being heated over
sodium, yielded a hydrocarbon fraction with boiling-point 180° to 190°
(11 mm.). Hydrochloric acid gas in ethereal solution was passed through
this fraction, when it afforded a tetrahydrochloride melting-point 129°
to 131°. The hydrocarbon which was regenerated from the hydro-
chloride possessed the following characters: boiling-point 177° to 178°
(6mm.); d2o° 0-8870; aD ± 0; n 1-50339. Combustion showed the
formula to be C20H32; the value (90'6) found for the molecular refraction
also agreed with the formula Co0H32/^ (90*48). This body, therefore,
is a monocyclic diterpene, which has been called a-camphorene by the-
authors. Regenerated, a-camphorene again formed a hydrochloride
melting-point 129° to 131°. Upon being reduced with platinum and!
hydrogen by the usual method, a-camphorene yielded octahydro-a-
camphorene, C20H40, boiling-point 174° to 176° (9 mm.); WD 1*46470.
In addition to a-camphorene the highest-boiling camphor-oil fractions
contain a second diterpene, to which Semmler and Rosenberg have
given the name of /?-camphorene. This camphorene can be regenerated
from the oily residues which are formed in the process of preparing
a-camphorene tetrahydrochloride. This diterpene has the following con-
stants : boiling-point 170° to 180° (7 mm.); ^2q^0'930 [a]D ± 0; molecular
refraction found 88*61; calculation for C20H32/ "T 88*77. Its hydrochloride
remains liquid.
It is a surprising fact that a-camphorene is capable of being built up
synthetically with comparative ease. In order to accomplish the syn-
thesis, Semmler and K. G. Jonas 2 heated myrcene for four hours in a
sealed tube to 250° to 260° by which they obtained a yield of 50 per
cent, of a fraction with boiling-point 175° to 195° (8 mm.) which afforded
a solid hydrogen chloride additive product, melting-point 129° to 130°.
When mixed with a-camphorene tetrahydrochloride obtained from the
blue camphor oil, the melting-point of this body was not depressed;
hence the synthetic hydrocarbon is identical with a-camphorene.
Semmler and Jonas have carried out another interesting synthesis
by heating a mixture of myrcene and isoprene in a sealed tube to 225°.
The result was a yield of about 30 per cent, of a hydrocarbon, boiling-
point 125° to 135° (8 mm.): d18o 0*8685; aD ± 0;ji» 1-49166; molecular
refraction found 68*10; calculation for C15H24/~ 67*86. This body is
without doubt a sesquiterpene and is perhaps identical with bisabolene.
Its trihydrochloride melts at 83°, but when it is mixed with bisabolene
trihydrochloride the melting-point is depressed by 12°. There is na
l
Berichte, 46 (1913), 768. *Ibid., 1566. Schimmel's Report, Oct., 1913.
VOL. I. 11
doubt that the synthesis of c^/cZoisoprene-myrcene represents the first
complete synthesis of a sesquiterpene.
Conversion of myrcene into a-camphorene by heating in a sealed
tube affords an excellent method for detecting the presence of myrcene,
especially when only a small quantity of the terpene is available.
Camphor oil distilled from trees growing in the Federated Malay
States and in Mauritius have been examined by the chemists to the
Imperial Institute.1
The camphor tree was first grown experimentally by the Depart-
ment of Agriculture in the Federated Malay States in 1904, when seeds
obtained from Japan were sown at Batu Tiga, Selangor. The seedlings
were planted out when about six months old at a distance of 10 ft. by
10 ft. The cpnditions at this place appear to be well suited to the tree,
and the growth of the plants is stated to have been equal to that seen
in Japan.
Distillation was first carried out experimentally in 1909, and has
been continued at intervals ever since. In 1911, by using a wooden
still of the Japanese type, a yield of 0*13 to 0*5 per cent, of camphor
and camphor oil was obtained from fresh green prunings. In subse-
quent experiments, using a galvanised iron condenser, fresh prunings
from four-year-old trees gave yields from 0*53 to 0*77 per cent., whilst
air-dry material from two-year-old trees gave 0'60 to 0*80 per cent, with
a metal condenser. The leaves and twigs distilled separately gave the
following results:—
Leaves. Twigs
Two-year-old trees . . 1/4 to 1-6 per cent. O'lO to 0-25 percent.
Four-year-old trees . . 1-3 ,, 1-7 „ 0-13 „ 0-22
The distillate in all cases consisted principally of camphor, with only a
small quantity of camphor oil.
In 1912 specimens of camphor oil and camphor produced in the
Federated Malay States were examined at the Imperial Institute, and
the oil was found to contain 19*3 per cent, of camphor, whilst safrol, the
.characteristic and valuable constituent of the Japanese oil, was absent.
In 1913 a further sample of camphor oil was received at the Im-
perial Institute which consisted of a pale yellow oil containing a con-
siderable deposit of camphor. By cooling the oil to - 12°, a yield of
14*9 per cent, of crystalline camphor was obtained, and the residual oil
possessed the following constants compared with corresponding figures
for the previous sample :—
1913 Previous
Sample. Sample.
Specific gravity (15°) 0'920 0'913
Optical rotation (100 mm. tube) . . . . + 38° 23' + 41° 1'
Acid value 1-1 —
Saponification value . . . . . . 3*6 —
„ ,, of acetylated oil . . . 25*7 —
On fractionating the residual oil about 4'3 per cent, of cineol was ob-
tained, and a further yield of 15'7 per cent, of camphor, giving a total
yield of 30*5 per cent. No safrol was detected, its absence being prob-
ably due to the fact that the oil was obtained from the prunings of
young trees. The camphor oil from the Federated Malay States differs,
i Bull. Imp. Ins*., xiv., 4 ; and P. and E.O.R. (1917), 173.
LAUBACEÊ 163
therefore, from the Japanese oil in that the camphor has not been
separated and that it contains no safrol.
CAMPHOR OIL FROM INDIA.
Simonsen and Ghosel report on experiments carried out on the dis-
tillation of camphor and camphor oil from the leaves of young trees
grown in various parts of India. They obtained from 0*25 to 2*01 per
cent, of camphor, and a varying amount of camphor leaf oil. This oil,
after separation of the camphor, contained d-alpha-pmeue, dipentene,
oineol, terpineol, caryophyllene, and a trace of cadinene, but no safrol.
CAMPHOR OIL FROM MAURITIUS.
The camphor tree is cultivated in the various botanic gardens and
forest plantations, but so far camphor has not been produced on a com-
mercial scale on the island. Distillation experiments have been con-
ducted in recent years, and specimens of the oil obtained have been
•examined at the Imperial Institute. The samples contained a consider-
able quantity of cineol, and differed greatly from the camphor oil of
commerce. They had the following characters :—
1. 2. 3.
Specific gravity (15°) . . . 0-907 0-906 0-925
Optical rotation (100 mm. tube) - 20° 4' - 21° 5' - 6° 20'
Gineol by resorcinol method 69 per cent. 65 per cent. 72 per cent
Five samples received in 1911 were described as follows :—
No. 1.—Camphor leaf oil.
„ 2.— . ,, root „
,, 2.— „ twig „
„ 4.- „ „ „
„ 5.— „ wood ,,
These had the following characters :—
No. 1. No. 2. No. 3. No. 4. No. 5.
Specific gravity at
15° ... 0-9162 0-9508 0-9143 0-9243 0-9164
Optical rotation . - 18° 38' + 13° 36' - 15° 22' - 11° 37' - 11° 26'
Percentage of oil ab-
sorbed by resorcinol 55 per cent. 38 per cent. 54 per cent. not determined
No camphor was separated on cooling to - 10°, but from No. 2 as
the result of fractionation about 6 per cent, of camphor was extracted,
and an appreciable amount of safrol. From the other oils no camphor
could be obtained and no safrol was detected.
These oils from Mauritius differ therefore from the camphor oil of
commerce in containing a considerable quantity of cineol, but no safrol,
and with the exception of No. 2 all were laevo-rotatory, instead of
dextro-rotatory. In view of these results, a comprehensive series of*
distillations were conducted in Mauritius by the chemist to the Depart-
ment of Agriculture. The results confirmed the previous experiments,
and showed that the camphor trees in Mauritius do not yield solid
camphor on distillation, and that the small amount present is readily
dissolved in the oil, and is not readily separated from it. It was thought
possible that the abnormal character of the oils might be due to the
trees not being genuine camphor trees, but specimens examined at Kew
J
P. and E.O.R., 1920, 301.
were found to belong to Cinnamomum camphor a trees. It is stated
that even in Formosa varieties exist which yield oil from which no
camphor separates, and it is proposed that fresh trials should be made
in Mauritius, and that fresh seed should be procured from selected trees-
in Ceylon or the Federated Malay States which are known to yield
camphor.
The essential oil of Hernandia peltata, a Madagascar plant known
as a false camphor, has been examined by Schimmel & Co.1 From the
stem wood from 1*03 to 2*06 per cent, of oil was obtained, having the
Specific gravity at 15° 0'958 to 0-963
Eefractive index 0-49695 ,, 1-50111
It contains from 75 to 80 per cent, of aldehydes (mostly dihydro-
cumic aldehyde), with traces of free acids and a small amount of esters.
In addition to dihydrocumic aldehyde, the oil contains a small amount
of the aldehyde myrtenal, which has a specific gravity 0*986 at 20°,
specific rotation + 13*6°, and refractive index 1-50618. The root wood
yielded 0'5 per cent, of oil having a specific gravity of 0P9667, optical
rotation -f- 126° 15', refractive index 1-50383 and aldehyde content
92'5 per cent. The whole fruit gave 0*5 per cent, of oil of specific gra-
vity 0-9528, optical rotation + 50° 10', refractive index 1*49554, and
aldehyde-content 49 per cent. The almond-like seeds gave T38 per
cent, of oil, having a specific gravity 1*0044, optical rotation + 87°, re-
fractive index 1-50614, acid value 7*3, and aster value 110*4. The fruit
oil does not appear to contain any dihydrocumic aldehyde. It is pos-
sible, however, that the aldehyde present is perillic aldehyde, and not
dihydrocumic aldehyde.
The leaves of the Japan camphor tree also yield an essential oiL
According to Hooper the yield is about 1 per cent., the oil having a
specific gravity about 0*930 and optical rotation + 4° 32'. It contained
10 to 15 per cent, of camphor. Another specimen contained 75 per
cent., and had a specific gravity -9314 and optical rotation + 27°. There
seems not to be much difference between this and the ordinary camphor
oil. The roots yield an oil of quite similar character. A sample dis-
tilled by Schimmel & Co. had a specific gravity "975, and consisted
chiefly of camphor—the liquid portion resembling commercial camphor
011 very closely.
OILS OF SHO-GYU AND Yu-Ju.
There are found in Formosa two trees which closely resemble the
ordinary camphor tree, which are known as Sho-Gyu and Yu-Ju, and
whose actual botanical differences from the true camphor tree are not
yet determined. Both these trees yield essential oils which have been
investigated by K. Nagai,2 who gives the following details of them :—
" ' Sho-Gyu Oil' is the name given to an essential oil with an aro-
matic odour, disti'led from a perennial tree popularly called by the
natives ' Chiun-Gru,'* growing chiefly in the highland forest regions of
Formosa. On account of its not producing camphor through the reg-
1
2
Schimniel's Bericht, April,
1915, 54.
3
Publication of the Monopoly
Bureau, Formosa. Taihoku, 1914.
Chin* or Shd = camphor tree; GH or Gyu = ox.
LAUEACEÊ 166
n
ular process of manufacture, the Chiu -Gu (Sho-Gyu), the source of the
oil has played so far a very insignificant part in the industrial world,
utterly failing to draw the attention of those connected with the in-
dustry. While the Sho-Gyu tree exhibits some features in common
with the Shiu-Shd tree,1 as' in the lack of solid camphor or in other
superficial indications, the latter luxuriates in the camphor-tree regions
and has aroused wide public interest as a highly valuable material for
industrial researches: whereas the former, thriving exclusively in an
isolated region beyond that of the camphor tree, was completely over-
looked, and even the essential oil it produces has hardly been the sub-
ject of discussion.
" Seen at a distance, the Sho-Gyu tree presents a strong resemblance
to the camphor tree. The natives in the locality of Kosempo (Kah-sien-
po) call it ' Gu-Chiun,' a term presumably corrupted from the savage
tongue. At the present stage of investigation, however, its scientific
name and classification are still a matter of conjecture and doubt, but,
following the opinion of Dr. Hayata based upon several specimens col-
lected in Kosempo, Taiko (Tai-fu), and Arisan (Ali-soan) districts, we
may assume that it belongs to the Laurinece. The * black camphor'
tree, as it is generally called by the manufacturers of camphor, appears
to be the same tree. There is, however, no proof of the assumption,
nor has any report ever been made regarding the collection of its
flowers—the blooming season is said to be from February to March;
hence it is evidently impossible to determine its scientific name. In
view of a future study of a collection of flower specimens, the discussions
are restricted here to the scope of external forms. The following are
the results of observations made on the tree as it flourishes in the thick
woods along the length of the old Arisan road (Ki-Jcoan-tdi) in Kagi
(Ka-g'i) prefecture, and in the vicinity of Heishana (Pi&ng-chia-nd)—a
mountainous region extending from a locality popularly called ' Cross
road' (Chap-ji-lo) up to the elevated region of Arisan, where conifers
thrive.
"The trunk of the Sho-Gyu tree usually attains a height of 40 to 50
shaku? the circumference of the larger ones often measuring, at a man's
height, from 15 to 20 shaku ; and the growth of the tree is, speaking
generally, uniform and vigorous with no dwarfed specimens. The
greater portion of the trunk is generally covered with lichens and
mosses, with a few exceptions where the bark is much exposed; also,
many are entwined by vines and climbers. The bark when compared
with that of the camphor tree, suggests at a glance a somewhat brownish-
red colour. The large branches have smooth longitudinal wrinkles and
furrows upon the greyish-white surface. A piece of Sho-Gyu wood
from Tebutegai was found equally covered with lichens and other para-
sites in spots upon the bark, displaying identical features in its external
peculiarities with specimens from Arisan. The longitudinal section of
the branch shows that the heartwood seems rather white in comparison
with that of the camphor, Shiu-Shd, or Yu-Ju tree. The wood is soft
and sappy, seemingly containing much moisture, and the solidity
naturally failing to equal that of the camphor tree, it can be sawed or
chopped with comparatively little exertion. Despite the extreme dif-
ficulty of distinguishing the tree from the camphor tree by mere observation
1 2
Shiu = stinking. 1 shaku = 0-994 ft. = 0'303 m.
of external appearances in the living states, the test can readily be
accomplished by shaving small pieces from the sapwood portion—parti-
cularly the root—of the two trees, and judging from their inherent odour.
This test has incidentally proved to be the most reliable method of detect-
ing the difference between the two. A simpler method, however, is the
examination of the leaves. The leaves of the Sho-Gyu tree have a
LAUEACEÊ 167
bright deep-green colour upon the surface and are much thicker than
those of the camphor tree (a large one often measuring about 13 cm.
in length, and 4'5 cm. in width), and are slender in form with a parti-
cularly pointed apex which frequently reaches a length of 1 cm. On
examination of a specimen collected in November, a large terminal leaf-
bud about 1 cm. in length and 0*5 cm. in diameter was found on the
upper end of every young branch, by observation of which the tree may
also be distinguished from the camphor tree. The latter test, however,
being only practicable when the shoots with leaves attached are within
reach, it is highly advisable to employ the former test at the same time,
in order to ensure a correct determination."
The following are the physical characters of a number of samples of
this oil, distilled from the wood of trees collected in various localities.
j Colour-
Place Reaction
of No. Colour. d at t°. aD at tot nD at ^ Odour. with
Origin. Mercuric
Sulphate.
Shinchiku 1 Faint yellow 0-908 9 4- 29-50i 5 1-47753 20£ Slightly re- Trace?
I sembling oil
of savin
»t 2 Colourless 0'910 ,, j-f- 23-25 }, 1-47478 19J Sweetish, and +
as that of j
No. 1 i
t| 3 Light yellow 0-911 + 15-88 1-47468 20 Same as No. 1 Trace?
4 »» 0-951 4- 14-90 1-48713 18 ,, 4-
M 5 Colourless 0-912 + 24-55 1-47567 20 Recalling oil 4-
of nutmeg
f , 6 Faint yellow 0-900 !+ 23-50 1-47665 19 — 4-
» 7 M 0-927 + 22-30 1-48133 20 — +
» 8 Colourless 0-945 + 18-50 1-48471 20£ — + i
9 Faint yellow 0-933 ? 4- 15-25 1*48094 20 — Trace? i
1f 10 » 0-914 , 4- 22-20 1-47694 19 — 4-
Kosempo — Yellow 0-910 11 + 34-45 ii 1-48326 ,, Reminding of +
1 oil of nutmeg
Arisan 1 Light yellow 0-968 25 + 12-83 25 1-49466 26 — Trace ?
>» 2 Faint „ 0-939 ,, 4- 14-40 ,, 1-48490 25£ — (?)
3 Light ,, 0-993 26 4- 8-55 26 1-50088 25 — Trace ?
4 Almost col- 0-949 M + 16-65 25 1-48971 ,} — n
ourless
5 0-993 $} + 13-25 „ 1-50227 »? — -f
»» 6 Bright red 0-925 25 4- 12-40 ,, 1-47912 Recalling oil (?)
of sweet
marjoram
Tebutegai 1 Faint yellow; 0*943 J? + 19-31 25* 1-48971 ,, — +
3 Light „ 0-970 26 + 16-251 „ 1-49693 25* — (?)
4 Faint ,, 1-030 4- 7-75 26 1-51302 25** — 4-
5 Light „ 0-993 + 11-05 ,, 1-50237 „ Reminding of Trace ?
oil of nutmeg
8 ,, 0-965 » + 13-34 „ 1-49429 „ — +
13 » 0-908 >i + 24-25! „ 1-47987 ., +
The acid value of this oil is always below 1 and the ester value does
not exceed 2'5. A large amount of free alcohols, however, is present,
the ester value after acetylation varying from 46 to 129.
The following constituents were identified in the oil : formaldehyde,
sabinene, dipentene, a-terpinene, y-terpinene, terpinenol-4, geraniol,
citronellol, safrol, and eugenol.
" Yu-Ju oil is a term applied to an essential oil which is obtained
from the so-called " Oil Tree," indigenous to southern Formosa, and
which is closely related to camphor oil in its properties. Its failure,
however, to yield camphor in the course of production is the chief
feature differing from camphor oil, and evidently indicates the reason
why the natives call the mother-tree, " Iil-chhiu " or " Oil Tr,ee".
Similarly, the term " Yu-boku " or " Yu-bun-boku," as frequently ap-
plied by the Japanese to the tree, which yields only a little camphor,
and a large quantity of oil, suggests the inconspicuously small percent-
age of camphor obtainable.
The Yu-Ju tree is identical, in its external forms, with the camphor
tree (Cinnamomum camphora Nees et Eberm.), and the camphor
manufacturers mainly rely, as the sole means of discriminating between
them, upon the odour of shavings taken from the root, outside of which
no particular method seems to be in current use.
The following are the physical characters of a number of samples of
Yu-Ju oil:—
Place of Origin. No. Colour. d at t°. a
o at t°. 7i
D at t°.
Shinkoko 1 Light golden-yellow 0-945 13 + 29-22° 13 1-47596 19

2 ,, 0-942 »» + 18-88° v 1-47457 »)
3 j 0-951 12 + 19-50° 12 1-47869 20
4 0-967 13J + 22-48° 13£ 1-48191 19
5 ,, 0-966 i» + 24-42° ,, 1-48568 20
6 Golden-yellow 0-961 14 + 29-85° 14 1-48045 20*
7 »j 0-961 M + 26-52° J} 1-48326 21
8 Light golden-yellow 0-963 15 + 26-95° 15 1-48326 »»
9 Golden-yellow 0-955 » + 25-35° » 1-47850 20
10 Light golden-yellow 0-947 + 27-30° 1-47567 19J
Daipauriau 11 (a) Slightly greenish- 0-954 16 + 21-00° 16 1-47694 19
yellow
J? 11(6) Slightly greenish 0-953 J5 -h 21-30° }J 1-47694 tt
• yellow
,, 12 (fl) Slightly greenish- 0-972 ,, + 30-80° j, 1-47746 n
yellow
,, 12(6) Light golden-yellow 0-951 Jt + 28-30° n 1-48278
I |
This oil contains furfurol, a-pinene, camphene, /2-pinene, cineol,
camphor, a-terpineol, and safrol.
OIL OF SHIU.
The Shiu-Sho tree, which thrives in the camphor regions of Formosa,
in association with the camphor tree, but which was formerly considered
as of no value, has recently been shown by scientific investigations to
be capable of playing a prominent part as material for the production
of camphor or linalol, furnishing a fair example of possible develop-
ment.
The tree is closely related to the camphor tree, but its exact botani-
cal relationship is not known.
The oil distilled from the wood of this tree is rich in linalol, and has
an odour recalling that of linaloe oil. It has the following characters :—
Specific gravity . . . . . . . 0'870 t o 0*895
Eater „ . 0-5 „ 30
Total alcohols as linalol 65 to 90 per cent.
LAUBACEÊ 169
l
An oil reported on by Keimazu is described as having a specific
gravity 0*9279, and optical rotation + 17°, but this appears to have been
mixed with camphor oil, so that his researches as to the constituents
present must be accepted with reserve. The principal body present in
the oil is the alcohol linalol (Keimazu found formaldehyde, d-a-pinene,
•cineol, dipentene, apopinol (impure linalol ?), camphor, eugenol, and
•safrol).
OIL OF GUIANA SANDAL-WOOD.
The wood of a tree growing in French Guiana, and known there as
•sandal-wood, yields an oil which has been investigated by Jean card and
•Satie.2 The tree is, in all probability, one of the Lauracea, but its
botanical relationships are unsettled. -
By steam distillation the wood yields oils very variable in character,
as will be seen from the following tables :—
Sample Sample General

A. B. Limits.
Specific Gravity at 15° C. 0-9630 1-0122 0-963 to 1-0122

Rotatory Power - 2° 10' - 0° 30' + 0° 30' to - 6°
Solubility {80 per Cent. Alcohol 1-1 0-8 0-8 „ 1-1
I'" »» >» 10 1-6 1-5 „ 12
Saponification Value 58-8 14-7 13 „ 65
,, ,, after Acetylation 114-1 72-1 65 „ 117
On fractionation in vacuo the following results were obtained :—

A. B.
Below 155° C. at 20 mm 27*4 per cent. 18 per cent.

155° to 160° C 59 80
Above 160° 13-6 2
The 155 to 160° fraction has the following constants :—

A. B.
Specific Gravity at 26° 1-024 1-037

Rotatory Power . . . . - 4° 20' - 6°
Solubility in 70 per Cent. Alcohol . 1-8 1-8
The oils appear to contain a common constituent in varying pro-

portion, which would explain the observed variations. To render this
more evident, the authors classified a large parcel of the wood into
three portions as follows :—
Wood No. I. consisting of branches.
Wood No. II. consisting of trunks split into two or three pieces
according to length.
Wood No. III. consisting of logs from which the bark had been
removed, and having the appearance of Indian sandal-wood.
1 2
Jour. Pharm. Soc. Japan (1903), 253 and 258. P. and E.O.R. (1911), 79.
The constants of the oils distilled from these several lots were :—
No. I. No. 11. No. III.
Specific Gravity at 15° . 0-9665 0-9806 0-9968

Rotation . . . . . - 6° 16' 0 + 0° 30'
Solubility in 85 per Cent. Alcohol 0-4 0-4 0-3
80 1 1 0-9
' )> 75 » » 1-7 10-8 20
Saponification Value 44-1 46-9 13-3
,, ,, after Acetylation 92-4 96-6 65-8
By careful fractionation they separated a body having the following,

characters :—
Boiling-point . . . . . 158° t o 159° a t 2 0 m m .
Rotatory power - 6°
Solubility in 70 per cent, alcohol 1 in. 1-6
65 2-7
60 6-5
This body, which is termed marionol, combines with sodium withi
evolution of hydrogen, and is probably a tertiary alcohol. On adding
to 10 grms. marionol dissolved in 10 grms. petroleum spirit, 1 grm. of
sodium, a brisk evolution of hydrogen takes place in the cold. On
warming over a water-bath solution is complete in the course of a day.
OIL OF CALIFORNIAN BAY.
The leaves of the so-called Californian Bay, a large forest tree
common on the mountains of California and the Pacific slope, yield
from 2*5 to 5'5 per cent, of an essential oil. The tree is also known as
the mountain laurel, the sassafras laurel, and the Californian olive.
Botanically it is Umbellularia Californica (Oreodaphne California)*
Acid value 3 „ 5
Ester ,, 5 „7
,, ,, (after acetylation) 50
It is soluble in 1'5 to 2*5 volumes of 70 per cent, alcohol.
Heaney * states that the yield of oil from the leaves is 4 per cent..
He claimed to have found about 35 per cent, of a hydrocarbon and 65
per cent, of an oxygenated body, which he termed oreodaphnol, in the
oil. This body, however, has never received confirmation, and it is very
doubtful whether the hydrocarbon he obtained was pure. He 2assigned
to it a specific gravity '894 and boiling-point 175°. Stillman, on the
other hand, claims that it contains terpineol and an oxygenated body of
the formula C8H12O, which he named umbellol.
Modern investigations by Power and Lees, however, have not con-
firmed this statement. These chemists have isolated from the oil the
following constituents : (1) Traces of free fatty acids including formic
acid; (2) 1'7 per cent, of eugenol; (3) 6 per cent, of pinene ; (4) 20 per
cent, of cineol; (5) 60 per cent, of a new unsaturated cyclic ketone of a.
2
*Amer. Jour. Pliarm., 47 (1875), 105. Berichte, 13 (1880), 630.
LAUKACEjE 171
mint-like odour boiling at 220°, of specific gravity 0*858 and optical
rotation - 37°. Its formula is C10H14O, and Power has named it
umbellulone; (6) a small quantity of safrol ; (7) 10 per cent, of eugenol
methyl ether.
The ketone umbellulone is a liquid, which when purified by re-
generation from its semicarbazide-semicarbazone has the following
characters:—
Refractive index . . . . . . 1-48325
Boiling-point 219° to 220° at 749 mm.
It forms a semicarbazide-semicarbazone and a normal semicarbazone
the former melting at over 200° and the latter at 240° to 243°. It forms
a dibromide melting at 119°.
OIL OF LAUREL LEAVES.
The leaves of the sweet bay, Laurus nobilis, yield from 1 to 3 per
cent, of essential oil, having an odour somewhat recalling that of caju-
put. The oil has the following characters :—
Specific gravity . 0-915 to 0-945 (usually 0-915 to 0*930)
Optical rotation . - 15° to - 22°
Refractive index . 1-4670 „ 1-4775
Acid value . . . . 1 „3
Ester „ 20 „ 50
The oil is soluble in 1 to 3 volumes of 80 per cent, alcohol. Some
oils, French oils especially, are soluble in 3 to 10 volumes of 70 per cent.
alcohol.
The following table, showing the characters of oils distilled in various
districts, is due to Schimmel & Co.::—
Ester
ttD W
Acid Ester No. Solubility.
^15°. - D20°, No. No. after
Acet.
0-915
to
- 15°
to
1-469
to
up
to
28
to
58-3
to
1-3 vol. 80 p.c.
)>-in alcohol, some (esp.
French) samples in
0-932 - 18° 1-477 2-0 43 77-7 3 to 10 vols. 70 p. c.
J alcohol. |
Fiume 0-9281 - 13° 52' \ 1-47156 1-0 o-i .q ) in 2-5 vols. 70 p. c.
f alcohol and more.
( 0-9177 - 16° 40' ! 1-46862 up 29-8 36-2 •\ in 1 vol. 80 p. c. alco-
Corfu . .{ to to ! to i to to to l hoi, mostly in 3 to 6
{ 0-9211 - 21° 40' 1-47107 1-5 43-8 82-5 j j vols. 70 p. c. alcohol.
Cyprus 0-9405 - 5° 40' 1-47372 1-6 o* Q OK r i) in 2 to 3 vols. 70 p. c.
ja-d y&-b j aicohol and more.
0-916 - 14° 1-46516 21 S in 1 to 2 vols. 80 p. c.
up 43-2 1 alcohol, some in 4
Palestine J to to to to to to
0-924 - 21° 1-46575 2-2 49 81-4 f to 7 vols. 70 p. c.
J alcohol.
Asia Minor . 0-9-68 - 15° 50' 1-46575 0-8 în 1 vol. 80 p. c. alco-
34-8 60-1 / hoi and more.
Dalmatia 0-9268 - 14° 36' — \in 2-5 vols. 70 p. c.
^ alcohol.
Syria 0-9161 - 14° 20' — — — — in 1 vol. 80 p.c. alcohol.
This oil contains a-pinene (?), principally as the laevo-rotatory variety,
and phellandrene. The oxygenated constituents include cineol, Z-linalol,
geraniol, eugenol, and methyl-eugenol. The highest boiling fractions
contain a lsesquiterpene and a sesquiterpene alcohol.
Molle has investigated the oil and found present acetic, isovalerianic,
and isobutyric acid in the free states. He also found a small quantity
of esterified eugenol. Acetic, valerianic, and caproic acids were found
in the form of esters, as well as a monobasic acid of the formula
C10H1402 melting at 146° to 147°. Molle does not confirm the state-
ment of Wallach, that pinene is present in the oil.
The leaves of a Java laurel tree, known as Trawas leaves, yield,
according to van Komburgh 2 an essential oil having the following
characters :—
Optical rotation - 0° 10' „ - 7°
The principal constituent of the oil is nonylene-methyl-ketone, which
forms a semicarbazone melting at 116°. The oil also contains methyl-
nonyl-carbinol and a second alcohol undecenol-l-ol-10 (specific gravity
0-835 ; boiling-point 233°).
PROTEACE/E.
OIL OF STIBLINGIA LATIFOLIA.
3
H. V. Marr has examined the oil distilled from the whole of the
shrub, Stirlingia latifolia, and finds it to have the following characters :—
BoiliDg-point 195° to 205°
Optical rotation +0*2°
The oil solidifies in crystals almost completely at 12°.
The oil was found to consist almost entirely of acetophenone.
The shrub grows freely in low-lying, sandy country from Geraldton
to Bunbury in Western Australia, and should form a useful source for
acetophenone.
MYRISTICE>E.
The only oils belonging to this family of the slightest importance
are those distilled from the nutmeg and mace, which are the products
of Myristica fragrans, the seed of which consists of the well-known
nutmeg enclosed in a testa, which is covered by an arillus (according
to Planchon, this latter is only an extension of the exostome, and there-
fore a false arillus, or arillode). The arillus is known as mace, and from
both this and the nutmeg essential oils are distilled.
This natural order is confined to the tropics, and Myristica fragrans
is the typical plant yielding the ordinary nutmeg. It is an inhabitant
of the Moluccas, being specially abundant in the Banda Isles, three of
which, Lontar, Pulo, Ai, and Pulo Nera, are often known as the " Nut-
meg Islands ". At one time the Dutch attempted to confine the culti-
vation to these islands, and when supplies were rather more abundant
than usual the excess was said to have been burned in order to keep up
prices. The seed was however conveyed elsewhere by the " nutmeg
1
2
Inaugural Thesis, Basle, 1903.
3
Konink Akad. Weten. Amsterdam, 28, 10 (1911), p. 325.
Private communication to the author.
MYEISTICEÊ 173
bird," who in swallowing the fruit digested the mace, but voided the
nutmeg uninjured. The tree has been successfully introduced into
numerous other places, for example, Java, Penang, Bourbon, Zanzibar,
and Singapore.
The following interesting account of this spice is acknowledged to
the Chemist and Druggist:—l
"The plant Myristica fragrans Houttuyn (N.O. Myristicacece), is a
member of the single genus containing over a hundred species which
comprises this order. It is, however, the only species of Myristica
worth cultivating, the seeds of other species having little or no aroma.
The true nutmeg-plant is a somewhat bushy, medium-sized tree of
pyramidal habit, attaining a height of 30 to 60 ft. In Penang the trees
are somewhat more compact, and not more than 20 or 25 ft. high.
The spreading branches are usually produced nearly to the base of the
trunk. The lanceloate leaves, which have a rather long, pointed tip,
are arranged alternately. They are about 4 ins. long and 2£ ins. wide,
somewhat leathery in texture, and with a dark green shiny upper sur-
face. The trees are usually unisexual, but occasionally they- bear both
staminate and pistillate flowers. The pendulous, shortly stalked male
flowers are produced in small cymes, arising a little above the leaf.
The female flowers are borne in similar positions, but usually not more
than one to three occur in a single influorescence. The light yellow
perianth of the flower is bell-shaped, with three lobes, and encloses
either a column of about twelve united stamens or a conical green
ovary terminating in a pair of white stigmas. The beautiful fruit is a
fleshy drupe, somewhat variable in form, resembling an apricot. The
smooth husk is about half an inch thick and of a pale orange-yellow
colour. It bears a groove down one side, along which it splits open
when the fruit is quite ripe. When the pericarp splits open it discloses
a bright crimson arillus, closely enwrapping the seed. This, which on
drying yields the mace of commerce, is somewhat leathery in texture,
cut into narrow finger-like portions of irregular size. The seed-coat is
deep brown, polished, and marked with shallow grooves corresponding
to the flaps of the mace. Inside this woody and brittle shell is the
kernel, or nutmeg itself, which is about an inch in length. When fresh,
the nutmeg practically fills its testa, but shrinks on drying and then
rattles. Our first photograph gives an excellent idea of the structure
of the fruits and the shape of the leaves.
" Nutmegs are cultivated in plantations from fresh seed sown in the
shell, as they soon lose their germinating power. Seeds that rattle are
rejected. The plants are generally cultivated near the sea, below the
1000 to 1500 foot level. Nutmegs have been grown on soil of widely
different types with remarkable success. In the Moluccas the rich
volcanic soil is a sandy friable loam, with a large proportion of vege-
table matter, while in Penang and Wellesley Province the trees grow
in a yellow loamy clay on the steep slopes of the granite hills; sodden
or excessively dry ground is, however, fatal to nutmegs. The tempera-
ture of Banda ranges from 76° to 92° F., that of Trinidad being some-
what similar; but in the Straits Settlements it is rather less regular.
A rainfall of 90 to 100 ins. per annum, well spread over the different
months^ with dry spells of not more than four or five days' duration, is
]
C. and D. (1914), 160.
the ideal for yielding heavy crops. Drought has a marked effect in
lessening the yield, while excessive spells of wet weather render the
plants liable to attacks of parasitic fungi. In the Banda Islands the
trees are shaded by canary-nut trees (Canarium edule), but in the
.Straits Settlements no shade-trees are planted.
" The seeds are usually planted in nursery beds of well-dug and
manured soil in rows from 12 to 18 ins. apart, at a depth of about 2-J
ins., with some form of shading, and frequent watering. The seeds
germinate in about a month or six weeks. They are planted out some
•six months later, when about 6 ins. high, at a distance of 26 to 33 ft.
apart, in holes which have been dug some 4 to 6 ft. wide and 3 ft. deep.
Some planters prefer germinating the seed in bamboo pots, as this faci-
litates their transport when they are big enough for planting out. The
sex of the plant is not known until it flowers, some seven or eight years
later. Male trees are usually exterminated with the exception of one
male to ten or twelve female trees, which is sufficient for pollination
purposes. Manuring is practised on the poor clay soils of the Malay
Peninsula, but in the rich ground of the Banda Islands this does not
appear to be necessary. The trees become productive when about eight
years old, but it may be earlier in the Straits Settlements, where the
whole life-history is shorter than in the Moluccas. They are at their
best when about thirty years old, and continue to fruit well for twenty
years more ; but trees over seventy years have been known to give good
crops. The fruits ripen in about six months from flowering. The fruit
may be allowed to fall, but it is more usual to gather it by hand. For
this purpose a long rod bearing a small basket, open at one side near
its apex, on which are two downward pointing prongs, is used to collect
the fruit in the Banda group. The nutmeg is caught between the
forked prongs, and as it is pulled off it falls into the basket. In the
Straits Settlements, where the tree is low, a hooked stick is used to
knock off the fruits. The operation of collecting nutmegs is shown in
our second photograph. The trees blossom and fruit throughout the
year, but it is customary to gather two crops a year, usually in May
and June, and again in August and September. The spring crop is
said to yield the best nuts. Only quite ripe fruits are collected. A
labourer in a full season can gather 1000 to 1500 nuts a day, and in the
Banda Islands two or three trees keep a man employed all day, while
in Malaya he may pluck from forty to fifty trees a day. In Grenada
the fruit is allowed to drop from the trees as it ripens. Good trees
should average from 1500 to 2000 nuts a year.
" The husk is usually stripped off on the spot by the collectors, and
the nuts forwarded to the drying-sheds. There the mace is carefully
removed either by hand or with the aid of a knife. It is dried in one
piece (' double-blade') or after separating into two halves (' single-
blade '), the former being preferred owing to its better appearance.
The mace after removal is flattened by hand or sometimes between
boards. In Banda, coolies tread upon it to flatten it, and it is then
dried in the sun in flat baskets or on mats or trays of bamboo, this pro-
cess taking from two to four days. The brilliant red colour changes to
a duller orange and finally to golden-yellow, while at the same time it
becomes horny and brittle. At nightfall the mace is placed in a drying-
shed to avoid wetting by dew. In rainy weather the drying is done by
artificial heat, usually over a smokeless fire of charcoal. The practice
MYRISTTCEJE 175
of sprinkling the mace with sea-water before putting it to dry seems to

have been discontinued; only in cases of mildew is it occasionally
washed with sea-water. It was claimed that this process kept the
mace in a more pliant condition.
" The nutmegs, after removal of the husk and mace, are dried in their
shells, as otherwise they run great risk of being attacked by beetles.
In the Banda Islands, where nutmegs are handled in large quantities,
it is usual to dry them over a charcoal fire in a drying-house. The
stands have four or five shelves arranged about 8 ft. from a slow char-
coal fire. The layers of seed spread on these are constantly turned and
eventually shaken on to the next lower shelf. Too much heat results
in shrivelled seed of less value. The drying takes from three to six
weeks, when the nutmeg rattles in its shell. In Malaya the seeds are
often merely dried by exposure to the sun in trays of basket-work.
Sometimes the seed is exported in the shell (e.g. from Minahassa and
Amboyna), but it is customary to remove the testa, which amounts to
About one-quarter of the weight of the seed, before packing for export.
The cracking of the shell is done with a wooden truncheon or hammer,
or by striking several seeds spread on a kind of drumhead with a flat
board. The seeds must be struck on end, otherwise oil-cells are rup-
tured, and a black bruise formed. The seeds are then sorted, the broken
nuts being first removed, then thin nuts, and finally the large sizes are
•separated from the medium. In Grenada the shelling is done by a
machine. This consists of a high, narrow box in which revolves a
wooden wheel whose rim forms a series of deep sockets. The nutmegs
are fed into the sockets, and the force with which they strike the bottom
•cracks the shell. The shelled seed is liable to attack by beetles, and in
the Moluccas it is still usual to dip nutmegs in milk-of-lime or sprinkle
them with powdered lime to protect them. In the Banda Island the
nutmegs are packed for about three months in wooden bins filled with
lime and water of the consistency of mortar. Tradition states that this
operation was intended by the Dutch to prevent the seed (which is
killed by the drying alone) from germinating. Mace is usually
packed in teak chests, containing about 280 lb., the mace being
trodden in. The graded nutmegs are packed in casks or in chests
which have been slightly smoked inside and coated with lime and
water."
The mace is detached from the seed with a knife, and is easily separ-
ated from it. When fresh it is of a brilliant red colour, tough and
leathery, and possessing a flavour recalling that of turpentine. It is
then dried in the sun.
Nutmegs are often imported limed, i.e. treated externally with lime,
with the object of preventing their germination and keeping them pro-
tected from insects. Although quite unnecessary, this practice is ap-
proved of in certain markets, so much so that Penang nutmegs, the
most valued in the London market, which are imported unlirned, are
frequently limed in London for re-exportation. The nutmegs of other
species are often used, both as nuts, mace, and oil, as a substituent or
adulteration of the ordinary product. Amongst these are the Bombay
nutmegs (from M. Malabarica) and New Guinea nutmegs (from M. Ar-
jgentea).
The mace from the Bombay nutmegs is sometimes used to adulter-
ate ordinary macs. It is of very faint flavour and of no pungency.
Nutmegs yield from 6 to 15 per cent, of essential oil, having the
Specific gravity -865 to 0'9250
The oil is soluble in 1 to 3 volumes of 90 per cent, alcohol, and
about 60 per cent, should distil below 180°. The oil usually carries-
over a little of the fixed oil of nutmeg on distillation, but this should be
present in traces only. Good oils, evaporated on the water-bath for
twelve hours should not leave more than from 1 to 2 per cent, of non-
volatile residue.
The oil distilled from the mace very closely resembles that from the
nutmegs, and distinction between the two is often impossible. Oil of
mace, however, rarely has a specific gravity below 0'890, and sometimes
it may reach 0'932.
The two oils are practically identical in their composition, and the
following details may be taken as referring to both oils. The early
researches on this oil may be disregarded, the chemistry of the oil
having now been carefully worked out by Power and Sal way l and by
Semmler,2 and to a lesser extent by other chemists.
The terpenes, a-pinene, camphene, /?-pinene, and dipentene have all
been isolated from the oil, as well as a small amount of cymene. The
body termed myristicol by Gladstone and Wright has been shown by
Power and Sal way to be a mixture of alcohols in which terpineol, lina-
lol, geraniol, and borneol have been identified. A small quantity of
terpineol-4 is present, and also a minute amount of safrol. An alde-
hyde smelling of citral, and yielding a /2-naphthocinchoninic acid melt-
ing at 248° has been isolated. Eugenol, isoeugenol, and formic, acetic,
butyric, and caprylic acid in the form of esters are all present in small
amount, as well as a non-volatile monocarboxylic acid of the formula
C12H17COOH. A body has been described by several chemists under
the name myristicin, but this name should be retained for the body
isolated by Semmler3 and examined by Thorns.4 This body has the
formula C11H12O3 and is, chemically, 4-allyl-6-methoxy-l . 2-methylene
dioxybenzene, of the constitution
O
G6H2(OCH3). C4H7
According to Power and Salway the quantities of the various constitu-

ents present are as follows :—
Eugenol a n d isoeugenol . . . . . . 0*2 p e r cent.
Pinene a n d camphene . . . . . . 80
Dipentene 8
A cohols about 6
Safrol 0-6
Myristicin . . . . . . . . . about 4
The other bodies are present in traces only.
5
3
Jour. Chem. See., 91 (1907), 2037. '2
4
Berichte, 23 (1890), 1803 ; 24 (1891), 3818,
Ibid. Ibid., 36 (1903), 3446.
MONIMIACEÊ 177
MONIMIACEÊ.
OIL OF PABACOTO BAKK.
Paracoto bark is derived from an unknown species of Monimiacea,
which is found in Bolivia. Its essential oil has a specific gravity 0*9275
and optical rotation - 2° 8'.
The oil has been investigated by Jobst and Hessel who isolated two
hydrocarbons which they termed a-paracotene and /3-paracotene, to
which they assigned the improbable formulae C12H18 and C11H18 re-
spectively. Cadinene and methyl-eugenol are present in the oil.
Wallach and Eheindorff2 consider that the two hydrocarbons above
mentioned were not pure individuals, but mixtures of terpenes. The
three bodies described by Jobst and Hesse as a-, /?-, and y-paracotol
have also been found to be mixtures of methyl-eugenol and cadinene.
OIL OF ATHEBOSPEKMA MOSCHATUM.
The leaves of Atherosperma moschatum yield from 1*7 to 2*7 per
cent, of essential oil, which has been investigated by Miss M. E. Scott.3
The tree flourishes in the gullies among the Victorian ranges, and a
yield of from 1*7 to 2-65 per cent, of oil is obtained from the leaves.
During the steam distillation of the oil it was noticed that the first
portion of the oil (about 30 per cent.) was lighter than water, whilst
that which subsequently passed over was heavier than water and sank
to the bottom of the vessel. The oil has the following characters :—
Opt.cal rotation + 7-5°
The oil was distilled at 100 mm. pressure and divided into 16
fractions boiling from 99° to 183°. The optical rotation of fractions
1 to 9 ranged from + 61*7° to 1*7°, the remaining fractions being optically
inactive. The specific gravity of the first fraction was 0*881 and that
of the last 1*034, the corresponding refractive indices being 1*4687 and
1*5322.
The sixteen fractions were subsequently subjected to repeated frac-
tional distillation at ordinary pressure and the following compounds
identified:—
(a) Pinene C10H16. A fraction was obtained boiling at 157° to 158°.
Its combustion figures agreed very closely with the formula C10H16, and
it yielded a hydrochloride melting at 130° and a nitrosochloride melting
at 103°.
(b) Camphor C10H16O. Five successive fractions yielded a solid
substance, which, when freed from adherent oil, was white and crystal-
line, and possessed the characteristic odour of camphor. It melted at
174° to 176°, and had a specific rotation of 4- 40*66° in 10 per cent,
alcoholic solution. Its combustion figures agreed with those for C10H16O.
(c) Eugenol methyl ether C11HJ4O2. The greater portion of the oil,
after repeated fractionation was a pale yellow liquid distilling at 251°
to 252° at 755 mm. pressure. Its combustion figures agreed with the
formula CnH14O2, and it formed a bromo derivative melting at 75°. Its
identity with eugenol methyl ether was therefore established.
l 2
Annalen, 199 (1879), 75. Ibid., 271 (1892), 300.
3
Jour. Chem. Soc. (1912), 1612.
VOL. I. 12
(d) Safrol C10H10O2. The fractions- of the oil with the highest
boiling-points were found to be a mixture of eugenol methyl ether with
another compound, the separation of which was effected by repeated
fractional distillation. A nearly colourless liquid was obtained which
boiled at 233°, and had the characteristic odour of safrol. Its combus-
tion figures agreed well with those for C10H10O2. On exposing the oil
to the temperature of boiling ammonia, it congealed to form white silky
needles, melting at 8° to 12°. It was thus definitely identified as safrol.
The composition of the oil is therefore as follows: Eugenol
methyl ether, 50 to 60 per cent.; pinene, 15 to 20 per cent. ; camphor,
15 to 20 per cent.; and safrol, 5 to 10 per cent.
BOLDO LEAF OIL.
The dried leaves of Pneumus Boldo yield about 2 per cent, of an
oil resembling wormseed oil in odour. The oil has the following
characters:—
Optical rotation . . . . . . . . - 2° ,, + le
Kefractive index . . . . . . . . 1-4798
Acid value 1 to 3
Ester ,, 11-2
According to Schimmel & Co.1 this oil contains ^-cymene, cineol,
and ascaridol, C10H16O2. Traces of terpenes and phenols are also
present. Tardy has reported on an oil under this name which had a
specific gravity 0*876, and optical rotation - 6° 30'. It contained
a-pinene, dipentene, terpineol, cumic aldehyde, eugenol, sesquiterpenes,
and acetic esters.
EUPHORBIACEjE.
OIL OF CASCARILLA.
The barks of Croton Eluteria and Croton Caacarilla form the Cas-
carilla bark of commerce. These trees are found in the Bahamas, and
the bark on distillation yields from 1 to 3 per cent, of essential oil. The
Acid value 3 9
Ester ,, 5 12
(after acetylation) 67 72
The oil is soluble in all proportions in 90 pei cent, alcohol. The
older researches on this oil are not to be depended on. According to
Fendler2 the oil contains about 2 per cent, of free acids, of which the
principal is cascarillic acid, C^HgoOg, melting at - 18°, and isomeric
with undecylenic acid. Palmitic and stearic acid were also found in
traces. Traces of a phenol, Z-limonene, an unidentified terpene, cymene,
and two sesquiterpenes were also found present in the oil. A sesqui-
terpene alcohol C15H23OH was identified in the high boiling fractions.
OIL OF CATHETUS FASCICULATA.
Cathetus fasciculate Lour. (Phyllanthus cochin-chinensis Muell.)
one of the Euphorbiacese which is found in Southern China and in
1 2
Schimmel's Bericht, April/1888, 43. Arch, der Pharm., 238 (1900), 671.
SANTALACE^ 179
Cochin China, contains an essential oil of which a small sample from
Annam, where the plant is known by the name of Bruyere d'Annam
has been examined by Schimmel & Co.1 The oil was of a bluish green
<x>lour, and possessed an odour reminding somewhat of cajuput oil.
Its constants were as follows : di5o O8897; ao - 4° 34'; ^020°; 1*47544 ;
acid value T9; ester value 3 - 7; ester value after acetylation 44'8 = 12'7
per cent. C10H 8O ; soluble in O5 volume a.m. of 90 per cent, alcohol.
Among the constituents is cineol, which was identified from the iodol-
compound (melting-point 112°). Judging by the odour of the oil,
cymene and linalol are also present.
A sample of oil previously examined under the name of " Essence
de Bruyere du Tonkin" possessed precisely similar characters, with the
exception of the rotation : di5o 0*8787; aD + 10° 32';raD2o°1'47009; acid
value 1-7; ester value 5*9; ester value after acetylation 45*2; soluble in
0*3 volume a.m. of 90 per cent, alcohol.
According to Murat, the plant is in full flower in the month of
August. Distillation commences towards the end of January and gives
different results according to the localities in which the cutting is made
whether the plants be fresh or dry. The essential oil obtained is then
tjometimes of a green colour, sometimes of a pale yellow colour. This
divergence would appear2 to be attributable to the nature of the soil.
Koure-Bertrand Fils have examined each of these two varieties of
the oil of Cathetus fasciculata. They possess the same odour, slightly
•camphoraceous, but recalling at the same time that of cineol. The
yellow oil is slightly less dense than the green oil; it differs from it,
further, in its lower optical rotation and acidity. Below are the
analytical characters of the two samples :—
Green Oil. Yellow Oil.
Specific gravity at 15° C. . 0-8871 0-8862
Optical rotation . - 4° 40' - 1° 22'
Rotation of the acetylated oil - 4° 36' - 1° 14'
Solubility in 85 per cent, alcoho 4-5 volumes and over 3 volumes and over
Acid value . . . . 4-2 0-7
Saponification number 8-4 4-2
Ester number 4-2 3-5
„ „ (after acetylation) 42-0 49-5
About 30 per cent, of cineol was found in the oil.
SANTALACEÊ.
OIL OF SANDAL-WOOD.
The sandal-wood oil of commerce, which is largely employed in
medicine and perfumery, is the product of distillation of the wood of
Santalum album. This oil is known as Bast Indian sandal-wood oil.
Probably the Macassar oil is the product of the same tree. Santalum
album is a native of the mountainous parts of India, but is especially
found in Mysore, Malabar, and Coimbatore. It likewise grows on the
•Coromandel coast, in Madura and Assam. In the Madras presidency
and Mysore it is now grown on Government plantations from seeds.
The wood is sold at the Government auctions, and the latest classifica-
tion—for the various woods are not of equal value—with which the
-billets are marked is as follows :—
1 2
Report, April, 1914, 102. Bulletin, April, 1914, 3, 9, 5.
1. First Class Billets (or Vilayat Budh). Consists of thoroughly sound billets
weighing not less than 20 lb., and not exceeding 112 pieces to the ton.
2. Second Class Billets (or China Budh). Consists of slightly inferior billets weigh-
ing not less than 10 lb., and not exceeding 224 pieces to the ton.
3. Third Class Billets (or Panjam). Consists of billets having small knots, cracks,
and hollows, weighing not less than 5 lb., and not, exceeding 448 pieces to the
ton.
4. Clwtla (or billets of short length). Consists of short sound pieces, no limit as to
weight or number.
5. Chat Badala. Consists of billets with knots, cracks, and small hollows at either
end weighing not less than 10 lb., and not exceeding 240 pieces to the ton.
6. Bagaradad. Consists of solid pieces, without limit as regards dimensions, weight,
or number.
N B.—Billets of Classes 5 and 6 are not planed nor are their edges rounded off.
7. Roots (First Class). Consists of pieces weighing not less than 15 lb., and not
exceeding 150 pieces to the ton.
8. Roots (Second Class). Consists of pieces weighing not less than 5 lb., and not
exceeding 448 pieces to the ton.
9. Roots (Third Class). Consists of small and side roots below 5 lb. in weight.
10. Jugpokal (First Class) (or Badala). Consists of hollow pieces weighing not less
than 7 lb., and not exceeding 320 pieces to the ton.
11. Jugpokal (Second Class). Consists of hollow pieces weighing not less than 3 lb.
12. Ain Bagar. Consists of solid, cracked, and hollow pieces, weighing not less than
lib.
13. Ceria (or large Chilta). Consists of pieces and chips of heartwood weighing not
less than £ lb.
14. Ain Chilta. Consists of pieces and small chips of heartwood.
15. Hatri Chilta. Consists of heartwood chips and shavings obtained by planing.
16. Milwa Chilta. Consists of pieces and chips having in fair proportions heartwood
and sapwood.
17. Basola Bukni. Consists of small heartwood and sapwood chips.
18. Sawdust (or Powder). Obtained in sawing the santal-wood.
Santalum album is a small evergreen tree, which grows to a height
rarely exceeding 40 ft. It is found in the drier parts of Mysore, Coim-
batore, and Salem, and as far south as Madura and as far north as
Kohlapur. It flourishes best at elevations of 2000 to 3000 ft. above sea
level. Being somewhat delicate, it flourishes best when protected by
hedges or jungle. When cultivated outside these districts it loses much
of its highly valued aromatic heartwood. The cultivation is a Govern-
ment monopoly.
Much discussion has taken place as to the best method for growing
sandal-wood, and the general conclusions arrived at appear to be as fol-
lows : The sandal-fruits are gathered whilst fresh, spread out to dry and
then stored in a dry place until the commencement of the rains. The
seed is then sowed on tilepot beds and covered with a mixture of sand
and leaf mould. The seedlings are not transplanted for a year, and are
then kept shaded from the sun. Transplanting commences in the fol-
lowing year, as soon as the ground is thoroughly moistened by the early
rains. The tree is a slow grower, and in the first year or two often
suffers from animal depredations. During the first year the trees in the
nurseries should grow to about 10 ins. in height, and by the end of the
second year should, if well attended to, attain a height of 2 ft. The tree
attains its commercial maturity, that is, the age at which it pays to cut
it down, in from twenty-seven to thirty years. By this time the heart-
wood is well developed—as a rule, at about 2 ins. below the surface;
and after this time the growth of the wood is so slow that it does not
repay the attention bestowed upon it, and the commercial interests in-
volved are such that it now pays to cut the tree down. It is generally
felled at the end of the year, the largest roots, which contain a very fine
SANTALACEJE 181
quality of wood, being cut out, and the tree is stripped of its bark, and
the logs thus obtained are sent to various depots, where they are cut into
the usual sized billets and dressed and sorted for the auction sale. The
pieces which are straight and have most heartwood fetch the highest
prices, as they contain the highest percentage of essential oil.
The amount of oil obtained from the wood is very variable, generally
from 1*5 to 6 per cent., but usually from 3 to 5 per cent. Briggsl has
described the following method of determining the amount of oil in the
wood and gives the results of twelve samples of wood obtained from My-
sore, representing the various grades there obtainable. Sandal-wood oil
contains a large amount of fixed oil as well as volatile oil, and both are
extracted by ether. The essential oil cannot be separated by distillation
in vacuo, unless glycerine is added to assist in carrying over the last
traces of oil. The latter can be extracted from the glycerine by means
of chloroform. The process adopted was as follows : 100 grams of the
finely powdered drug was extracted in a Soxhlet for twelve hours, or until
completely exhausted. The ether extract was transferred to a 200 c.c.
distillation flask with side neck, and the ether evaporated by the aid of
a current of air. Twenty-five c.c. of glycerine was then added, and the
mixture distilled in vacuo until about 25 c.c. distilled over. Seventy-five
c.c. of water was added to the distillate, and the mixture extracted with
three successive quantities of 25 c.c. of chloroform, and the chloroform
evaporated over a water-bath with the aid of a stream of air. The
residual oil was then dried in a vacuum desiccator over sulphuric acid
and weighed. From 3*5 to 8*3 per cent, of oil was obtained from the
twelve samples of wood. In the course of this investigation it was noted
that the oil obtained by this method had an optical rotation of - 18° or
over, whereas the same wood, distilled with steam, yielded an oil with an
optical rotation of - 14° or less. It was also noted that the oil obtained
by the assay method above described was readily soluble in 5 volumes
of 70 per cent, alcohol, whereas the oil obtained by the ordinary distilla-
tion method required more than 5 volumes. The results of distilling
500 grams of sandal-wood with steam, showing the characters of each
day's running, are of particular interest:—
Specific Refractive Optical Solubility in 5 Vols.

Gravity. Index. Rotation. 70 per Cent. Alcohol.
1 0-969 1-5017 - 12° 34' Soluble at 40° to 50°

2 0-970 1-5020 - 12° 22' 25°
3 0-972 1-5027 - 12° 46' 25°
4 0-974 1-5030 - 12° 54' 25°
5 0-976 1-5035 - 13° 10' 25°
6 0-978 1-5037 - 12° 36' 25°
7 0-978 1-5045 - 11° 8' „ 25°
8 0-9795 1-5046 - 10° 4' 26-5°
9 0-981 1-5046 - 9° 10' 29°
10 0-9815 1-5046 - 8° 20' 32°
11 0-982 1-5045 - 7° 45' 35°
12 0-983 1-5045 - 7° 8' 38°
13 0-983 1-5046 - 6° 34' 44°
The refractive index and specific gravity gradually increased whilst

1
Jour. Ind. Eng. Chem. (1916), 420.
the optical rotation steadily decreased after the first five days. The
solubility, with the exception of the first day's running, was constant
until the eighth day, after which it decreased. In order to show the
effect of prolonged boiling, a sample of oil having an optical rotation of
- 20° 40' was boiled continuously for several weeks in a glass flask with
reflux condenser, and another portion with a 10 per cent, solution of
sodium chloride. The optical rotation steadily decreased to - 13° 16'
in three and a half weeks, and the change in the brine solution was
much less, being reduced to - 16° 40' in the same length of time. It
is concluded that prolonged contact with water brings about a decided
change in the composition of sandal-wood oil and greatly reduces the
optical rotation.
East Indian sandal-wood oil is a thick, colourless or slightly yellow
liquid, of powerful aromatic odour, and having the following characters :—
Acid value 0-5 to 2 (rarely up to 6)
Ester „ 6 to 20
Total alcohols (as santalol, 90 to 97 per cent.
These values may, of course, be slightly exceeded when the oil is not
a complete distillation. As it is very heavy and takes many days for the
wood to be exhausted on distillation, it is not uncommon to find com-
mercial specimens which in fact represent the principal fractions of the
oil, when the optical rotation may sink to about - 11°.
The oil is soluble in 6 volumes of 70 per cent, alcohol; indeed nearly
all pure samples are soluble in 5 volumes and many in 3*5 to 4 volumes.
The oil is frequently adulterated with small quantities of castor oil
and other oils. These adulterants present no difficulty when present in
appreciable amounts, but when present in small quantity are exceedingly
difficult to detect. Oils which only just satisfy the minimum require-
ments as to solubility, specific gravity, optical rotation, and santalol
value should be regarded with considerable suspicion. Glyceryl acetate
is sometimes used as an adulterant, and is detected by the high ester
value of the sample (for which see Vol. II.). Benzyl alcohol is also
sometimes used, but this will be indicated by an abnormally high
" santalol value " and also by the distillation results. With pure sandal
oil nothing distils below 280° at ordinary pressure (or 150° at 14 mm.),
whilst benzyl alcohol distils at a much lower temperature. Cedar-wood
oil is indicated by its insolubility in 70 per cent, alcohol, by its low
" santalol value," and by its high optical rotation. Further, a consider-
able distillate is obtained below 280°. The so-called West Indian sandal
oil (q.v.) is also a somewhat common adulterant, which is easily detected
by the alteration of all the constants of the oil, as well as by its de-
creased solubility and " santalol value ".
Three samples distilled in Mauritius have been examined by Schimmel
& Co.1 Two of the samples were distilled from heartwood, the third from
sapwood. As will be seen from the subjoined table, all three were re-
markable for their high santalol-content, and their other characters also
agreed with those of East Indian oil, except that the optical rotation was
a little higher:—
1
SANTALACEÊ 183
1
Colour. d15o.
Acid Ester Ester Ester v. Total
after Santalol.
«D. 2,jO . v. v. Santalol. Acet.
Per Cent. Per Cent.

Heartwood, Pale 0-9786 - 21° 50' 1-50698 1-9 5-6 2-2 207-2 96-5
„ „ Dark 0-9816 - 20° 55' 1-50651 1-9 5-6 2-2 207-2 96-4
Sapwood, Palo . 0-9808 - 21° 15' 1-50670 1-9 5-6 2-2 206-2 95-8
All the samples gave a clear solution with 3'5 volumes of 70 per cent,
alcohol.
The author and Bennett have recently examined a number of oils
offered at low prices, and although the better samples, at prices very
close to that of the pure oil, have so far evaded any attempt to discover
the adulteration, if any, of them, in the lowest grade there is little doubt
that there is present the so-called West Indian sandal oil, or, probably, a
fractionated oil with the more insoluble portions removed. Two
oils of this type which were examined exhibit the characters as
follows:—
1. 2.
Specific Gravity . . . . 0-976 0-9755

Optical Botation . . . . - 10° - 9° SO'
Refractive Index . . . . 1-5070 1-5068
Esters (as Santalyl Acetate) . 5-7 per cent. 5 per cent.
Total Santalol . . . . 82-2 83 „
Solubility in 6 vols. 70 per cent. Alcoho Soluble Soluble
Specific Gravity of Acetylated Oil 0-983 0-9846
Rotation - 8°
Refractive Index . . . . 1-4952 1-4963
The oils were by distillation separated into ten fractions of 10 per

cent. each. The characters of these fractions show that one was dealing
with a body having the properties of sesquiterpene derivatives, and the
odour of the first fractions suggested West Indian oil:—
Fraction. Specific Gravity. Optical Rotation. Refractive Index.
1 0-963 - 7° 1-5040
2 0-969 - 6° 30' 1-5060
3 0-973 - 5° 30' 1-5070
4 0-976 - 5° 30' 1-5080
5 0-977 - 5° 40' 1-5082
6 0-977 - 7° 1-5085
7 0-978 - 8° 30' 1-5089
8 0-980 - 10° 25' 1-5090
9 ! 0-984 - 14° 45' 1-5103
2.
1 0-965 - 5° 1-5036
2 0-967 - 5° 1-5048
3 0-972 - 4° 30' 1-5062
4 0-975 - 4° 30' 1-5075
5 0-976 - 5° 50' 1-5079
6 0-978 - 6a 1-5083
7 0-978 - 8° i 1-5080
8 0-981 - 10° 10' 1-5090
9 0-983 - 14 1-5095
These figures should be compared with those obtained with genuine

samples of sandal-wood oil. Four samples of authentic origin gave the
following results :—
A.
1 0-970 - 19° 30' 1-5055

2 0-970 - 17° 20' 1-5060
3 0972 - 16° 1-5060
4 0-974 - 16° 1-5065
5 0-977 - 15° 30' 1-5068
6 0-978 - 15° 1-5068
7 0-980 - 16° 40' 1-5079
8 0-980 - 18° 1-5080
9 0-984 - 21° 1-5084
B.
Fraction. Specific Gravity. Optical Rotation. Retractive Index
1 0-975 - 19° 1-5000

2 0-969 - 18° 1-5044
3 0-969 - 18° 1-5068
4 0-972 - 16° 1-5070
5 0-979 - 14° 1-5072
6 0-979 - 15° 30' 1-5080
7 0-982 - 16° 1-5080
8 0-984 - 17° 20' 1-5075
9 0-982 - 21° 30' 1-5085
c.
1 - 21° 1-5067
2 0-970 - 17° 1-5064
3 0-970 - 15° 1-5063
4 0-974 - 15° 1-5071
5 0-977 - 15° 1-5075
6 0-978 - 15° 1-5080
7 0-978 - 15° 1-5080
8 0-979 - 17° 1-5082
9 0-980 - 20° 1-5086
SANTALACEJE 185
D.
1 0-977 - 18° 1-5078

2 0-964 - 17° 1-5038
3 0-969 - 16° 1-5051
4 0-975 - 15° 1-5068
5 0-979 i - 153 1-5072
6 0-980 - 14° 1-5078
7 0-981 - 16° 1-5083
8 0-981 - 18° 1-5083
9 0-978 - 22° 1-5086
A comparison of these figures will prove of the utmost service to the

•Analyst.
It is obvious that a dextro-rotatory oil is present in these adulterated
•samples, which makes the optical rotation of the fractions very much
lower than is the case with normal pure oils. The divergence between
the fractions in pure oil is but little, and in no case was the optical
rotation below - 14°.
The principal constituent of santal oil is a mixture of alcohols, which,
<for the purposes of analytical determination, are classed as " santalol "
and returned for the purposes of calculation as of the formula G15TL24O.
The following are the constituents which have, so far, been isolated
•from the oil:—
1. Isovaleric Aldehyde.—Traces of this fatty aldehyde C4H9CHO
-have been isolated, and recognised by its thiosemicarbazone, melting at
49° to 53°.
2. Santene.—This body is a hydrocarbon of the formula C9H14. It
is, therefore, apparently a lower homologue of the terpenes. The purest
•specimen so far prepared had the following characters :—
3. Nortricycloeksantalane.—This body is a hydrocarbon of the
tformula CnH18. A specimen purified by distillation over sodium was
iound to have the following characters :—
Molecular refraction . . . . . . . . 46-74
Boiling-point . 183°
4. Santenone.—This compound is a ketone of the formula C9HUO,
isolated from the oil by Muller. It forms a semicarbazone melting at
"224°. It is a solid body, with an odour recalling that of cineol and
camphor, and having the following characters :—
Melting-point . 58° to 61°
Boiling „ . 193° „ 195°
Specific rotation - 4° 40'
Oxime liquid
Semicarbazone melting-point 224°
5. Santenom Alcohol.—This alcohol, also termed norisoborneol, is, in
all probability, the alcohol corresponding to the ketone santenone. It
has been isolated by means of its phthalic acid ester, which melts at 230°..
It is a solid body, melting at 58° to 62° and boiling at 196° to 198°.
6. Teresantalol.—This is also an alcohol having the formula
C10H]60. It is a solid, melting at 111° to 112° when recrystallised from
petroleum ether, and boiling at 210° to 220°. When purified by sub-
limation it melts at 112° to 114°.
7. Nortricycloeksantalal is an aldehyde of the formula CUH16O. It
can be isolated as its bisulphite compound. When so purified it has the
„ 220° to 224° „ 761 mm.
It forms a semicarbazone melting at 223° to 224°, and a liquid oxime
boiling at 135° to 137° at 7 mm.
8. Santalone.—This is a ketone of the formula CnH1(.O, also isolated
by Miiller. It has the following characters :—
It forms a semicarbazone melting at 174° to 176°, and an oxime
melting at 75°.
9. A ketone of the formula CnH16O, so far unnamed. It forms a
semicarbazone melting at 208° to 209° and an oxime melting at 97°
to 99°.
10. Santalene, C15H24.—This sesquiterpene was first discovered by
Von Soden and Miiller,1 but afterwards found by Guerbet to consist of
two isomeric sesquiterpenes. Schimmel & Co.2 have also investigated
the mixture, and the following characters are assigned by the two
authorities to the compounds in question :—
a-Santalene. ^-Santalene.
Guerbet. Schimmel. Guerbet. Schimmel.
Specific Gravity . 0-913 at 0° 0-9 13 at 15° 0-914 at 0° 0-894 at 20°

Rotation -14° - 3° 34' - 28-5° - 41° 3'
Boiling-point 252° at 753 mm. 125 at 7 mm.
Refractive Index . — * 1-49205 — 1-4946
3
Semmler gives the following figures for the isomeric santalenes :—
a-Santalene. /3-Santalene.
Specific gravity . 0-8984 at 20° 0-892 at 20°
Optical rotation . - 15° - 35°
Refractive index . 14 HO 1-4932
Boiling-point 118° to 119° at 9 mm. 125° to 127° at 9 mm.
11. Santalol, C15H26O or C15H24O.—This is a mixture of isomeric
alcohols, the characters of which are not clearly established. Guerbet
(loc. cit.) gives the following as the characters of a-santalol and /3-santalot
and their acetates :—
1 2
Comptes Rendus, 130 (1900), 417. Schimmel's Bericht, October, 1910, 107.
*Berichte (1907), 3321.
SANTALACEÊ 1ST
(a) a-santalol, boiling at 300° to 301° at 760 mm., or at 162° to 163°

at 13 mm. ; of specific gravity 0-9854 at 0° and optical rotation - 1° 20'.
(b) 0-santalol, boiling at 170° to 171° at 14 mm., or 309° to 310° at
760 mm. ; of specific gravity 0*9869 at 0° and optical rotation - 56°.
a-santalyl acetate boils at 308° to 310°. /3-santalyl acetate boils at
316° to 317°.
Schimmel & Co., on the other hand (loc. cit.), give the following
characters for the two bodies : —
a-Santalol. /3-Santalol.
Specific gravity ..... 0-9788 at 15° 0*9728
Optical rotation ..... + 1° 13' - 41° 47'
Refractive index ..... 1-49915 1-5091
Boiling point at 5 mm ..... 148° 158°
/?-santalene boils at 125° to 127° at 9 mm., has a specific gravity
0*892 at 20°, refractive index 1-4932, and optical rotation - 35°.
Semmler and Bode l have shown that santalol is a primary alcohol
(or alcohols), by its oxidation to santal aldehyde. According to these
chemists this aldehyde boils at 152° to 155° at 10 mm., has a specific
gravity 0-995 at 20°, refractive index 1*51066, and is dextro-rotary. Its
semicarbazone melts at 230°.
Santalyl chloride, obtained by the action of phosphorus pentachloride
on the alcohol, has a specific gravity 1-0398. Its formula is C15H23C1
according to Semmler, who regards santalols as C15H24O.
Semmler regards a-santalol as a tricyclic compound, which, when
heated to 160° with alcoholic potash for two hours, is ruptured at the
double bond in the side chain, and the tricyclic compound is converted
into a dicyclic alcohol which he calls dicycloeksantalol. The formulae
for the a and /2-santalols which he suggests are as follows : —
CH : CH . CH2 . CH . CH2 . OH.
a-Santalol.
CH : CH . CH 2 . CH 2 . CH 2 . OH.
0-Santalol.
These abstruse points are dealt with fully in the following papers—
Berichte, 1907, 40, 1120, and 1907, 40, 1124.
By means of the strychnine salts, Paolini and Divizia 2 have separated
the two alcohols in a pure state. The mixture of the two alcohols as
found in sandal-wood oil is first carefully fractionated and the fractions
separately treated with sodium and converted into the hydrogen phthalate,
in the usual manner. The strychnine salts are then formed and recry-
stallised until the melting-point and rotatory power are constant. The
pure isomerides are then obtained by saponification. The purity ia
confirmed by reconverting into the strychnine salts, which should yield
on saponification a santalol of identical properties. The strychnine
phthalate of a-santalol melts at 155°, and has an optical rotation of
1
Berichte (1907), H24. * Alt. R. Acad. Lin. (1914), 23, 226.
- 1*4°. The a-santalol prepared from it boils at 159° (10 mm.), has a
density of 0*979, optical rotation + 1*1°, and refractive index 1*499 (19°).
The strychnine phthalate of /3-santalol melts at 134° to 135°, and has an
optical rotation of - 30*43°. The /?-santalol prepared from it boils at
168° to 169° (10 mm.), has a density of 0*9729, optical rotation - 42°,
and refractive index 1-5092 (19°).
12. Santalal, C15H22O, has been reported as a constituent of santal
oil, but its presence is doubtful.
13. Teresantalic Acid. —This body exists in very small amount in
santal- wood oil. It forms part of the small quantity of free acids
present, and has the formula C^HÔg. It forms well-defined prisms
melting at 157°, and, according to Miiller, boils at 150° at 11 mm. Its
specific rotation in alcohol solution is - 70° 24'. It exists in the free
state in the oil to the extent of 0*5 per cent., and can be extracted by
means of dilute caustic alkali solution.
14. Santalic Acid. —This acid, of the formula C15H«5202, is a second
of the free acids isolated from santal-wood oil. tt is, according to
Guerbet, a thick liquid boiling at 210° to 212° at 20 mm. pressure.
In addition to the above-described oil, the following santal oils, or
so-called santal oils, have been examined : —
NEW HEBRIDES OIL.
This is probably not distilled from Santalum album. It has the
Specific gravity . 0*9675
Optical rotation
Eefractive index 1-5089
Acid value 1-8
Ester „ 3-6
Santalol 92-4 per cent.
TAHITI OIL.
This oil is probably distilled from Santalum Freycinetianum and has
Specific gravity. . . . 0-9748
Acid value 2-0
Ester „ . 5-1
Santalol . 94-4 per cent.
NEW CALEDONIA OIL.

This oil is obtained from Santalum austro-caledonicum. It has the
Optical rotation ....... + 6° 29' „ - 21° 42'
Befractive index 1-5062
Acid value 0-9 to 6-4
Ester ,, 3-2 „ 5-4
Santalol 90-5 to 96-2 per cent.
FlGI OIL.
This oil is obtained from the wood of Santalum Yasi. It has a
specific gravity 0*9768 and optical rotation — 25*5°.
SANTALACE^ 189
WEST AUSTRALIAN OIL.
This oil is the product of one or more species of tree, being chiefly
derived from the wood of Fusanus spicatus. Several other species
are found in West Australia, but they are much less common than
Spicatus, which alone is used to any extent for distilling. This tree
was originally known as Santalum cygnorum. Although only a tree
of small dimensions, it forms an important factor in the timber in-
dustry of Western Australia. The species, as the author has seen it
growing in the interior of this colony, has a low depressed habit, and
is usually very branchy and heavily topped. It is generally from 12
to 20 ft. high, and from 6 to 10 ins. in diameter. The stems usually
weigh .from 1 to 6 cwt. It is found fairly well distributed in the
interior of the colony, except in the extreme south-west. It may be
seen growing fairly freely on the most barren sandy soil, where one
could not see a blade of grass nor a drop of water for miles round.
The greater part of this wood is exported to China, but one or two
santal oil distilleries have been started in the colony. The author
has examined four samples of oil distilled from either Fusanus
spicatus or from this tree with other species mixed, and found they
had the following characteristics :—
Specific Gravity. KOH for Esters. Iodine Absorption.
1 ... -9650 1-46 200-0
2 . . . -9644 1-15 204-5
3 . . . -9632 1-66 198-2
4 . . -9643 1-35 197-6
There was found only from 65 to 75 per cent, of alcohols in these

oUs, as against 90 per cent, in the Bast Indian oil. The optical
rotation is usually about + 5° to + 8°. The distillation water of this oil
contains traces of methyl alcohol, diacetyl and furfurol.
Claims that this oil can be rectified so as to yield an oil correspond-
ing with the requirements of the British Pharmacopoeia, have recently
been made. They are, of course, unfounded.
SOUTH AUSTRALIAN OIL.
This oil is distilled from Santalum preissianum, but it yields an oil
quite different to the ordinary santal-wood oil. It has a specific gravity
of about 1*02, and becomes solid when cooled.
Berkenheim 1 has isolated from this oil a solid alcoholic constituent of
the formula C15H240, melting at 101° to 102°, and yielding crystalline esters.
WEST INDIAN OIL.

This oil is the product of a Venezuelan tree which has been identified
as belonging to the N.O. Eutaceae, but as the oil somewhat resembles
true santal-wood oils, it may be conveniently described here. Its
specific gravity is lower than that of the true santal oil, and it is far
more insoluble in alcohol. It is dextro-rotatory and contains much less
alcoholic constituents than does the oil of Santalum album. Five
samples gave the following figures :—
1
Jour. Oheni. Soc. (1893), ii. 666.
Specific Solubility in Alcohols as

70 per Cent. Rotation. Santalol.
Gravity. Alcohol.
Per Cent.
•962 1 in 80 42
•966 1 „ 55 + 25° 30' 50-5
•953 Insoluble in 80 4- 8° 30-1
•963 80 + 30° 20' 32-1
•962 80 + 25° 7.V
Mr. E. M. Holmes examined the plant yielding this oil, and named
it Schimmelia oleifera after the firm who obtained the specimens for
him, but Urban has now proved definitely that the plant belongs to the
genus Amyris, and has identified it as Amyris baisamifera.
It is now well recognised that the alcoholic body or bodies of West
Indian santal oil differ from the alcohols of the East Indian oil.
This alcohol has now been isolated by H. von Soden and named by
him " amyrol". It forms an almost colourless, viscous liquid, which
forms a clear solution with 3 to 3-J parts of 70 per cent, alcohol. Specific
gravity at 15° = 0'98Q to 0-982 ; aD = + 27°. Boiling-point at 748 mm.
pressure = 299° to 301°, at 11 mm. 151° to 152°.
Amyrol cannot be esterified with phthalic acid anhydride ; quanti-
tative acetylation is equally impossible. Amyrol is probably a ses-
quiterpene alcohol, C15H26O. In addition to this body, West Indian
=sandal-wood oil contains a sesquiterpene, whose nature has been
investigated by E. Deussen. He introduced hydrochloric acid gas up
to saturation into the oil dissolved in dry ether, and obtained crystals
of cadinene dihydrochloride. The corresponding compounds of hydro-
gen bromide and iodide, of which the constants are given below, were
produced in a similar manner:—
Per Cent.
Melting-point r»i//
\a\a.
Cl. Br. I.
Dihydrochloride . 117° to 118° 25-65 - 36*65°

Dihydrobromide . 124° „ 125° 43-64 - 36-26°
Dihydroiodide 105° „ 106° 54-96
It has more recently been found that amyrol, like santalol, is not a
uniform body, but that by frequently repeated fractional distillation it
•can be separated into different alcohols. The higher boiling, very
viscous compound has a faint, characteristic, fragrant odour; its
formula C15H25OH. Specific gravity about 0*987; aD = about -f- 36°;
boiling-point 299°. The lower boiling alcohol appears to have the
formula C16H23OH, and to be optically inactive.
The liquid obtained on saponifying the original oil, when acidified
with sulphuric acid, yielded an oil, partly congealing in crystalline
form, with an odour strongly reminding of acetic acid. This oil was
shaken with carbonate of sodium solution to remove the acid. The
remaining crystals, after recrystallisation from methyl alcohol, melted
at 117°. This new body, to which the name amyrolin was given,
contains neither nitrogen nor methoxyl groups; its composition is
C14HliO3. Amyrolin dissolves in alcoholic potash solution with a
yellowish-green fluorescence, absorbs bromine, and yields with the
ARISTOLOCHIACE^ 191
latter an amorphous, white dibromide of the melting-point 157° to 159°.
In view of its behaviour amyrolin appears to be a lactone-like body of
the aromatic series.
EAST AFRICAN SANTAL OIL.
A so-called santal oil has been distilled in East Africa, and examined
by Haensel and by Schimmel & Co. It is the product of species of
Csyris (probably 0. tenuifolia) and has the following characters :—
Optical rotation . - 40-6° „ - 61°
Acid value . 1-7
Ester „ 8-1 to 17'9
Santalol . 30-5 per cent.
ARISTOLOCHIACE/E.
OIL OF SNAKE-WOOD (EUROPEAN).
The ordinary European snake-wood oil is distilled from the root of
.Asarum europaeum, which yields about 1 per cent, of a thick dark
brown oil of sweet aromatic odour. The specific gravity of this oil
varies from 1*015' to 1*07. According to Petersen, when frozen it de-
posits crystals of asarone.
The oil contains pinene, methyl-isoeugenol, and a compound termed
4warone. This body has the following constitution :—
2
OCH3( )
X
OCH3(*)
OIL OF SNAKE BOOT (CANADIAN).
This oil is distilled from the rhizomes of Asarum canadense, a plant
growing in the Northern United States. The yield is from 3 to 5 per
•cent, of an aromatic oil. The plant is also known as Indian wild
.ginger. The oil has a strong nondescript aromatic odour and taste,
•and varies in characters. The oil distilled from the rhizomes without
•the rootlets has the following characters :—l
Specific gravity . . . . . 0*9516 t o 0'9520
Optical rotation - 2° 50' , - 10° 42'
Acid value . 3-1,3-7
Ester „ 86 , 117
„ „ . after (acetyiation) . . . 126 , 137
The oil distilled from the rhizomes with the rootlets has the follow-
ing characters:—
Specific gravity . 0'951 to 0'952
Optical rotation - 10° 30' - 22°
Acid value . 3-7 4-7
Ester 74-7 115-9
(after acetyiation) 125 140
The oil from the rootlets alone, which was obtained to the extent of
1*2 per cent., had the following characters :—
1
Schimmel's Report, April, 1908, 99; April, 1909, 85.
Acid value 2-2
Ester „ 39-2
The oil contains a phenol of the formula C9H12O2 a-pinene,
lol, borneol, Z-terpineol, geraniol, methyl-eugenol, acetic, palmitic, and
other fatty acids, and a lactone of the formula C14H20O2.
OIL OF SNAKE-KOOT (VIRGINIAN).
The roots of Aristolochia serpentaria, the North American serpentary,
or Virginian snake-root, yield from 1 to 2 per cent, of essential oil, having
Specific gravity . . 0'960 to 0'990
Optical rotation . . + 20° , + 26°
Befractive index . . 1-4972 , 1-4980
Acid value . . 2 , 3
Ester „ . 65 , 80
„ „ (after acetylation) . 105 , 115
Borneol has been detscted as a constituent of this oil.
LABIATVE.
OIL. OF LAVANDULA VERA (LAVENDER OIL).
This oil is obtained by distilling the flowers of Lavandula vera, the-
well-known lavender, a native of southern Europe. The plant is found
on the stony declivities of the Provengal Alps, the lower Alps of
Dauphine and Cevennes (and even so far north as latitude 46°), in
Piedmont, Switzerland, the mountains of Liguria and Etruria, and
various other places. Peculiarly enough, the plants come to their
greatest perfection and yield a much finer essential oil when transferred
from their native soil, and carefully cultivated in certain districts in
England, which produces the finest lavender oil in the world. The
principal lavender plantations in England are in the neighbourhoods of
Mitcham, Ampthill, Hitchin, and Canterbury.
Attempts have been made to establish plantations in Southern
France from young plants taken from parent stems in England; but
the plants quickly reverted to their original condition, and "English"
lavender oil can so far only be produced in England. For the details
of the methods of cultivation adopted, the reader is referred to the ex-
cellent monograph in Sawyer's Odorgraphia, vol. i. p. 361. A great
deal of the finest lavender oil is distilled with water over an open fire,
and, so long as care is taken that the plants themselves are not burnt>
the fine quality of the resulting oil largely justifies the process. Modern
distilleries, in which steam distillation replaces the old water distilla-
tion, give, however, a larger yield of oil, and, in general, these have
higher ester values than the water distilled oils. This point will be
referred to later. In England it is usual to allow the body of the still
in which the flowers are distilled to be very shallow as compared with
its width, in order to allow the oil to pass over rapidly and get away
from the source of heat, which might damage its odour. If a naked
fire be used, it is customary to suspend the charge of flowers in a
basket of sheet copper, with perforations all over it to allow the free
LABIATE 193
circulation of water. This basket, of course, holds a large charge, and
is manipulated by means of a pulley or swing-crane. The basket should
be about an inch from the bottom and sides of the still, and have copper
legs to rest upon. Sufficient, water is used with each charge to cover
the top of the basket. The finest portion of the oil condenses during
the first half-hour to hour of the distillation, and is usually reserved,
the remainder being collected separately. Eectification of lavender oil,
which renders it colourless, does not improve it. The somewhat
11
herby " odour of the fresh oil soon passes off, and if the oil be kept in
cool dark places it improves by maturing for several years, and matured
oils are often sold according to the date of their preparation. After a
certain time it is said to deteriorate unless a little alcohol is added to it.
This oil, in common with several others distilled from plants of the
natural order Labiata, is one of those whose characters are altered
to a very remarkable degree by changes in the conditions of growth.
An expert now will usually distinguish a lavender oil distilled from
plants in and around Mitcham from one distilled in Cambridgeshire
or Hertfordshire, and although the ester value of all English oils is
fairly constant, foreign distilled oils invariably have much higher
ester values. This difference in ester value is brought about by entirely
different conditions from those which bring about a reduction in esters
where the plants yielding the oil " s'aspiquent". There it is a case of
cross-fertilisation of the two species of lavender.
The conditions of the lavender oil industry in France are well de-
scribed by Lamothe.1
He gives a botanical description of the various Lavandula species^
and discusses the conditions which are most favourable for the existence
of lavender, the nature and treatment of the soil for laying out the planta-
tions, and the manner of doing so. According to him Lavandula species,
are divided as follows :—
1. Lavandula latifolia Vill., Lavandula spica. var. /3 L. (grande
lavande, 1. male, 1. branchue, spic, aspic).
2. Lavandula officinalis Chaix, Lavandula vera D. C., Lavandula,
spica, var. a L. (lavande veritable, 1. femelle).
Jordan classifies the latter into two sub-divisions, viz. :—-
Lavandula fragrans (lavande odorante, 1. moyenne).
Lavandula Delphinensis Jordan (petite lavande, 1. fine).
The first of these two varieties is widely distributed. It occurs at the
lower altitudes, whilst Lavandula Delphinensis is found exclusively in
the highest regions.
In addition to these, there occurs a cross between Lavandula lati-
folia and Lavandula fragrans, which Eeverchon calls Lavandula
Hybrida, and Chatenier Lavandula fragrans x latifolia (gross lavande,
1. batarde, lavandin, spigoure).
The distillers, according to Lamothe, have the following designa-
tions for th - various lavender species :—
1. Petite lavande. This yields the best oil, is more hardy, and less
fastidious than the next two which occur in lower regions.
2. Lavande moyenne. Yields a less fine but still useful lavender oil.
3. Gross lavande. Bastard, yields an inferior oil. Not to be con-
fused with the grande lavande (spike).
1
Lavand et Spic., 2nd edition, 1908.
VOL. I. 13
Lavender oil is frequently judged, as to quality, entirely on its ester-
content. There is, however, abundant evidence to show that this is a
mistake, and lavender oils can only be so classified, provided that oils
from the same district are under consideration. The fact that the true
lavender and the spike lavender grow more or less together in the same
district, causes a good deal of hybridisation to take place.
In dealing with the influence which the cross-fertilisation of
lavender and spike on the essential oil of these plants, A. Birckenstock
has also dealt with the ester question. He has pointed out that there
are also good lavender oils which contain only 20 to 30 per cent, ester.
Such oils are found in the Alps near the Franco-Italian frontier, and
the annual production (about 5000 kilos) is in Birckenstock's opinion of
sufficient importance to take the particular properties of these oils into
account. They have according to him a very fine bouquet, but little
" body". The content of linalol amounts to about 50 per cent., and is
therefore normal, but, as already mentioned, the ester content is only
20 to 30 per cent.; they are also characterised by a low specific gravity
(0*878 to 0-882), and by a considerable laevo-rotation (- 8° to - 9°);
they are, moreover, very readily soluble in alcohol (in 10 to 12 volumes
60 per cent, alcohol).
According to Birckenstock, if lavender comes below 2300 to 2600
ft. it crosses with spike, "elle s'aspique"; the hybrids thus formed
are known among distillers by the names of " lavandin " or " spigoure,"
and they represent every possible transition between lavender and
spike, according to the conditions due to altitude and state of the soil.
In this connection Birckenstock's statements on the morphological
differences between lavender and spike are interesting; lavender has a
non-ramified stalk, which is rarely longer than 16 ins.; the blossoms
are blue-violet, and have thin, heart-shaped, pointed sepals which are
shorter than the bluish calyx.
The spike plant is larger than the lavender. The stalks frequently
have several ramifications, and grow to a height of up to 32 and 36 ins.
The sepals are linear and of the same length as the calyx, which in this
case is not bluish, but whitish.
The influence of cross-fertilisation also shows itself in the proper-
ties of the essential oils, which behave entirely like mixtures of lavender
oil and spike oil. Birckensfcock has in the course of his observations
examined a whole series of oils, from typical lavender oil to typical
spike oil. He then found at the same time that as the oil approaches
true lavender oil not only the ester content and alcohol content increase,
but that also a gradual change takes place in the proportion of borneol
to linalol and geraniol; whereas in spike oil borneol predominates, it
diminishes towards lavender oil more and more as compared with
linalol and geraniol. The following are the properties of two charac-
teristic lavandin oils :—
1. ^150 0'9027; OLD - 0° 43'; ester-content, 6'23 per cent.; alcohol-
content (C1(;H18O), 34-8 per cent.; soluble in 3 volumes 65 per cent,
alcohol.
2. di5o 0-8995; aD - 1° 35'; ester-content, 9'12 per cent.; alcohol-
content, 36'5 per cent.; solublel in 3 volumes 65 per cent, alcohol.
According to Zacharewicz lavender thrives best on a light, flinty-
1
Bull, mensuel du Synd. Agric. Vaucluse, 23 (1907), 280, and Schimmel's Report.
LABIATE 195
-clayey, stony, and sunny soil, at an elevation of about 1200 to 3700 ft.
At lower-altitudes lavender languishes, yields an oil less rich in ester,
and has moreover a tendency to bastardise and finally to degenerate
V,.'"
into spike, whilst at increasing altitudes the ester-content of the oil,

and with it its value, increases.
By suitable cultivation at the proper elevation, both the growth of
lavender and the production of blossoms can be increased. The laying*
out can take place either by rearranging an existing natural lavender-
field, or by starting from seed or from layers (eclats).
In the former case, in the field grown with lavender, either in the
autumn or in March, furrows are ploughed, or in the more recent way,
cut with a hoe, so as to leave at distances of one metre strips with
lavender plants growing on them. In this manner some lavender
plants are no doubt destroyed, but this loss need not be considered at
all in view of the rapid development of the plants, which, when suitably
fertilised, now give almost double the yield.
Besides in the foregoing manner, the cultivation can also be started
with layers or with seed. Whichever is to be preferred in an individ-
ual case, depends entirely upon the circumstances. The sowing-out is
no doubt cheaper, but against this, layers give a greater yield in the
first four years, so that the net cost is about the same.
The planting of the layers can take place either in the autumn or in
the spring; the latter is advisable (owing to the frosts) if the field is
situated at a great altitude. The plants are placed in rows at distances
of 60 cm., the rows being 1 metre apart, so that about 16,600 plants
go to a hectare. The sowing can also be done either in the autumn or
in the spring, and where the winter is not severe, the spring is pre-
ferred. The seed is sown at a depth of 2 to 3 cm. in rows 1 metre
apart. One grm. of seed is calculated for an area of 1 sq. metre, which
comes to 10 kilos per hectare. The cultivation requires the soil to be
turned twice a year, once at the commencement of the winter, and once
in March; during the latter, the manure which had previously been
distributed between the rows, is worked into the soil. Zacharewicz has
shown by comparative experiments that the fertilisation promotes both
the growth of the lavender and the wealth of blossoms, and that the
yield has thereby been raised from 2000 to 3500 kilos per hectare.
Distillation showed that the blossoms from the fertilised soil were also-
richer in oil. Zacharewicz states that the harvest commences on
1 August, and ends in the first days of September.
Lamothel has recently drawn attention to the fact that the bastard
lavender "lavandin," referred to above, is being cultivated on an in
creasing scale.
Its flowers develop about a fortnight later in the season than those
of the true lavender, which is ascribable to its hybrid character; spike,
for example, flowers still later, in the beginning of September. Lavan-
din occurs principally in the region of the holm-oak, and even spreads
beyond the boundaries of the latter, traversing in a broad belt the De- .
partments of the Drome, Vaucluse, Basses-Alpes, etc., where it covers
the southern slopes of several mountains up to the top.
Like all hybrids, lavandin is an extraordinarily hardy plant, and in
its prolific development constitutes an actual danger to the true laven-
der, which it robs of air and nourishment. The fact that this hybrid
is gaining ground year by year gives cause for serious concern, the
more so because pasturing sheep and goats shun it on account of its
acrid odour and bitter taste, whereas in the true lavender these animals
find an occasional welcome substitute for grass.
But in spite of this same bitter, herbaceous, and camphor-like
1
Parfumerie Moderne, 5 (1912), 9.
LABIATE 197
flavour, which places it far behind lavender as an odoriferous plant,
very considerable quantities of lavandin are cut for distilling.
Lamothe estimates that the lavandin oil which is brought to market
•every year amounts to about 20 per cent, of the total output of lavender
*>il or, in weight, to about 12,000 kilos. He regards this as most re-
grettable and utters an emphatic warning against the distillation of
lavandin flowers, for although they yield a better return than true
lavender, and with less trouble, their oil is decidedly inferior and may
easily injure the present predominant position of French lavender oil.
Lamothe gives a very interesting comparison of the respective outputs,
which deserves to be quoted here. In the same time which is required
to collect about 55 kilos true lavender flowers, nearly 400 kilos of the
freer-flowering lavandin can be gathered without trouble. And where-
as for the production of 1 kilo lavender oil 145 kilos of flowers are needed,
from 77 to 80 kilos of flowers suffice to produce 1 kilo of lavandin oil.
With regard to the properties of lavandin oil, Lamothe states that
the samples distilled by him had an average ester-content of 24 per
cent.
Lavender oilds a pale yellow oil having the following characters :—
Specific gravity . . . . . . . . 0'879 t o 0-900
Kefractive index 1-4600 „ 1-4660
With regard to any further tests to be applied to the oil, the place
of origin must be taken into consideration. An English oil will not
give an ester number outside the limits 7 to 10 per cent., calculated as
linalyl acetate, whilst foreign oils yield about 25 to 44 per cent., or even
higher values under certain conditions. This fact is exceedingly im-
portant in discriminating between English and mixed lavender oils.
The usual adulterants of lavender oil used to be spike oil and turpen-
tine. Neither of these oils contains appreciable quantities of ester, so
that the ester determination affords much information here. Spike oil
being usually dextro-rotatory causes a diminution in the rotatory power
of the oil. American turpentine has the same effect, whereas French
turpentine increases the laevo-rotation. Mixtures of spike oil and
French lavender oil can be made having the same ester content as
English oil, but the optical rotation is interfered with (the specific
gravity is slightly raised also, but not necessarily above the limits for
normal oil). To-day, however, the most dangerous adulterant one has
to guard against is spike oil, or a similar oil, enriched with artificial
esters.
The esters used are, in general, glyceryl acetate, terpinyl acetate,
ethyl phthalate, ethyl succinate or ethyl citrate, most of which yield a
saponification value indicating a much greater amount of linalyl ace-
tate. The specific gravity of the oil is raised by these additions, un-
less this is counterbalanced by the suitable addition of a low gravity
oil. Schimmel gives the following method of detecting ethyl succinate.
About 2 grms. of the oil are saponified and the insoluble oil washed
fcway with ether; the aqueous solution is neutralised with hydro-
chloric acid and diluted to 50 c.c. Ten c.c. of cold saturated solution
of barium chloride are added and the liquid warmed on the water-bath
for two hours and then cooled. The formation of any crystalline pre-
cipitate indicates adulteration, since the barium salts of acetic and
butyric acids (which are present as natural esters) are soluble. This,
test applies to most of these artificial esters, such as ethyl oxalate, etc.
But more recently Schimmel has found that the following method
is more reliable than the use of barium salts: 10 grms. of the oil to be
examined are saponified on the water-bath for one hour with alcoholic
potash, the contents of the flask then placed in a porcelain dish, and
the bulk of the alcohol evaporated. After this the liquid is washed in
a separating funnel with about 100 c.c. water, the oily portions removed
by extraction with ether, the aqueous solution returned to the porcelain
dish, and the bulk evaporated on the water-bath. When the alka-
line solution is cooled down, it is acidified with sulphuric acid, and the
organic acids thus liberated absorbed with ether. The ethereal solution
is placed in a dish and the ether evaporated. For the purpose of re-
moving volatile acids (acetic acid) the residue is still heated for some
time on the water-bath, then cooled, and digested with ether. In this
manner a fine crystalline residue remains behind undissolved. On re-
crystallisation from a small quantity of alcohol, white crystals are
obtained, and the melting-point can be determined. On fractional
distillation the artificial esters will be found in the residues left after
distilling off the more volatile portion and will be found to have a very
high specific gravity and low refractive index. A comparison with
similar fractions of a normal oil will at once reveal the characteristic
differences.
Delphin l has found an artificial ester as an adulterant of lavender
oil which he believes to be the ethyl ester of the fatty acids of cocoa-
nut oil. He has also definitely identified ethyl phthalate as an adul-
terant.
The effects of some of the common adulterants on the characters of
the oil are as follows :—
Turpentine oil lowers specific gravity and solubility; further, the
rotation is affected, the laevo-rotatory French turpentine oil (D - 20°
to - 40°) raising, and the dextro-rotatory American oil (CXD up to -f- 15°)
lowering it.
Spike oil increases the specific gravity and lowers the rotation; the
solubility remains the same.
Spanish lavender oil behaves like spike oil, but has a less marked
influence on the rotation.
Eosemary oil also causes similar alterations to spike oil, but renders
the lavender oil less soluble.
All the additions mentioned above considerably reduce the ester
content.
Lavender oil is practically neutral. An acid value over about 3 in-
dicates the addtiion cf oaids, such as benzoic or salicylic added, to bring
up the apparent ester value.
Generally speaking, pure lavender oil is soluble in 2'5 to 3 volumes
of 70 per cent, alcohol at or under 20°, but old oils—and rarely even
freshly distilled oils, require up to 4 volumes for complete solubility, or
even in rare cases up to 7 volumes.2
Oils are not infrequently found with a very high ester value, the
following being amongst those so recorded.
1
Svensk.Farm. tid. (1908), 22; (1912), 5.
2
P. and E.O.R. (1914), 130; (1915), 314.
LABIATE 199
Giaconi has distilled oils in the Dalmatian Archipelago at an alti-
tude of 900 metres, having the following characters:—
Optical rotation - 8° 30' „ - 10°
Esters . 57-1 to 61-6 per cent.
Schimmel & Co.1 give the following analyses as indicating the effect
of certain of these artificial esters on the analytical values of the oil.
In this connection, the methods for the detection of artificial esters
(Vol. II.) should be taken into consideration :—
No. 1. 2. 3. 4. 5.
Lavender Oil. Shaken 15 c.c. 10 c.o.

! Original ^WITH Original
f&i once
Oil. Steam. 0lL with 5°/0 Seminormal
Alcohol. Potash Solution.
<u 0-9007 0-6946 0-9072 0-8932 0-8992

. • . - 3° 55' - 2° 34' - 5° 14' - 5° 37' - 4° 32'
0-8913
OD . . - 8° 43'
Soluble in 70 per
Cent. Alcohol 2-5vols. 2-5 vols. 1-9 vols. 2-2 vols. 2-5 vols. 4*5 vols. —
a.m. a.m. a.m. a.m. — a.m.
a.m.
Acid value 0-3 0-5 0-8 0-5 0-3 0-3
Ester value after 1 h.
sap. with 10 cc.
} n. Solution 78-4 83-3. 100-5 102-5 90-0 87-0 145-7 143-4
Ester-content (calc.
for Linalyl Ac.) . 27-4 «/0 29-2 35-2 °/0 35-9 °/0 31-5 °/0 30-4 °/0 Ol°/o 50-2°/0
sap. with 20 c.c.
4 n. Solution 82-7 87-6 104-2 104-6 ;919 146-0 146-0
sap. with 10 c.c.
J n. Solution -f 25
c.o. Alcohol . 69-7 77-0 99-0 100-6 91-1 144-1 132-9
Difference 13-0 10-6 5-2 4-0 0-8 — 1'9 13-1
Sap. value 102-5 —
7K-7 b3-8 101-3 90-5
Acid value II. 75-7 83'7 96-7 100-6 90-6 — —
Difference 3-0 0-1 4-6 1-9 —
Terpinyl Acet. con- —
tent about . 6
°/o 4%. not ascertainable —
Esters of spar. vol. 1 —
Acids . Vdoubtful not ascertainable
not ascertainable
Glyceryl Ester not ascertainable J not asc. present — — —
The following remarks are applicable to the samples referred to in

the table. Nos. 1 and 2 contained terpinyl acetate; No. 3 was a pure,
but old resinified oil, as the analysis performed on it after steam distil-
lation proved; No. 4 contained glyceryl acetate ; No. 5 was a pure oil,
N
but as its ester-content is so high, 10 c.c. of -~- alkali is insufficient for
a proper saponification, so that the only reliable indications are those
when 15 c.c. of N/2KOH are used.
Schimmel & Co.2 have examined a number of oils distilled by them-
selves at Barreme, which had the following characters:—
1 2
Report, April, 1912, 86. Schimmel's Bericht, April, 1907, 73.
Optical rotation - 7° „ - 9° 33'
Esters 47 to 56 per cent.
English oil of lavender is quite different in its odour and chemical
characters from Continental lavender oil. It is generally valued at a
very much higher rate than French oil and is esteemed more highly
than any other type of lavender oil.
The chief difference between English and French oils of lavender
lies in the fact that the former contains only about 7 to 10 per cent, of
esters calculated as linalyl acetate, whereas the latter contains up to 44
per cent, and over. Messrs. Schimmel have actively endeavoured to
establish this ester-content as the basis of the valuation of the oil.
They maintain the superiority of fine French oil over English oil, and
go so far as to say that the latter cannot compete with the former.
The author, in common with most others, holds the opposite opinion,
and considers that no comparison can be made between the two oils
on the basis of their ester-content. This is much accentuated, if such
were necessary, by the fact that linalyl acetate is not the odoriferous
ingredient of oil of lavender. It is so much modified by the presence of
other bodies, as to be regarded as only one of the odoriferous com-
pounds in the oils. Pure linalyl acetate has a marked bergamot odour,
and may be regarded as the characteristic ingredient of that oil. The
fact that English oil fetches a very much higher price than French oil
speaks for itself. For a comparison of oils grown in the same locality,
the ester comparison may, however, be of service. The oils produced
in the South of Europe are finer according as the plants are growing at
greater elevations, and according to Schimmel & Co. the very finest oils
are produced from the higher valleys of the Savoy Alps, yielding 44 per
cent, of ester. The fine oils yielding 38 to 40 per cent, of ester are
usually obtained from the Alpes Maritimes and the Basses Alpes, close
to the Italian frontier. Less fine, but still excellent, oils with 28 to 32
per cent, of ester are obtained from the French Departments of the
Gard, Dr6me, and Herault. §
These statements, however, are based only on a comparison of the
ester values, and are in direct opposition to the views and experience
of several of the leading distillers of this oil. Lautier, for example, says
(Etudes sur quelques precedes et products de parfumerie) : " No one
can deny that the oils from Drome or Vaucluse are of far inferior odour
to those from the Alps. Yet the former contain 35 to 40 per cent, of
esters." It is also true that some of the oil distilled on the Italian
frontiers with 25 to 30 per cent, of esters is of the finest grade, and
Umney, who in the main agrees with Schimmel on this question, ad-
mits that with an ester value of much over 40 per cent, the oil* may be
rank. The " ester theory" has induced a considerable amount of adul-
teration with artificial esters and should be accepted only within very
definite limitations.
English lavender oil, on keeping, especially in the presence of traces
of moisture, alters considerably in character.
Brewis and Umney l have recorded the following figures for a series
of samples of known authenticity :—
l
P.andE.O.R. (1912), 5.
SOME LABORATORY SAMPLES OF OLD ENGLISH LAVENDER OILS.
S. G. Opt. Rot. Refractive Apparent Remarks.

Sample 100 m/m. Index Acids as Esters as
Marked @ Acetic. Liualyl
15°. @15°. @ 25°. Acetate. Storage. Colour of Oil. Condition of Oil.
1903 A 0-&915 - 9-5 1-1667 0 10 4^5 °/0 Narrow- mouthed Pale yellow Limpid.
corked bottle
1904 A 08855 - 9-0 1-4638 0 8-76 °/0 »f
"
1905 MA 0-9092 - 8-0 1-4668 0-36 8-46 °/0 „ Dark yellow Slightly viscid and resinous.
1906 M 0-9481 - 6-2 1-46S7 1-8 14-95 °/0 » Viscid and resinous.
1907 M & A 0-9021 - 8-3 1-4695 0-24 8-54 «/ 0
1907 M 0-8879 - 9-4 1-4672 0 8'34 °/0 ,, Pale yellow Limpid.

1908 M 0-8864 - 8-5 ] 1-4655 0 7-20 °/0
1908 B 0-9885 - 4-6 1-4712 3-22 21-65 °/0 Wide-mouthed Dark yellow Very viscid and resinous.
corked bottle
1909 M 0-9851 - 4-8 1-4715 3-22 22-7 °/0 " " Slightly less viscid and resinous
than 1908 B.
1910 M 0-8859 - 9-4 1-4658 0-12 7-37 °/0 Narrow-mouthed ; Pale yellow Limpid.
corked bottle
1911 0-8&59 - 8-5 1-4638 0 7-96 «/0 „ Very pale "
yellow.
fcO
o
Those samples in which very high ester values had developed were
of such acid and disagreeable odour as to be unfit for use. These ob-
servations are confirmed by the following analyses by Passmore, the
original analysis being made on comparatively freshly distilled oils, and
the second analysis after a period of several years on the same oil:—
Original Second Analysis

Analysis. (1912).
Al/03 . Acidity nil nil

Ester Value 11 -0 per cent. ll'O per cent.
Al/04 . Acidity nil 2-00
Ester Value 8-8 per cent. 21-2
M/05 . Acidity nil 1-31
Ester Value 7*5 per cent. 17-7
LM/08 . Acidity nil 2-29
Ester Value 8*7 percent. 22-7
LM/09 . Acidity nil 2-68
Ester Value 8'8 per cent. 20-2
The Constituents of Lavender Oil.—The earliest systematic investiga-

tion of this oil was that of Proust and Dumas,1 who found a camphor
(lauro-camphor) present. There is little doubt, however, that the oil
they examined was not a genuine lavender oil, but contained other oils,,
possibly including spike oil.2
Bertram and Walbaum found that linalyl acetate was the principal
constituent of French lavender oil, and that linalol was also present in
the form of esters of butyric, valerianic, and caproic acids. A small
amount of free linalol is also present in the oil.
Semmler and Tiemann 3 have isolated limonene and a sesquiterpene
from the oil. This sesquiterpene has later been identified as caryophyl-
lene. Very small amounts of a-pinene are present, as well as a small
quantity of geraniol, probably in the form of esters.
Cumarin is present, in traces only, and furfurol, an aldehyde which
is probably valeric aldehyde, amyl alcohol, ethyl-n-amyl-ketone, and
d-borneol are all constituents of the oil, but in very small amount.
According to Elze4 nerol and thymol are present in lavender oil,
but Schimmel & Co. deny that thymol is a constituent of the pure oil,
and consider that Elze was working on an adulterated specimen.
Traces of cineol may be present, but this is doubtful.
The principal difference between English and French oil of lavender
is that the former contains only a very small quantity of linalyl esters;
whilst cineol appears to be a normal constituent of English oil. Semm-
ler and Tiemann 5 have isolated from English oil the terpene limo-
nene, linalol, and Z-linalyl acetate. Cineol and a sesquiterpene are also
normal constituents of the oil.
OIL OF LAVANDULA DENTATA.
This oil is not commercially distilled from the unmixed herb, but
there is no doubt that the flowers are to some extent gathered promiscu-
ously and distilled with other lavender species in Spain—and to a smaller
extent in France.
l 2
8
Annalen 6 (1833), 248. 4
Jour, prakt. Chem., 11, 45 (1892), 590.
Bericht, xxv., 1880. Chem. Zeit., 34 (1910), 1029.
6
Bericht, 25 (1892), 1186.
LABIATE 203
The oil resembles rosemary oil rather than lavender oil in odour,
having a distinctly camphoraceous smell. The dried flowers yield about
0*8 per cent, of essential oil which has the following characters :—
Optical rotar-ion . . + 32° , + 44°
Acid value 1,8
Eater „ . 12 , 25
„ „ (after acetylation) . . . . . 65 , 75
The oil contains d-camphor, d-fenchone, and probably fenchyl-
alcohol
OIL OF LAVANDULA STOECHAS.
Lavdndula Stoechas is the herb known as Eomero santo (holy rose-
mary) by he Spaniards. The essential oil is very similar in odour to
that of Lavandula dentata, resembling rosemary rather than lavender.
Refractive index . . . . . . . . 1:4700 „ 1-4730
Acid value 2 ,, 4
Ester „ 95 „ 110
It contains cineol, a ketone which is probably pino-camphor, and a
highly laevo-rotatory alcohol.
OIL OF LAVANDULA PEDUNCULATA.
This oil has been obtained from lavender plants growing in Portugal.
It has no commercial value. It has a specific gravity 0*939, optical
rotation - 45°, and contains about 39 per cent, of esters. It is soluble
in an equal volume of 80 per cent, alcohol. It contains cineol, and prob-
ably thujone.
OIL OF LAVANDULA BURMANNI.
Two samples of this oil from plants grown in India have been ex-
amined by Schimmel & Co.1 One was distilled from the flowers only,
the other from the leaves. The oils had the following characters :—
Leaf Oil. Flower Oil.
Optical rotation - 0° 40' -H 1° 40'
Acid value 9-9 1-9
Ester „ 36-3 115-7
Samples of these oils have been examined at the Indian Institute of
Science at Bangalore and found to have the following characters :—
Leaf Flower
Oil. Oil.
07°
Specific gravity at —o 0-895 0-921
Refractive index at 25° 1-4S30 1*4683
Saponification value 44-25 149-5
„ „ (after acetylation) . . . . 141-5 199
1
SchimmePs Bericht, October, 1913, 110.
OIL OF LAVANDULA SPICA (L. Latifolia).
This oil, known as spike lavender oil, is a commercial article of con-
siderable importance, and is used very largely in cheap perfumery.
Its odour is camphoraceous, and far less pleasant than that of true
lavender oil. Lavandula spica flourishes, generally speaking, in the
same districts as Lavandula vera, and grows to a very large extent and
very freely in Spain. The yield of oil from the flowers varies from
0*5 to 1*0 per cent.
Spike lavender oil is a pale yellow or almost colourless oil having
French Oil. Spanish Oil.
Specific gravity . . . . 0-900 to 0-921 0-903 to 0-922
Optical rotation . . . . - 2° „ + 7° - 5° „ + 12°
Kefractive index . . . . 1-4640 „ 1-4680 T4640 „ 1-4670
Ester value 3 „ 22 4 „ 27
Dalmatian spike oil resembles Spanish oil in characters.
Pure spike oil will dissolve in 2 to 2*5 volumes of 70 per cent, or in
3 to 4 volumes of 65 per cent, alcohol to a perfectly clear solution.
The most important feature of spike oil from the perfumer's point of
view, is the amount of free alcohols contained therein, which is usually
returned as borneol (calculated from the acetylation results). This
will, in genuine spike oils, rarely be less than 30 per cent. Spanish
spike oils frequently show rather less than this—28 to 29 per cent.,
but it is probable that this is due to the fact that other Labiate flowers
grow in close proximity with the lavender flowers, and are to some ex-
tent distilled with them, without any intention of fraud, but because it
is in practice impossible to separate them. Umney l has recorded the
analyses of about a hundred samples of spike lavender oils, with a borneol
value varying from about 23 to 41 per cent. Any sample with less than
28 per cent, should be viewed with suspicion, and samples containing
much less than this are undoubtedly adulterated.
If spike oil be fractionally distilled (preferably in a flask as illus-
trated (fig. 24), with the lowest bulb holding about 125 c.c.), using 50 c.c.
for the purpose, the first 10 per cent, obtained is usually dextro-rotatory,
and not differing more than about 2° in rotation from the original oil.
The author and Bennett have shown that (as is especially the case
with Spanish oils) pure spike oil may be slightly laevo-rotatory up to
- 3°, and also yield a laevo-rotatory fraction on distillation as above.
The following classification of spike oils grown in different districts
by Birckenstock (see under Lavender Oil) confirms this statement. So
that the statement that pure oils are always dextro-rotatory is incorrect.
Birckenstock distinguishes the following groups : Ardeche, H6rault,
Drome, Gard, Basses-Alpes, Alpes-Maritimes, and Var. Whilst, accord-
ing to the author, the first-named group represents the spike type
proper, and yields oils of the following properties: d15o 0'918 to 0'921;
aD + 7° 48' to 9° 36'; aD of the first 10 per cent, of the distillate + 8° to
4- 10°; ester-content 4 to 5 per cent.; alcohol-content 21 per cenfc.;
soluble in 3 volumes 67 per cent, alcohol,—the " Var " group some-
what approaches the lavender type : dl50 0*9035 to 0'905 ; OD - 1° 10' to
0°; aD of the first 10 per cent, of the distillate + 2°; ester-content
2 to 3 per cent.; alcohol-content 20 to 32 per cent.; soluble in 5 to 6
ôlumes 60 per cent, alcohol. The other groups represent intermediate
1
P. and E.O.R. (1916), 239.
LABIATE 205
Specific gravity and rotation therefore become less, whilst
alcohol content and solubility increase ; inasmuch as the borneol greatly
preponderating in the " Ardeche " type is gradually substituted towards
the " Var " type by linalool and geraniol. The laevo-rotation of the last-
mentioned oil is also remarkable, but Birckenstock considers that up to
- 1° 10' this is still normal, provided that the first 10 per cent, of the
distillate rotate to the right.
Our knowledge of the chemistry of this oil is chiefly due to*
Bouchardat,1 who showed that it contained pinene and cineol (euca-
lyptol). Later, he proved the presence of camphor, linalol, borneol, and
camphene. Terpineol and geraniol are also present in small quantities.
Probably a sesquiterpene also exists in this oil, but its presence has not
yet been definitely proved. The similarity of the odour of this oil to
true lavender and rosemary is easily explained when one considers that
FIG. 24.
the chief ingredients of the oil are cineol, borneol, linalol, and camphor.,
Linalol is an important ingredient of lavender oil, whereas cineol,
borneol, and camphor oil are all present in rosemary oil.
Spike oil is largely alterated with turpentine, and probably, ac-
cording to Umney, with the commoner varieties of rosemary oil. The
former is detected by the adulteration in specific gravity and solubility,,
whilst the latter interferes with the solubility and the percentage of free
alcohols present. Spike oil is largely used in cheap perfumery and in
the manufacture of certain kinds of lacquer for fine china manufacture.
It is also largely employed as an adulterant of ordinary oil of lavender.
EOSBMABY OIL.
This oil is distilled from the flowering tops of the plant Rosmarinm
officinalis, a native of the south of Europe. The rosemary is a plant,
1
Comptes Rendus, 106 (1888), 551; 117 (1893), 53 and 1094.
largely influenced, as are most of the plants of this natural order, by
variations in soil and climate, and the marked differences in English
and foreign oils is more than can be explained by care in the method
•of production. The plant is grown in a few places in England, but
English rosemary oil is almost negligible as an article of commerce, the
.greater part of the commercial oil being produced in the south of
Europe. Several countries on the Mediterranean littoral produce small
quantities, but after the south of France the chief source of the oil is
the Dalmatian Islands. Spain, however, now produces a quantity of
rosemary oil. The Dalmatian produce is chiefly brought into com-
merce vid Trieste, and this is the oil usually known in trade as Italian
rosemary oil. The English oil is by far the most valued, and commands
an infinitely higher price than the foreign oil. The Italian (Dalmatian)
and Spanish oil are the least valuable. In England and the south of
France rosemary is distilled as quickly as possible after it is cut, and
in the same manner as lavender flowers. Care is taken to exclude the
woody parts of the plant, as not only do these take up unnecessary
room in the stills, but also yield a less valuable oil. The best oil is that
which distils over during the first hour of the process. The finest
French oil comes from the departments Gard and H6rault, and the
•neighbourhood. The supply of oil from the Dalmatian Islands is some-
what irregular, and, according to Schimmel & Co., the reason of this
is that the rosemary woods, as they are called, are municipal property,
.and are leased to the peasants and distillers, but with an effective con-
trol as to harvesting. This follows a regular rotation, the general crop
being gathered in one year and very sparing crops for the next two
years. The richest plants grow on the island of Solta, but the success-
ful cultivation of vineyards has nearly replaced the rosemary industry.
A little is cultivated on the island of Lissa, but the majority comes from
Lesina. The total production of these islands varies from 15,000 to
50,000 Ib. per annum. The plants are usually sun-dried before distilla-
tion, and the process is carried out in very primitive apparatus,
which facts possibly account largely for the inferior quality of the oil.
The adulteration practised on this oil appears to commence at Trieste,
and not on the islands. The usual adulterants are turpentine and
petroleum oils, although the finer qualities are at times adulterated with
spike oil.
Spanish rosemary oil is now largely employed in cheap perfumery,
but its odour is not sufficiently fine for high grade work. This is, no
doubt, to some extent due to the fact that other Labiate plants,
especially Lavandula spica and Salvia lavandufolia grow in profusion
with or near the rosemary plants, and are cut with the last named, so
that the oil is frequently a mixture of Labiate oils in which rosemary
predominates.
Kosemary oil of excellent quality is also produced in considerable
quantity in southern Tunis, notably in the Bled. The Tunisian oil is
far softer than Spanish oil, although perhaps not quite so fine as the
best French distillates.
The English market takes something like 50,000 kilos of rosemary
oil per annum, while America and Australia are steadily increasing
their demands. French continental production, on the contrary, is
restricted more and more, for the cost of collection and distillation is
becoming too great for remunerative working. Whole ranges of hills in
LABIATE 207
tke Alpes-Maritimes remain uncultivated; in the region of Draguinan

and Lorgues vast tracts of the Basses-Alpes put enormous quantities of
fragrant rosemary at the disposal of the distiller, but the cost of the pro-
duct would barely repay the expense of labour and fuel.
The average yield of essential oil is from 1 to 1*8 per cent.
Eosemary oil has been examined by several chemists. Bruylants l
claimed to have isolated a terpene from the oil, but as the oil on which
he worked had a specific gravity 0'885, it was probably adulterated with
turpentine, so that his results cannot be accepted with confidence.
Gildemeister and Stephan2 have, however, isolated pinene from the
lowest boiling fractions of the oil, which is probably a mixture of dextro-
and laevo-a-prnQue. Camphene has also been definitely identified as a
4X>nstituent of the oil. These two terpenes have been identified, not only
in French, but also in Dalmatian oil. Weber 3 has isolated cineol, and
has also prepared dipentene dihydrochloride from a terpene fraction of
the oil, which makes it probable that dipentene is also present. Cam-
phor 4 and borneol5 are important constituents to which the oil owes
much of its odour. Traces of esters, probably of borneol, are also
present.
Pure rosemary oil has the following characters :—
French Oil of Rosemary.
Optical rotation - 4° to + 13° (rarely to - 9C)
„ „ (of 1st 10 per cent, distilled) . - 6° „ + 14° ( „ „ - 18°)
Refractive index 1-4660 to 1-47*5
Acid value 0-5 ., 2
Ester 3 „ 14
Biters per cent 1 „5
Total alcohols (as borneol) 8 „ 19 per cent.
The oil is usually soluble, with at most faint turbidity, in from 1 to
K) volumes of 80 per cent, alcohol.
Dalmatian Rosemary Oil.
Optical rotation - 1° to -f 7° (rarely to + 12°)
(of 1st 10 per cent, distilled) - 1° to + 8°
Ester „ . 5 20
Esters per cent. 1-8 7 per cent.
Total alcohols 8 18 „
The solubility is identical with that of French oil.
Spanish Rosemary Oil.
(of 1st 10 per cent, distilled) - 6° to f 6° (rarely a little higher)
Acid value 1 „2
Ester „ 2-3 „ 17-5
Esters per cent. 0'8 „ 6 per cent.
Total alcohols 10 „ 20 „
l
Jour. de Pharm. etde Ghim., iv. 29 (1879), 508.
*Arch der Pharm., 235 (1897), 586. * Annalen, 238 (1887), 89.
*8 Ibid., 114(1860), 197.
Jour, de Pharm. etde Chim., iv., 29 (1879), 508.
[Very many samples of Spanish " rosemary" oil have figures well
outside the above limits. They are usually, however, distillates fron*
a mixture of sage with rosemary flowers—and are accepted as " com-
mercial " Spanish rosemary oil.]
Tunisian Rosemary Oil.

Befractive index 1-4660 „ 1-4695
Acid value 1„2
Ester , 5 „ 10
Total alcohols 12 to 17 per cent.
English Rosemary Oil.

Be ractive index 1-4650 „ 1-4690
Esters . . about 5 per cent.
Greek rosemary oil does not differ materially from Dalmatian or

Spanish rosemary oils; but Corsican and Sardinian oil have the peculi-
arities of having a high optical rotation (up to + 18°), high ester value
(about 10 to 13 per cent.), and a high percentage of alcohols (up to-
25 per cent.).
Up till recently laevo-rotatory rosemary oils, or oils yielding a laevo-
rotatory first 10 per cent, on distillation, were regarded as adulterated.
The above figures indicate the incorrectness of this view. The whole
question of the fractional distillation of this oil has been studied by the
author and C. T. Bennett,1 who had consigned to them authentic speci-
mens of rosemary herb grown in Spain and France respectively (some
300 Ib. in all), and the oil from these was distilled in the laboratories,
of Wright, Layman & Umney, Ltd., under the direct supervision of
Mr. J. C. Umney. The results of the examination of these oils prove
beyond doubt that a laevo-rotatory oil is consistent with purity, and
also a dextro-rotatory oil giving laevo-rotatory fractions.
It is customary in France to distil the oil from herb which has been
collected after the flowering period (February and March) and dried for
about eight days in the sun. In Spain the distillation goes on all the
year round, and some variation is therefore to be expected. Both fresh
and dried herbs are employed, the latter when the supply is greater
than the capacity of the stills and when it has to be carted from a long
distance. In the dry state the leaves can be readi'y separated from the
stalks by threshing, but in the fresh condition it is impossible so to-
separate them. The yield from the fresh herb is from 0*4 to 0*75 per
cent, while the dried leaves yield about 1 per cent, of oil, which is of
finer quality than that from the fresh herb. The characters of three;
typical samples were as follows :—
1
Chemist and Druggist (1906), 137.
LABIATE 209
1 (Spanish). 2 (French). 3 (French).
Source . Leaves alone Leaves and stalks Leaves alone

Specific Gravity 0-917 0-897 0-914
Optical Rotation + 5° 30' 8«30' - 3°
Esters calculated as Borny
Acetate 3-2 per cent. 3-0 per cent. 3-6 per cent.
Total Borneol . 19-7 „ 10-9 18-5 „
Optical Botation of first 10 per
cent. (100 mm.) . - 1° - 12° 'r& - 10°
No. 1 was distilled from herb collected towards the end of last
summer and dried in the sun. It consisted entirely of leaves which
were well developed and of a fine green colour. The yield was 0'89>
per cent.
No. 2 was distilled from stalky herb in the dried condition, collected1,
in February last. The proportion of stalks amounted to nearly 60 per
cent. Yield of oil 0*4 per cent.
No. 3 was distilled from the same consignment as No. 2, but the-
stalks were separated and the leaves alone distilled. They yielded 1'09»
per cent, of oil, containing a high proportion of borneol. The leaves,
were somewhat discoloured, probably owing to some fermentation hav-
ing taken place.
The stalks alone yielded very little on distillation, showing that they
contain a much smaller percentage of oil and that of little odour value-
These results show tbat the laevo-rotatory constituent (laevo-pinene)
occurs in greater proportion when the stalks are included, and that an
inferior oil is then obtained. It is evident that oils derived from care-
fully picked leaves yield fractions which are laevo-gyrate.
The following are the results of fractionation of the above oils:—
No 1.
Specific Refractive Boiling-point

Fraction. Gravity. Rotation. Index. Commencing
at
Per Cent.
1 10 0-884 - 1° 1-4676 153° C.
2 10 0890 - 1° 10' 1-4680 156° C.
3 10 0-895 - 1° 20' 1-4681 159° C.
4 10 0*902 + 1° 1-4682 162° C.
6 10 0-903 + 1° 20' 1-4683 163° C.
6 10 0-911 + 2° 1-4686 165° C.
7 10 0-922 + 2° 30' 1-4700 169° C.
8 10 0-940 + 3° 1-4736 177° C.
Residue 20 Partially crystallised 1-4885 185° C.
VOL. I. 14
No. 2.
Fraction. Specific Gravity. Rotation. Refractive

Index.
Per Cent.
1 10 0-874 - 12° 30' 1-4660
2 10 0-878 - 13° 1-4670
3 10 0-879 - 13° 30' 1-4670
4 10 0-883 - 12° 20' 1-4670
5 10 0-886 - 11° 20' 1-4670
6 10 0-891 - 10° 30' 1-4670
7 10 0-896 - 8° 30' 1-4678
8 10 0-909 - 5° 30' 1-4702
Residue 20 — — 1-4859
•
No. 3.
Fraction. Specific Gravity. Rotation. Refractive

Index.
Per Cent.
1 10 0-885 - 10° 1-4660
2 10 0-888 - 10° 1-4680
3 10 0-891 - 9° 20' 1-4685
4 10 0-896 - 7° 70' 1-4686
5 10 0-900 - 6° 70' 1-4686
6 10 0-909 - 4° 50' 1-4686
7 10 0-921 - 1° 1-4686
8 10 0-938 + 2° 1-4697
Residue 20 Partially crystallised
It is therefore quite clear that the borneol is derived principally, if

not entirely, from the leaves, and a genuine laevo-rotatory oil containing
a comparatively low percentage of borneol may be assumed to have been
-distilled from the leaves and stalks, since the leaves alone yield an oil
-which has a finer odour and higher borneol-content.
According to Gutkind,1 the optical rotation of Spanish rosemary oil
is very variable, even when the plants are grown in the same locality.
He states that the rosemary on one hill-side frequently yields an oil of
;an opposite rotation to that on another hill-side, although, as a rule, the
ôptical rotation is constant for each particular hill-side. In this respect,
therefore, it differs from the observations made by Henderson on the
oils of rosemary distilled at Hitchin, which he found in some instances
to be dextro-rotatory and in others laevo-rotatory.
J. C. Umney 2 gives the following particulars of a sample adulterated
with camphor oil, and compares it with pure French oil. Where, how-
ever, camphor oil is used as an adulterant, it is usually the light variety,
free from safrol, which lowers the specific gravity and greatly diminishes
the solubility.
The oil appeared to smell slightly of safrol, and was found to have
:a somewhat high specific gravity, -916 being high for a natural French
oil of rosemary. The oil, submitted to fractional distillation, afforded
.the following figures :—
1 2
Private Communication from J. C. Umney. P. and E.O.R., April, 1913, 271.
LABIATE 211
Adulterated Oil.
Optical rotation +14°
Total alcohols 19-3 per cent.
Esters 1-6 „
Solubility, 1 in 2 volumes of 80 per cent, alcohol.
Fractionation :—
Fraction. Specific Rotation. Refractive

Gravity. Index (25°).
Per Cent
1 . .10 •883 + 14° 1-4660
2 . .60 •894 + 16° 1-4675
3 . .10 935 + 15° 1-4750
4 . .10 •961 + 12° 1-4822
5 Residue 10 -978 — 1-4950
No crystallisation occurred in the higher fractipns.

Pure French oil fractionated under the same conditions:—
•Total alcohols 15-1 per cent.
Esters 2-2 ,,
Fractionation :—
Fraction. Specific Rotation. Refractive

Gravity. Index (25°).
Per Cent.
1 . .10 0-880 - 4° 1-4643
2 . .60 0-897 + 3° 1-4650
8 . .10 0-938 + 13° 1-4690
i 4 . .10 0-953 + 13° 1-4725
5 Residue 10 0-955. 1-4835
Fraction 4 partially crystallised on cooling.

From a comparison of these figures it will be seen that the highest
boiling fractions of the adulterated oil have a high specific gravity, a
high refractive index, and, further, do not crystallise.
He was able to obtain a considerable bulk of the oil, which has been
most carefully fractionated, and from which it was possible without
difl&culty to obtain, not only safrol, confirming the suspicion of the pre-
sence of camphor oil, but further undoubted proof of the presence of
terpineol, which is a constituent of camphor oil, and not hitherto de-
tected in rosemary oil.
PEPPEKMINT OIL.
Peppermint oil is produced in numerous countries, the principal
supplies of the world being derived from the United States and Japan.
English peppermint oil is, however, the most highly esteemed of all
and commands by far the highest price. France, Italy, Russia, Ger-
many, and other countries now produce appreciable quantities of
peppermint oil, some of which are of very fine quality and are highly
esteemed.
The oil distilled in America and Europe is derived from varieties of
Mentha piperita, chiefly Mentha piperita, var. vulgaris or " black mint,"
and Mentha piperita, var. officinalis or " white mint". The former ia
the hardier plant and yields the greater quantity of oil, whilst the latter
yields less oil, but of more delicate odour and flavour. The parent plant
of Japanese peppermint is Mentha arvensis, var. piperascens Holmes, or
Mentha canadensis, var. piperascens Briquet, which yields an oil much
inferior to that of Mentha piperita.
From a commercial point of view, peppermint oil appears to have
commenced its history about 1750, when cultivation was commenced at
Mitcham in Surrey. To-day the English peppermint fields are chiefly
located in this district, and in the neighbourhoods of Market-Deeping in
Lincolnshire, Hitchin in Hertfordshire, and Wisbeach in Cambridgeshire.
The oil produced by English-grown plants bears the same relation to
most of the foreign oil as is the case with lavender oil, although it i&
claimed that certain distillates of German plants approach the English
variety in fineness of odour, as they certainly do in price. Distillation
of the oil in America, which is now the most important producer of
peppermint oil, commenced in the early part of last century, when a
small distillery was erected in Wayne County, New York State. To-day
many thousand acres are under cultivation, and the principal districts
producing the oil are Wayne County (New York), various portions of
the State of Michigan, especially Wayne County (Michigan), Van Buren,
St. Joseph's and Kalamazoo Counties ; St. Joseph's County, Indiana;
and to a smaller extent in some of the counties of Ohio and in some
parts of the south of the Canadian province of Ontario. The whole of the
peppermint cultivation in America is thus confined to the north-east
portion of the United States and extreme south of Canada. In Germany,
plantations have been successfully established at Miltitz, and in the neigh-
bourhood of Leipzig, by Schimmel & Co., and a fine oil is obtained from
the plants grown there. A fair amount of oil is also produced in France,
in the departments of the Yonne and du Nord. Japan and, to a certain
extent, China produce large quantities of peppermint oil. Mr. E. M.
Holmes identified the Japanese plant as Mentha arvensis, and as the
Chinese plant differs slightly from the Japanese, he retains, for the sake
of distinction, the names Mentha arvensis, var. piperascens, for the Ja-
panese, and Mentha arvensis, var. glabra, for the Chinese plant.
There appears to be some slight confusion in regard to the Japanese
peppermint plant. This plant was brought over to England by the late
Mr. Thomas Christy, and this plant was considered by Mons. Malui-
vaud, the French authority on mints, to be a variety of Mentha arvensis,
and in this Mr. E. M. Holmes acquiesced, and it was named Mentha
arvensis, var. piperascens Holmes. Dr. Thorns has recently carried out
some cultivation experiments at Dahlem, near Berlin (which will be re-
ferred to later), with plants received from Japan and examined by Dr.
Briquet, the German authority on mints, who considered it to be a»
variety of Mentha canadensis, and he named it Mentha canadensis, var.
piperascens Briquet, but stated that in his opinion it was identical with
Christy's plant. This was probably a misunderstanding arising from his
not having seen the particular plant grown by Christy, for as grown at
Sydenham, and also by Holmes at Sevenoaks, it showed a very decided
difference.
LABIATE 213
The chief Japanese plantations are located North of Yokohama, and
southward into the provinces of Bingo-Bitchin. The largest centre of
cultivation is in the province of Uzen, which produces more oil than all
the other provinces put together. Uzen is in the north-east of the island
of Hondo, the chief of the Japanese islands. After Uzen, Bingo is the
most important producing province. The following map (reproduced by
the courtesy of the editor of the Chemist and Druggist) illustrates the
ohief peppermint districts in Japan :—
Oil dT Peppermint
FIG. 25.
American Peppermint Oil.—According to the United States Depart-
ment of Agriculture, the United States produce—mostly in Michigan,
Indiana, and New York—rather under half of the world's total output
of mint (peppermint and spearmint) oils, or approximately 250,000 Ib.
out of a universal production of 600,000 Ib.
The Agricultural Department affirms that on the muck lands of
Southern Michigan and Northern Indiana, where mint culture has
become highly specialised, the cost of establishing an acre of new mint
and caring for it during the first season is placed air about $30. In
subsequent years the cost per acre would be about $15. These esti-
mates do not make any allowance for fertilisers, taxes, interest on the
land, equipment, superintendence, and other charges of this character.
In Wayne County, New York, where mint is cultivated on uplands, the
cost of preparing the land is somewhat less, but the tillage costs, on the
other hand, are higher because of the greater quantity of labour re-
quired. The industry in the New York district, however, appears to-
be declining in extent. It is now carried on in rather a small way
chiefly by co-operation between landowners and practical mint-growers.
In Michigan and Indiana, on the other hand, many of the growers have
invested considerable capital in the business, and have provided them-
selves with an equipment which enables them to handle the product in
an economical manner.
. The yield of oil per acre varies widely, ranging from almost nothing
to nearly 100 Ib. About 325$IM?*^ peppermint are required to pro-
duce a pound of oil in commercial practice.
Peppermint thrives best in deep soils which are rich in humus and
retentive of moisure, but fairly open in texture and well drained. It
may also be grown successfully in well-prepared upland soils, such as
those suitable for corn or potatoes. The area selected should be cropped
for one or two years with some plant that requires clean and frequent
tillage. The tillage is also continued as long as possible during the
growth of the mint, for successful mint-growing implies clean culture
at all stages of progress. The crop is cut at the time of full bloom,
which, with new plantings, is usually early in September. It is, as a
rule, allowed to dry partially in the field before being hauled to the still.
Laboratory experiments show that this results in an appreciable loss of
oil, but the loss is not regarded by growers as sufficient to offset the in-
creased cost of handling and distilling the green herb. Exposure to
frost, however, must be avoided, as frozen mint yields scarcely one-half
of the quantity of oil which could otherwise be secured.
Nitrate of soda, applied at the rate of 50 to 150 Ib. to the acre, and
potash have been widely used as fertilisers to stimulate the growth of
mint, and potash is particularly useful against a form of chlorosis, due,
apparently, to too much water in the soil. On the other hand, ground
bone, acid phosphate, and lime do not seem to be of marked benefit.
Few diseases and pests trouble peppermint. During very wet seasons
a rust fungus sometimes appears, and crickets, grasshoppers, and cater-
pillars may always do some damage. On suitable soil, and with proper
cultivation, yields of from 2 to 3 tons of mint herb per acre may be ex-
pected. The yield of oil is extremely variable, and large yields can only
be expected from fields that are in the best possible condition. A fair
average for well-managed commercial plantings may be said to be 30
Ib. of oil per acre.
Eabakl has investigated the effect of cultural and climatic conditions
on the yield and quality of American peppermint oil. The following
tables indicate the differences in the oil distilled from the fresh and the
dry herb at various stages of growth, and also those of the oils when
distilled from the entire herb, the tops, and the fresh leaves at various
stages of growth :—
J
U.S. Dept. Agric., Bull. 454 (1916).
LABIATE 215
PHYSICAL PROPERTIES AND CHEMICAL COMPOSITION OF PEPPERMINT OIL
DISTILLED FROM THE FRESH AND FROM THE DRY HERB AT VARIOUS
STAGES OF GROWTH DURING SUCCESSIVE YEARS.
Physical Properties. Chemical Composition

(per Cent.).
Year and i
Description of Solubil- Ester
Material. Rota- ity in Free Menthol.
Specific tion, Refrac- 80 Acid (Men-
Colour. Odour, and per thyl
Taste. Gravity. 50mm. tion. Cent. (as A- Ace-
Tube. Alcohol. cetic). tate). Free. Total.
1908.
Fresh Herb: °C. Vols. i !

Budding . Pale yellow ; pleasant 0-912 -15-8 1-4696 1-5 0 9-55 30-561 38-08-
menthol-like odour ;
cooling taste
Flowering . Pale yellowish-green ; •924 - 4-5 1-4728 1-25 0 14-50 23-97 35-39
pleasant ester-like
odour ; very pun-
gent taste
Fruiting . Y e l l o w i s h - green ; -918 -21 1-4681 1-5 0 2440 34-33 53-55
p l e a s a n t minty
odour ; less pungent
and cooling taste
1909.
Fresh Herb :
Budding . Golden-yellow ; pleas- -9158 - 9-2 1-4738 1 •10 6-72 30-1 35-39
ant, faint odour ; i
slightly pungent
and cooling taste •
Flowering . Pale yellow ; agree- •9203 -10-6 1-4662 1-2 •21 7-07 46-5 52-09
able menthol-like
odour ; p u n g e n t
minty taste
Fruiting . Straw coloured ; very •9151 - 8-3 1-4676 •8 •10 12-37 33-8 43-58
flowery odou r;
m i n t y , pungent,
taste
Dry Herb :
Budding . Greenish - y e l l o w ; 1 -9337 -13-1 -1-4695 3 1-2 •17 13-26 36-07 46-38
strong minty odour ;
p u n g e n t , minty
taste
Flowering . G o l d e n - y e l l o w ; 1 -9163 -13-5 2 l-4695 •16 12-73 37-37 47-44 j
minty odour ; pun-
gent, minty, slight-
ly fatty taste
Fruiting . Yellow ; unpleasant 1 '9344- - 8-1 2 1-4718 8 1 •36 17-68 34-2 48-16
minty odour; strong,
p u n g e n t , minty
taste
1 2 3
At 22° C. At 25° C. Turbid in excess.
4
Turbid in 1 volume absolute alcohol; insoluble in 80 and 90 per cent, alcohol in any proportion.
5
Turbid in 2 volumes or more.
PHYSICAL PROPERTIES AND CHEMICAL COMPOSITION OF PEPPERMINT OIL
DISTILLED FROM THE FRESH AND FROM THE DRY HERB AT VARIOUS
STAGES OF GROWTH DURING SUCCESSIVE YEARS (continued).
T,. . , ,. .. Chemical Composition

Physical Properties. (per ^
Year and
Description of Solubil Free E.s er
Material. Rota- ity in Acid (Men- Mei thol.
Colour, Odour, and Specific tion, Refrac- 80 per (asA- thyl
Taste. Gravity. 50 mm. tion. Cent. cetic). Ace-
Tube. Alcohol tate). Free. Total
19iO.
Fresh Herb :
Budding . Dark golden ; not 3
-9155 -121 ! 1-4718 4.7 •86 16-62 43-76 56-85
f r a g r a n t , minty
odour; slightly bit-
ter, pungent, minty,
baste
Flowering . Pale yellow; mild, 3
-9273 - 5-7 1 1-4320 2-6 •03 11 67 30-94 40-18
agreeable odour; fat-
ty, strong, cooling,
pungent taste
Fruiting . Y e l l o w i s h - green ; 3
-9250 - 7 * 1-4712 5.3 1-14 20-86 12-7 29-14
very fragrant flow-
ery odour ; very bit-
ter and slightly
pungent taste
Dry Herb :
Budding . Light golden ; herb- :i
-9167 -11 1
1-4724 5.6 1-20 19-80 39-41 55-01
like, faint, minty
odour ; slightly bit-
ter, pungent, minty
taste
1
Flowering . Pale brown ; herb- — 1-4765 3-20 30-41 —
— — —
like odour ; pungent
and cooling taste
3
Fruiting . Golden-yellow ; fra- -9383 - 3-3 / 1-4713 «-5 •56 20-51 —
grant, pleasant —
odour ; very bitter
and slightly pun- 1
gent taste i
1911.
Fresh Herb :
j — —
Budding . — -06 12-02 32-37 41-84
Flowering . — , — — — — -20 13-79 34-11 44-97
1 2 3
At 22° 0.
5
Turbid in 2 volumes or more. At 24° C.
4
Turbid in 4 volumes or more. Turbid in 1J volumes or more.
* Turbid in If volumes or more.
LABIATE 217
COMPARISON OF THE PHYSICAL PROPERTIES AND THE CHEMICAL COMPOSITION OF
PEPPERMINT OILS DISTILLED FROM THE FRESH LEAVES, FROM THE TOPS,
AND FROM THE \ ENTIRE FRESH HERB AT THE VARIOUS STAGES OF GROWTH.
Physical Properties. Chemical Composition

(per Cent ).
Year and
Description of Solubil Ester
Material. Rota- ity in Free (Men- Menthol.
Colour. Odour, and Specific tion, Refrac- 80 per Acid thyl
Taste. Gravity 50mm tion. Cent. [as A- (Ace-
Tube. Alcohol. cetic) tate). Free. Total.
1909.
Budding stage : Vols.
Herb Golden-yellow; 1
0-9158 - 9-2 2 1-4738 o-io 6-72 30-1 35-39
p l e a s a n t , faint
odour, s l i g h t l y
pungent, cooling
taste
1
Leaves . Straw coloured ; frag- -9143 -12-1 2 1-4713 4
1-4 •014 9*9 37-7 45-67
rant but faint
minty odour ; fatty,
pungent, slightly
bitter taste
1 1 5
Tops Straw coloured ; very -9151 - 12 1-4718 1 •116 8-84 31-8 38-76
f r a g r a n t minty
odour; fatty, bitter,
pungent taste
Flowering stage :
Herb Pale yellow ; agree- 1 -9203 -10-6 2 1-4662 6
1-2 •21 7-07 46-5 52-09
able menthol-like
odour; p u n g e n t ,
minty taste
Leaves . Straw coloured; pleas- 1 -9389 -11 2 1-4706 6
1-2 •52 17-3 141-7 55-38
ant, minty odour;
pungent taste
fi
Tops Straw coloured ; flow- 1 -9370 -10-3 2 1-4732 l •48 15'9 37-75 50-29
ery odour ; pungent
taste
fruiting stage :
Herb „ . Straw-coloured ; very 1 -9151 -8-3 2 1-4676 5.3 •10 12-37 33-8 43-58
flowery o dou r ;
• minty, p u n g e n t
taste
Leaves G o l d e n - y e l l o w ; 1 -9373 -9-6 1-4730 4
1-5 •32 19-8 37-58 53-18
pleasant, m i n t y
odour; minty, pun-
gent taste
Tops Light straw coloured ; 1 -9223 -9-5 1-4723 5
1• •16 15-56 34-8 47-08
pleasant, flowery
odour; minty,
slightly pungent '
taste
1 2 3 4
At 22° C. At 25° C. Clear in excess. Turbid in 3 volumes or more.
5 6
Turbid in 1$ volumes or more. Turbid in 2 volumes or more.
218 . THE CHEMISTKY OF ESSENTIAL OILS
COMPARISON OP THE PHYSICAL PROPERTIES AND THE CHEMICAL COMPOSITION OP
PEPPERMINT OILS DISTILLED FROM THE FRESH LEAVES, FROM THE TOPS,
AND FROM THE ENTIRE FRESH HERB AT THE VARIOUS STAGES OF GROWTH
(continued).
*
Chemical Composition
Physical Properties. (per Cent.).
Year and
Description Solubil- Ester
of Material. Rota- ity in Free (Men- Menthol.
Colour, Odour and Specific tion, Refrac- 80 per Acid thyl
Taste. Gravity. 50mm. tion. Cent. (asA- Ace-
Tube. Alcohol. cetic). tate). Free. Total
1910.
i
Budding stage : 1 j
Herb Dark golden ; not 3
-9155 - 12-1 1 1-4718 4.7 •86 16-62 43-76 56'85
f r a g r a n t , minty
odour ; slightly bit
ter, pungent, minty
taste
3
Leaves Golden-yellow ; faint -9156 - 13-1 1 1-4710 4
-6 •90 19-80 18-79 34-89
not especially
m i n t y od our ;
slightly bitter, pun-
gent taste
Tops Golden-yellow; agree- — — — — •13 13*44 29-19 39-78
able, minty odour ;
strong, pungent,
bitter, cooling taste
Flowering stage :
Herb Pale yellow ; mild 3
-9273 - 5-7 1 1-4820 2-66 -03 11-67 30-94 40-13
agreeable o d o u r
fatty, strong, cool-
ing, pungent taste
Leaves Pale yellow : strong •9231 - 9-4 1-4753 •7 1-90 122*27 37-83 55-38
i
mi n ty odo u r ;
slightly fatty, bit-
ter, pungent, cool-
ing taste
Tops Pale yellow ; frag- •9242 - 6-5 1-4780 •8 1-43 22-98 48-60 66-71
rant, a g r e e a b l e
odour ; fatty, bitter,
pungent, cooling
taste
Fruiting stage :
Herb Y e l l o w i s h green ; •9250 - 7 1-4712 .'8 1-14 20^86 12-7 29-14
very fragrant flow-
ery odour ; very
bitter, slightly pun-
gent taste
Leaves Golden-yellow; —
1-4720
—
4-80 43-40 1 —
—
strong minty — i
odour; bitter, cool-
ing, slightly pun-
gent taste
Tops Greenish - y e l l o w ; —
— 1*4738 — 3-30 28-29 —
agreeable, flowery —
odour; bitter,
slightly pungent,
cooling taste
1 2
At 22° C. Turbid in 3 volumes or more.
3 4
At 24° C. Turbid in 4 volumes or more.
LABIATJE
Eabak draws the following conclusions as the results of his ex-
periments :—
Conditions of soil and climate are influential factors in the forma-
tion of oil and its constituents in the peppermint plant. Light sandy
or loamy soils appear to be most favourable for the production of an oil
of high quality.
The yield of oil distilled from fresh plants apparently decreases as
the plant matures. Drying the plant before distillation results in a
considerable loss of oil. The largest proportion of oil is found in the
leaves and flowering tops.
The percentage of esters in the oils increases as the plants approach
maturity. The menthol-content of the oil bears a close relationship
to the ester-content. The free acidity and ester-content of the oil
distilled from dry plants is considerably higher than in the oil from
fresh plants. The drying of the plants causes changes favourable to
esterification, while the percentage of free and total menthol in oils-
distilled from dried plants is also uniformly high.
The formation of esters and menthol takes place most readily in
the leaves and tops of the plant, the metabolic processes showing
increased activity as the plant matures.
The effect of shade upon the peppermint plant is to decrease
esterification and the formation of menthol, and is due possibly to
the lessened activity of the elimination of water by the plant.
The action of frost noticeably increases esterification and the
formation of menthol.
The mint is usually left in the sun in small cocks for a short time
before distillation. With regard to the advisability of drying the plants
before distillation, thus reducing the bulk and so increasing the charge
of a still, Mr. Todd, a well-known Michigan grower, carried out experi-
ments on a very large scale, and came to the following conclusions:—
1. No loss of essential oil of peppermint through diffusion in the
atmosphere is occasioned by thorough drying of the plants and pro-
longed exposure to atmospheric action prior to distillation. (This con-
clusion, however, does not appear to be quite correct.)
2. Such exposure does not increase the crystallising tendency of the
essential oil.
3. A heavy and insoluble resinoid is produced by oxidation, increas-
ing the specific gravity of the oil and affecting the boiling-point and
solubility, by raising the former and decreasing the latter.
4. To obtain the best results as to the quality of oil produced and the
facility of handling and distillation, the plants should be dried as thor-
oughly as possible without endangering the loss of leaves and blossom;.
distillation should then take place as soon as convenient to prevent the
formation of resin.
The earliest elaborate research on the composition of American
peppermint oil is that of Power and Kleber.1 The oil examined by these
chemists was distilled from the dried plant and had the following char-
acters :—
Menthol as esters 14-12 per cent.
Free menthol . . . . . . . . . 45*5 ,,
1
Pharm. Rundschau, 12 (1894), 157.
220 THE CHEMISTEY OF ESSENTIAL OILS.
On fractional distillation, the following fractions were obtained :-
To 200° 2-6 per <:ent.
200° to 205° 2-4
205° 210° 8-6
210° 215° 18-8
215° 220° 24
220° 225° 19-6
225° 230° 9
230° 235° 3-6
Residue 12-2
The following compounds were identified in the oil:—

Acetic aldehyde CHS. GOH (about 0-044 per cent.).
„ acid CH ? . COOH.
o-pinene (inactive) C10H16.
Limonene (laevo) G10H16.
Menthone C10H18O.
Menthyl acetate G10H19.
Gadinene C15H24.
A menthyl ester C10H19. C8HnO2.
Iso-valerianic aldehyde C4H9. GOH (about 0*048 per cent.).
„ acid C4H9 . COOH.
Phellandrene CIOH16.
Cineol G10H18O.
Menthol C10H19. OH.
Menthyl-iso-valerianate C10H19. C5H9O2.
A lactone C10H16O2, melting at 23°.
Amyl acetate and dimethylsulphide have also been detected in traces.

Pure American peppermint oil has the following characters :—
Specific gravity at 15° 0-900 to 0-915 (rarely to 0'925)
Optical rotation . - 18° to - 35° (rarely below - 18°).
Refractive index . l-4600,to 1-4640
Menthol as esters 5 to 14 per cent.
Total menthol 50 „ 62 „
Menthone 9 to 19 per cent, (rarely to 25 per cent.)
An examination of nine samples by Kleber1 indicates that the

menthone is usually lower as the menthol is higher. The following are
his v figures :—
a
D. Total Menthol. Menthone.
0-8995 25° 27' 49-7 per cent. 18*8 per cent.
0-8983 24° 20' 48-4 16-8
0-900 24° 14' 51-7 17-98
0-904 24° 28' 50-2 16-98
0-902 24° 30' 50-2 17-7
0-905 23° 18' 53-5 14-0
0-901 26° 12' 56-1 13-9
0-902 25° 30' 55-8 16-7
0-903 23° 49' 56-4 15-2
The following table is due to Power, and includes a few oils other
than American distillates. Samples No. II. and Ila. are so abnormal
that some suspicion as to their genuineness may well be forgiven:—
1
Schimmel's Report, April, 1914, 77.
CHARACTER OF PEPPERMINT OILS (POWER).
From 50 c.cm, of Oil there Distil in c.cm. be-

li tween the Temperatures noted :
Specific Optical
Designation of the Oil. Gravity Rotation in Free Total
at 100 mm. Menthol. Menthol. Q o* 0« 0. 0- o» 0*
ci a?
15° C. Tube. 1^
"rt S o 0 i—i rH <N <N w 00
£
&'i
^t2 vo 6 <J> ui
^
3 CN
^ S ^ <N £1 (N
• Co.
j Per Per Per

Cent. Cent. Cent.
I. F. B., from Dry Herb . . . 0-9140 - 32° 0' 14-12 45-5 59-6 1-3 1-2 4-3 9-4 12-0 9-8 4-5 1-8 6-1
la. F. B., from Fresh Herb 0-9130 - 30° 0' 11-25 43-2 54-5 0-6 1-2 5-7 8-5 11-6 9-2 4-2 2-2 6-7
16. Wayne Co., N.Y., 1892 0-9158 - 26° 45' 9-32 40-8 50*1 1-4 1-8 6'3 10-0 12-9 7-3 2-4 1-8 6-3 f1
Ic. „ „ 1893 0-9110 - 32° 30' 9-04 46-1 55-1 1-1 1-4 5-0 10-7 13-9 7-6 2-9 1-6 5-4 >>
Id. ,, „ Twice Rectified 0-9110 - 32° 45' 8-61 51-0 59-6 1-5 3-7 8-8 14-7 12-2 4-2 — 5-2 00
—
(F. S. & Co.) >>
le. V. B. Co., Mich., 1893 . 0-9067 - 29° 20' 6-39 43-6 50-0 1-9 5-0 9-4 13-2 12-4 2-3 5-1 t~3
If. Wayne Co., Mich., 1893
II. St. J. Co., Mich., 1893 (I.) .
0-9135
0-9135
-
-
28° 30'
9° 45'
7-73
3-63
50-3
28-9 .
58-0
32-6
1-7
1-9
1-6
2*6
5-5 9-6 12-2
12-0 14-0 11-6
8-9 3-2 3-1
4-4
5-8
3-3
N
lla. „ „ 1893 (II.) . 0-9083 - 19° 30' 4-23 29-6 35-8 3-4 7-0 7-6 13-2 10-1 — —
3-3 1-5 — 4-1
116. "RoseMitcham"^ 0-9050 - 23° 35' 4*37 44-2 48-6 4-4 9-6 13-4 17-1 3-2 2-5
He. •• Crystal White " V Michigan . 0-9105 - 23° 55' 6-74 44-2 50-9 1-7 5-8 9-9 15-4 9*4 3-4 — 4-1
lid. " Redistilled Oil " J 0-9105 - 23° 30' 8-59 46-5 55-1 3-3 6-5 8-1 8-8 9-9 5-2 — — — 8-7
III. Mississippi 0-9250 - 13° 40' 11-47 24-2 35-7 0-9 0-3 1-2 6-5 16-2 11-8 4-8 2-4 6-6
IV. Japanese, Normal 0-9100 - 34° 45' 3-45 72-7 76-2 0-7 0-4 3-4 22-0 17-2 2-1 1-0 — 3-5
V. „ Dementholised 0-9030 - 31° 20' 5-71 55-1 60-8 0-5 1-6 10-2 20-7 12-0 3-3 — 2-4
VI. Mitcham 0-9070 - 27° 55' 4-92 53-9 58-8 1-4 0-7 12-2 24-7 8-6 — — 3-7
-» —
VII. Saxon . . . . . 0-9100 - 26° 0' 6-38 61-2 67-6 1-7 10-9 21-3 11-6 2-1 _ _ 2-1
Russian O i l . . . . . .
0-905 to 0-915 - 17° to - 22° 5 45 50
French Oil 0-918 „ 0-921 - 6° „ - 10° 5 to 10 35 to 40 45 to 50 —
— — — — —
Italian 0-912 „ 0-925 - 2° „ -16° 10 46 50 „ 60 — — — — — 1 — —
—
to
Japanese Peppermint Oil.—This oil, as mentioned above, is distilled
from Mentha arvensis (Mentha canadensis), and forms an important
Japanese industry. The most important modern contribution to the
literature of this oil is by Naojiro Inouye.1 Nagasaki2 describes the four
following varieties of the plant which are cultivated :—
1. Akamaru.—The leaves of this plant are round, the stalk is reddish-
violet, and the flowers of a violet colour. The yield of oil and menthol
is greater in this than in the other varieties.
2. Aomaru.—The leaves are round, the stalk is blue, and the flowers
violet.
3. Akayanagi.—The leaf is violet on the under surface, the stalk is
blue and the flower white. The yield of oil is low.
4. Aoyanagi.—This variety resembles the wild plant. Its stalk is
blue and flower white.
The following details3 of peppermint cultivation are o'f interest;
•" Peppermint is cultivated in different parts of Japan, mostly on the hill-
sides, although that grown on low-lying ground which can alternately
be used for rice is richest in crystals. As the-oil which has been freed
from menthol crystals is inferior both in taste and odour to English and
American oil, experiments have been made in the cultivation of English
and American peppermint, but unfortunately without success. The best
oil is produced in the districts 'of Okayama and Hiroshima, where three
cuts are made yearly: in May, June, and August. The first cut yields
about 47 per cent, of crystallised menthol (i.e., by freezing only), the
second about 53 per cent., and the third about 60 per cent. In the dis-
trict of Yamagata only two, and in Hokkaido only one cut is made, but
in the last-named district the area under cultivation is considerably larger
than in the other, so that, in spite of a single crop and a crystallised-
menthol-yield of only 45 per cent., more than one-half of the total output
of menthol is produced in the province of Hokkaido.
" The method of distilling is the same everywhere. It lasts four hours,
the yield from 82 Ib. of dry leaf of the first cut being 14, of the second
24, and of the third 21 oz. of oil, or 1*07, 1*83, and 1*60 per cent, respec-
tively. The value of course fluctuates, being dependent both upon the
quality and the dryness of the leaves. The second cut is always the
most prolific; thus, for example, a field which produces 300 Ib. of leaves
in the first cut will yield 800 Ib. in the second and 600 Ib. in the third.
The production per acre is about 5000 Ib. of dry leaves, yielding about
80 Ib. (= 1-60 per cent.) of oil.
" The price of the leaves, like that of the oil, varies and the distillers
•only make small profits. The oil is collected by brokers, and resold to
the large refineries, of which there are two of importance. In the dis-
tricts of Odashitsuki, Okujoto, and Bingo there are so-called peppermint-
guilds, who test the oil and give certificates of weight and purity. In
the other districts the refiners must take the oil as it comes."
E. Marx 4 has made an elaborate report on the distillation of the oil
in Japan.
From this report it appears that the industry has not benefited by the
introduction of European methods, although it is a considerable one.
1
Communication from the Laboratory of Prof. Kremers, Madison, Wisconsin,
1908. 2 3
4
Yamagata, S. 1. Board of Trade Journal, 79 (1912), 78.
Gessell. fur Natur. und Volkirkunde Ostasiens (1896), 6, 355.
LABIATE 223
It is Marx's opinion that the substitution of an improved method for

that now followed would benefit both the quantity and quality of the
oil produced. The apparatus universally adopted in Japan consists of
cast-iron broad-edged boilers, A, I, H ; wooden vats, B; and condenser,
C. Generally there are three sets of stills, etc., combined in one battery
with a common furnace. They are arranged in steps, so that the lowest
is built into the ground.
The process is begun by filling the boilers, A, I, H, with water; then
the vats, B, which have perforated bottoms, are placed on the broad
FIG. 26.—Peppermint stills (section).
FIG. 27.—Peppermint stills (ground plan).
FIG. 28.—Bamboo syphon.

and surrounded with straw bands and soft clay. It is in these
vats that the peppermint is placed. Next, the inverted condenser, C, is
put on and filled with water and the furnace, E, lighted. The heat
passes from E below A, I, and H, and disappears through the chimney,
N, on which the distilling begins. The boilers I and H, are properly
heated by the fumes as they pass, and sufficiently so, as H is smaller
than I, and I smaller than A. The steam, penetrating the herb, carries
with it the essential oil, and condenses on the outer side of C, being
collected in the vessel,^K, hanging upon it, from which the condensed
water containing the oil passes through a bamboo reed, L, inserted in K
to the florentine flasks, O. Each of these consists of a little wooden
container in which a glass cylinder (an old bottle without bottom or neck)
is inserted. In this, the water separated from the oil runs through the
little pipe, P, again into the boilers, A, H, I. As soon as the water in
C becomes hot, the workman replaces it with cold water. The empty-
ing is effected by a bamboo syphon. The workman inserts the short
arm in the inverted cooler, closes the lo'wer opening and sucks the syphon
until the water flows into it. According to the inborn easy-going nature
of the Jap workman, who likes to pause in his work for a smoke, it
often happens that the cooling water in C begins to boil and steam runs-
through instead of the condensed water saturated with oil, so that the
atmosphere in the neighbourhood becomes so impregnated with pepper-
mint that anyone near loses sight and sense of smell. The workman
does not go unpunished, as he burns his mouth by sucking up the boil*
ing water; that, however, does not prevent him from going on smoking,
and the same thing happens again. In addition to the direct loss of oil
caused by this negligence, it often happens that the water-boiler be-
comes dry, and then the herb in the still is burnt, in spite of the straw.
This sometimes happens in spite of all precautions, as the flames fre-
quently overheat the boilers if the water runs too low, and the products
of burning straw get over with the distillate, which explains why Japanese
peppermint oil sometimes has a peculiar empyreumatic flavour.
Japanese oil of peppermint contains a very high proportion of
menthol, a large amount of which is frequently removed, and the de-
mentholised oil sold as such. The term Japanese peppermint oil is
understood on the market as meaning the dementholised oil. The usual
manner in which the menthol is obtained is by a simple process of freez-
ing, whereby the crystals separate, and are freed from the adherent oil
either by pressure or centrifugal treatment. To purify them they should
be recrystallised from a suitable solvent, such as alcohol. If it is wished
to extract the maximum quantity of menthol, it is advisable to distil off
the terpenes, etc., under reduced pressure, and then freeze the residual
oil.
The crude distillate, containing the whole of the menthol, is known,
in Japan as Torioroschi.
Japanese peppermint oil was first carefully investigated by Beckett
and Wright.1 They found present in the oil besides menthol, a body iso-
meric with menthone but which was not identified as menthone. Other
bodies found by these chemists were almost certainly mixtures and not
chemical individuals.
Murayama 2 detected Z-limonene in the oil, and Schimmel & Co.3
isolated from it the alcohol ethyl-amyl carbinol C2H5. CH(OH)C6Hllr.
and 4 also the ketone A'-menthenone.
The identity of the ethyl-amyl carbinol found in the oil has been
settled5 by the preparation of the same body synthetically. Schimmel
& Co. heated normal caproic aldehyde with magnesium methyl-iodide,
and thus obtained ^-ethyl-w-amyl carbinol, which was found to possess
characters substantially identical with those of the natural compound.
1 2
Jour. Chem. Soc. (1876), 13. Jour. dePharm. et Chim., vii. 1 (1910), 549*
^Report, April, 1912, 103. *Ibid., October, 1910, 97.
, April, 1913, 82.
LABIATE 225
l
Pickard and Littlebury have isolated from the oil an isomer of
menthol, which occurs in small quantity, and which they have named neo-
menthol. This body is of particular interest in regard to the stereo-
chemistry of this important body.
These chemists pointed out that a ketone of the configuration of
menthone should exist in both the cis and trans forms, one of Which
may be termed menthone, the other isomenthone. When the keto-
grouping is reduced to the carbinol complex, two optically inactive
menthols should exist for each of the ketones, and each of these should!
yield its pair of optically active menthols. It is proposed to term the
optically inactive alcohols menthol and neomenthol in the case of men-
thone, and isomenthol and isoneomenthol in the case of isomenthone.
They artificially prepared the isomers, menthol and neomenthol, and re-
solved each into its optically active varieties, so that the characters of
four out of the eight possible optically active menthols are, to some ex-
tent, known. They have also shown that, in addition to Z-menthol,
tf-neomanthol is present in Japanese peppermint oil.
The starting-point of the experimental work was the reduction pro-
duct of thymol, by finely divided nickel. The unchanged thymol is
removed by washing with a solution of soda; alcohols are transformed
into hydrogen phthalic esters, which are then removed by sodium car-
bonate. The ketones remaining are treated with semi-carbazide in the
usual manner, and a mixture of two semi-carbazones obtained, from/
which menthone and isomenthone can be obtained. Fractional crystal-
lisation of the hydrogen phthalic esters from acetic acid yielded two pure
products—the less soluble melting at 177° and the more soluble one at
130°. The former on hydrolysis yields pure neomenthol (inactive) v
melting at 51°.
The ester melting at 130° yields inactive menthol melting at 34°.
Pure menthol (inactive) is characterised by its melting-point (34°),
and by those of its hydrogen phthalate (130°), and hydrogen succinate
(85° to 86°). It also forms a phenyl-carbamate melting at 102° to 104°.
By repeated recrystallisations of the brucine or cinchonine salt of the
hydrogen phthalate ester, from acetone or alcohol, the nearly pure
laevo-rotatory form can be obtained, whilst by the use of cinchonidine,.
the dextro-rotatory variety can be separated. .L-menthol was found to-
be identical in melting-point and specific rotation with the natural
menthol, which forms the principal ingredient of the peppermint oils,,
etc., whilst ^-menthol has the same melting-point and an equal rotation^
but in the opposite direction. Strangely enough, the dextro and laevo
varieties differ considerably in odour, and each forms a crystalline
benzoate, whilst the benzoate of the inactive variety is an uncrystallis-
able oil.
Neomenthol in the inactive condition melts at 51°, and forms a
hydrogen phthalate melting at 177°, and a phenyl-carbamate melting at
114°. On oxidation it yields menthone, identical with that formed by
the oxidation of menthol, thus proving that the two bodies are stereo-
isomers. By fractional crystallisation of brucine salt of the hydrogen
phthalate, the dextro variety was obtained, whilst by similar treatment
of the quinine salt of the hydrogen succinate Z-neomenthol was obtained.
The specific rotation of these optically active neomenthols is + 19'6°..
1
Jour. Chem. Soc., 101 (1912), 109.
VOL. I. 15
'Curiously enough, the menthones resulting from the oxidation of these
active neomenthols are optically active in the opposite sense to the
menthols themselves.
The characters, therefore, of two of the optically inactive and four of
the optically active isomeric menthols have been fixed with certainty.
By treating the alcoholic residue of Japanese peppermint oil, from which
the bulk of the ordinary Z-menthol had been removed, with phthalic
anhydride in the usual manner, the authors obtained a mixture of
phthalic acid esters, from which after twenty-eight recrystallisations
from 95 per cent, acetic acid, a fraction was obtained which melted at
141° to 144°, and had a specific rotation of + 57*16° in chloroform. This
substance was the phthalic acid ester of ^-neomenthol, containing a little
of the ordinary Z-menthol ester. This was proved (1) by mixing it inti-
mately with artificially prepared d-neomenthol hydrogen phthalate, when
the melting-point was practically unchanged, and (2) by hydrolising the
ester and oxidising the resulting menthol, when almost pure Z-menthone
was obtained, having a specific rotation - 28*33°, and yielding a semi-
carbazone melting at 187° to 189°. Japanese peppermint oil therefore
contains Z-menthol, together with a small amount of d-neomenthol.
Walbaum l has isolated from the fraction of the oil boiling at 250°
to 310° the acetic ester of 3 hexen-I-ol, of the formula
CH2(C6H5)C02. CH 2 . CH 2 . CH : CH .CH2. CH2
which, when pure, has the following characters :—
„ 290° „ 760 mm.
Specific gravity a t 1 5 ° . . . . . I'OOO
Refractive index a t 2 0 ° . . . . 1 '4981
It is a liquid with an onion-like odour.
Pure, natural Japanese peppermint oil, containing all the natural
menthol, has the following characters :—
Specific gravity at 15° 0-900 to 0'912
Befractive index 1-4600 ,, 1-4635
Acid value 0'5 ,, 2'5
Menthol as esters . . . . . . . 3 to 8 per cent.
Total menthol 70 ,, 90 „
Solidifying-point 16° to 28°
The dementholised oil of commerce has the following characters :—
Optical rotation - 24° „ 36°
Acid value 0-5 „ 3
Total menthol . 45 to 55 per cent, (rarely higher)
Various colour reactions have been proposed with a view to dis-
tinguishing between Japanese and other peppermint oils. These are of
doubtful value, but there is no question that all peppermint oils other
than Japanese give the following reactions to a marked extent, whilst
Japanese oil either gives no reaction, or at most a very slight one. A
colour reaction, however, would be of great use if it were negative with
the Other peppermint oils, and positive with Japanese oil, which is the
cheapest variety obtainable.
]
Jour, prakt. Chem. (1917), 96, 245.
LABIATE 227
Umney 1 heats 1 c.c. of the oil with 0*5 gram of a mixture of equal
parts paraformaldehyde and citric acid over a water-bath. With
Japanese peppermint oil there is no coloration, whereas with American,
English, Italian, and Saxon oils a purple colour develops.
If five drops of oil are dissolved in 1 c.c. of glacial acetic acid a blue
colour results within one hour with peppermint oils, except in the case
of Japanese oil.
Many experiments have been undertaken with a view to transport
peppermint plants from a country where the oil has developed a parti-
cularly fine odour and flavour, into other countries. Few plants, how-
ever, appear to alter to so great an extent under these conditions as those
of the natural order Labiatae, and when once the soil and climate suit the
plant, transplanting it to different conditions causes the oil to assume
different characters. Thus Mitcham plants, transplanted to France, will
not yield an oil which is necessarily identical with Mitcham oil. Eecent
experiments, however, have been to some extent successful, and oils
having characters very similar to English oil have been obtained from
Mitcham plants grown in Italy. The most complete experiments, how-
ever, in2 this direction have been carried out with Japanese plants by
Thorns, with a view to determine whether oil containing as much
menthol as is present in Japanese oil could be obtained in Germany or
in German colonies. The Japanese plants were cultivated at Dahlem,
near Berlin, and at Okahandja, South-West Africa.
At Dahlem cuttings were made, the first on 17 July and the second
on 10 August. The yield of oil from the July crop was 0*74 per cent.,
and that from the August crop 0*624 per cent. The oils had the charac-
ters given below, which are compared with those of the oil distilled from
plants harvested in the summer of 1911:—
July Crop, August Crop, Summer Crop.
1912. 1912. 1911.
Specific Gravity 0-8987 at 18° 0-903 at 16° 0-8954 at 22°

Solidifying- point 13-5° 14-75° 14-5°
Optical Rotation - 35-22° - 35-29° - 34-75°
Acid Value 2-66 2-73 4-01
Ester „ . 12-96 13-80 12-74
Acetylation Ester Value 283-8 280-1 283-2
Combined Menthol 3-78 °/o 3-56 '/0 3-50 «/0
Free Menthol . 75-20 °/0 75-65 °/0 75-27 °/0
Total 78-98 °/0 79-21 % 78-82 °/0
A sample of oil distilled from plants grown at Witzenhausen, the

yield being just under 1 per cent, on the dry herb, had the following
characters :—
Specific gravity at 15-5° 0-9042
Solidifying-point 14-5°
Acid value 3-3
Ester „ 15-15
Acetylation ester val 16 291-6
Combined menthol 6-99 per cent.
Free menthol . • 74-16
Total „ . . .81-15
J
a
P.and E-.O.R., 2 (1911), 275.
H. Thorns, Ber. deutsche pharm. Ges., 20 (1910), 424; Arbeit. Pharm. Instit.
Univ. Berlin, 8 (1911), 93.
In dealing with the experimental cultivation at Okahandja, in German
South-West Africa, the herb was divided into the leaves and the stems,
which were distilled separately. The leaves yielded 1*225 per cent, of
oil, and the stems 0*2 per cent. Calculated on the whole plant the yield
was 0*866 per cent. Both oils were very similar, and were characterised
by a very high menthol value, in each case over 84 per cent. They had
Leaf Oil. Stem Oil.
Specific Gravity at 20° 0-904 0-9000

Solidifying-point . 20*75° 21°
Optical Rotation . - 35-29° - 35-3°
Acid Value . 1-56 2-77
Ester „ 8-29 6-15
Acetylation Ester Value 306-6 304-1
Combined Menthol 2-31 °/o 1-71 °/0
Free Menthol 83-01 °/0 82-93 °/0
Total . . . , . , 85-32 °/0 84-64 °/0
No less than 57| i per cent, of menthol could be separated by freezing

from these oils.
CHINESE PEPPERMINT OIL.
A small quantity of peppermint oil is distilled in the neighbourhood
of Hong-Kong, from a plant which is, in all probability, Mentha cana-
densis, var. glabrata. This oil has been examined by the Imperial
Institute,1 by Schimmel & Co.,2 and by Shino Saki.3 The three samples
1. 2. 3.
Specific gravity 0-918 0-9187 0-9091
Optical rotation - 44° 40' - 44° 2' -35°
Menthol as Esters 13-55 per cent. 12-6 per cent. 8-08 per cent.
Total menthol. 64-24 64 78-65 „
FRENCH PEPPERMINT OIL.

Peppermint oil is distilled at Grasse, Cannes, Vence, Cagnes, and
Villeneuve-Loubet, as well as in the Basses-Alpes, Var, and Haute-
Garonne, etc. The French varieties of Mentha piperita are not identical
with those cultivated in England. According to A. and E. G. Camus,4
Mentha piperita is not a separate species, but is a hybrid of Mentha
viridis and Mentha aquatica. Two well-defined forms are cultivated
in the south of France which are termed by Camus Mentha piperita
officinalis, var. pallescens, and Mentha piperita officinalis, var. rubescens.
These, however, do not agree in characters with the forms described by
Planchon and Collin as "blanche" and "noire"—nor are they identical
with our own "black" and "white" mints. These facts illustrate the
very great variability of the peppermint plant. The following figures
illustrate the characters of the two oils:—
1 2
3
Bull Imp. Inst., 11 (1913), 434. Report, October, 1910, 96.
4
/. Chem. Ind. Tokio, 1919, 22, 458.
Boure-Bertrand Fils, Report, October, 1911, 3.
td
FIG. 29.—Cultivation of peppermint in Vaucluse. to

fcO
J/M.V.] [Pa rf-u-nierie Mudenu,
Ordinary Peppermint, Red Peppermint,

Pallescens. Rubescens.
Specific Gravity 0-9191 0-9184 0-9170 0-9136

Rotation . . .. - 10° 54' - 8° 2' - 16° 38' - 13° 44'
( 1 vol. 1vol.
Solubility in 80 % Alcohol \ afterwards afterwards
I clouding —
clouding
Acid Value 0-8 0-8 1-0 1-2
Ester „ 40-5 31-7 18-9 17-5
Menthol Acetate 14-3 o/0 11-2 °/0 6-7 °/0 6-2 °/0
Ester Value after Acetylation 160-8 169-1 180-2 185-6
Total Menthol 50-9 °/0 53-9 % 58-0 °/0 60-0 °/0
Free 39-6 °/0 45-1 °/0 52-8 °/0 55-1 °/0
Menthone 7'3 °/ 16-8 o/o
The limit values for French peppermint oils are, however, wider
than those indicated for these two particular varieties. Most—if not
all—genuine oils will have characters which fall within the fol-
lowing :—
Optical rotation . . .• - 5° ,, - 35°
Total menthol 48 „ 70
Many French oils are not soluble in 3 volumes of 70 per cent,
alcohol, but will generally dissolve clearly in 4 volumes.
In rare cases where the plants have been attacked by certain insect
pests, oils have been obtained which are dextro-rotatory up to + 7°.
French oil of peppermint contains,1 in addition to8 menthol and its.
esters, isovaleric aldehyde, isoamyl alcohol, Z-pinene, A -^-menthene and
cineol.
ENGLISH PEPPERMINT OIL.
Two varieties of the plant are grown in England, known as " black "
and " white" mint. Of these the former is the coarser plant, rarely
flowering in England, and yielding more oil of somewhat less delicate
aroma than the white mint. These appear to be forms of Mentha
piperita, var. officinalis, but are certainly not identical with the French
forms (vide supra) named by A. and E. G. Camus rubescens and
pallescens, although these botanists believed them to be so. The herbs
are distilled in the green state, although sometimes left for a day or two
in heaps, after being cut. In England most of the stills used hold from
4 to 8 cwt. of herbs, and have a false bottom which is covered to the
depth of 2 ft. with water, and direct heat is then applied. The distilla-
tion is carried on for about five hours. The yield varies according to the
season from about •£• to 1 per cent.
According to the Journal of the Board of Agriculture? from 500 to
1000 acres are under peppermint cultivation in England. In this country
black mint yields twice as much oil as does white mint, and as a result
the cultivation of the latter has been supplanted to a considerable extent.
Peppermint grows best at a height not exceeding 200 ft. The principal
1 2
Roure-Bertrand Fils, Report, April, 1909, 33. 15 (1908), No. 5.
LABIATE 231
production is in the districts of Ewell, Cheam, Carshalton, and Mitcham;
smaller quantities are also obtained in certain parts of Sussex, Kent,
Hertfordshire, and Lincolnshire, In England the plants are grown from
roots, not from seed. The land having been ploughed and manured
during the winter, the plants are dibbled in in May. A plantation lasts
from four to five years, the best output being in the second year. After
four or five years the land is not used again for mint growing for some
years.
The harvest begins early in September, when a red rust or " snuff "
appears on the leaves. After some slight drying the plants are distilled
for about six hours. The oil-yield per acre ranges from 8 up to 25 Ib.
In general, English oils have a specific gravity of about 0*900 to
0*912, and an optical rotation of - 23° to - 32°, and contain from 60
to 70 per cent, of menthol, or rather more than most American oils.
The refractive index of the oil varies from 1*4600 to 1*4640. The oil is
usually quite soluble in 3 to 4 volumes of 70 per cent, alcohol. Umney
has examined samples of " black " and " white " mint oils comparatively,
and gives the following figures for them :—
Specific Rotation. Menthol— Menthone.

Gravity. as Esters. Free.
Black . •9036 - 23-5° 3-7 59-4 11-8

White •9058 - -33° 13-6 51-9 9-2
Fluckiger and Power1 isolated two laevo-rotatory terpenes from

English peppermint oil, but their purity is doubtful. It is probable that
they were mixtures of pinene, phellandrene, and limonene. A dextro-
rotatory sesquiterpenei(cadinene?) is also present, as well as menthone,
and menthol, both in the free state and as acetate and isovalerianate.
ITALIAN PEPPERMINT OIL.
A certain amount of peppermint oil is distilled in Italy from plants
whose botanical origin is not yet clearly settled. This oil, which is of
excellent quality, has the following characters :—
Optical rotation . — 2° — 27°
Refractive index 1-4615 ',j 1-4685
Menthone . 8 „ 20

During the last few years, however, Mitcham plants have been
cultivated in Italy, and the resulting oil approximates, both in odour
and in general characters, much more closely to ordinary English dis-
tilled oil than the oils above described. This so-called Italo-Mitcham
oil is prepared at Messina and at Pancalieri, Piedmont, Northern Italy.
The oil has been examined by Umney and Bennett,2 and has characters
falling within the following limits :—
1
Pharm. Journ., iii. 11 (1880), 220.
2
Chemist and Druggist, 66 (1905), 945; 67 (1905), 970.
Total menthol . 40 „ 70
Menthone . 12 ,, 18
Umney and Bennett found the oil distilled from July-cut plants to
contain only about 40 per cent, of menthol, whilst oil from the later
FIG. 30.—Distillation of peppermint in Piedmont.

Carles ] [Parfumerie Moderne.
second cutting contained 7O5 per cent. But no generalisation is pos-

sible without the examination of a number of samples.
EUSSIAN PEPPERMINT OIL.
A certain amount of peppermint oil is distilled in various parts of

[Russia, most of which is used in the country itself; but it has recently
appeared on the English market, where its reception has been favourable.
It is distilled in Tambow, the Caucasus, Poltava, and the Ukraine. The
dried herb 1yields about 1*5 to 1*7 per cent, of oil.
Maisit states that peppermint oil is distilled in various parts of
European Eussia, generally in very primitive stills, with the result that
the oil is often burnt and of poor odour. During the past few years
peppermint plantations have been laid out in the Caucasus districts,
which, owing to favourable climatic and soil conditions, are very suitable
for the cultivation of numerous medicinal plants.
A yield of from T6 to 1*7 per cent, on the dried leaves and flowers
is the average obtained. Maisit has examined the oil distilled from one
year old and two year old plants. Both are pale yellow7 in colour,
not very soluble in 70 per cent, alcohol, and having the following
characters:—
1
Arch, der Pliann., 249 (1911), 637.
LABIATE 233
Oil from Specific Gravity Rotation. Acid Value.

at 20°.
One year old Plants 0-912 - 17° 42' 0-57

Two ,, „ . . . 0-913 - 17° 57' 0-56
The menthol values of the two oils are as follows: One year old
plants, 42*44 per cent, free menthol, 49*17 per cent, total menthol; two
year old plants, 41*33 per cent, free menthol, 50*07 per cent, total
menthol.
One hundred grams of the two year old plant oil has fractionated
with the following results :—
200° to 205° 8-0

205° , 210° 8-0
210° , 215° . . . . . . 17-5
215° , 220° 21-0
220° , 225° . . . 5-5
225° , 230° . 7-0
230° , 235° 4-5
Above3 235° 18*0
Maisit considers that a sesquiterpene is present in the high boiling

fractions.
; Those districts known as the Ukraine ( u Little " Eussia and Euthenia)
are exceptionally favourable to the growth of peppermint, and somewhere
about 20,000 Ib. of oil are distilled here every year, and the output is
increasing. A sample of this oil examined by Umney l had the following
characters:—
Total menthol . 53-8 per cent.
Menthyl acetate 6
It was soluble in 3 volumes of 70 per cent, alcohol.
Eussian peppermint oil will usually have values falling within the
following limits:—
Optical rotation. ' - 15° „ - 28°
Total menthol . 50 „ 60
In addition to menthol and menthyl esters, this oil contains men-
thone, principally in the dextro-rotatory form, Z-limonene, dipentene,
inactive a-pinene, and cineol. The esters are present as acetate and
isovalerianate.
GBEMAN PEPPERMINT OIL.
A small amount of peppermint oil is distilled in Germany, successful
plantations existing in Saxony especially. German oil has the following
^characters:—
1
P. and E.OM. (1914), 314.
234 THE CHEMISTKY OF ESSENTIAL OILS.
Specific gravity 0-898 to 0-915 (rarely to 0'930>
Menthol as esters 2*8 to 20-8 per cent.
DALMATIAN PEPPERMINT OIL.
French peppermint plants cultivated at Trieste yield an oil of good
aroma, which has been examined by Schimmel & Co.1 The crude and
rectified oils had the following characters :—
Crude Oil. Rectified Oil.
Specific gravity 0-907 to 0-913 0-909 to 0-914
Optical rotation - 15° 45' „ - 20° 58' - 11° 45' „ - 18° 12'
Refractive index 1-4623 ,, 1-4668 1-4604 „ 1-4678
Menthol as esters 3-4 to 4-8 per cent. 2-6 to 3-8 per cent.
Total menthol 46-3 „ 54-2 „ 39-6 „ 54-1 „
HUNGARIAN PEPPERMINT OIL.
2
Irk has described the oil of peppermint distilled in Hungary, and'
which resembles American oil in aroma. The dry plants yielded 1*17
per cent, of oil, having the following characters :—
Optical rotation . - 26° „ - 32-4°
Menthol as esters. 8 to 12-8 per cent.
Total menthol 56-4 „ 65-2 „
Menthone 7-4 „ 13-2
An interesting series of experiments on the value of manuring has
been carried out on Hungarian peppermint plants.3 These experiments
are summarised in the following table :—
Fresh Dried nil Weight of

Artificial Manure. Farmyard Herb Herb (per Oil
Manure. (kilos per • (kilos per Cent.). (kilos per
hectare). hectare). hectare).
None Without
/ With 4-240 1-300 0-77 10-01
6*760 2-000 0-88 16-40
With Sodium Nitrate Without
. | With 6-640 1-860 0-74 18-76
10-560 2-820 0-81 22-84
With Sodium Nitrate and Without 7-120 1-940 0-73 14-16
Superphosphate . With 8-980 2-320 0-84 19-94
With Sodium Nitrate, Super- Without 8-780 2-200 0-72 15-84
phosphate and Kainit With 13-080 3-140 0-93 29-83
Marshy ground at Admont
without manure 7-89 2-83 0-62 17-55
It will thus be seen that the yield of oil from a given area of com-
pletely manured soil was nearly double that from the same area which
1 2
Bericht, October, 1911, 69. Kistrlettigyi Kozlemdnyek, 13 (1910), 8.
s
Plwrm. Post (1912), 2.
LABIATE 235
had received only farmyard manure, and nearly treble that from land
which was not manured at all. It is interesting to note that the yield
from the natural unmanured marshy ground was the lowest calculated
on the amount of material employed, but was fairly good when referred
to the area of land concerned. The mint grown on a plot without any
manure and attacked by Puccinium gave oil containing the highest
percentage of esters, equivalent to 13*57 per cent, of menthyl acetate.
The same unaffected by the blight gave 10*73 per cent. The oil grown
on the natural unmanured marshy ground had the highest percentage of
total menthol, 64*25 per cent. The puccinium-attacked plant gave oil
containing 62*28 of total menthol, and coming next. The lowest menthol-
content, 57*69 per cent., was obtained from the plot manured with sodium
nitrate and superphosphate without any farmyard manure.
JAVAN PEPPERMINT OIL.
This oil is distilled from Mentha arvensis, var. Javanica. It has the
following characters :—l
Specific gravity at 15° C 0-9979 '2
Rotatory power (I = 100 mm.) + 0° 24'
Soluble in 1J volumes of 70 per cent, alcohol, and the
solution remains clear on the subsequent addition
of the same alcohol.
Soluble in all proportions of 80 per cent, alcohol.
Esters, as menthyl acetate . . 1 7 * 5 per cent.
Combined menthol 13-8
Total menthol 48-2
Free „ 34-4
Ketones and aldehydes . none, or traces
BRITISH EAST AFRICAN PEPPERMINT OIL.

A sample of peppermint oil distilled from Mitcham plants grown at
Molo, in the highlands of British East Africa, has been examined 3 and
found to have an excellent aroma and a very high menthol value. It
had the following values :—
Total menthol 67 -5 per cent.
The most important determination to be made in the examination of
peppermint oil is that of the total menthol, but the menthone value is
also frequently required. This is best obtained by determining the total
menthol in the oil, and then reducing the menthone, *in a separate
portion, to menthol by means of sodium, and determining the menthol
in the reduced oil. If M2 be the total menthol in the reduced oil and
Mx be that in the original oil the percentage of menthone present is
(M2 - MJ154
156
The factor yf | representing the difference in the molecular weights of
menthone and menthol, may usually be neglected.
, g Peppermint oil is frequently adulterated. American oil is sometimes
1
2
Roure-Bertrand Fils, Bulletin, 3 (1910), 1, 59.
This is probably a misprint for 0*8979. A sample examined by Wielen had a
specific gravity 0*921 and optical rotation -f- 4° 40'.
*P.andE.O.R. (1915), 4.
enriched by the addition of Japanese menthol, which is usually cheaper
than American oil. Camphor oil is occasionally used as an adulterant.
The author and Bennett have found cedar-wood oil and oil of African
copaiba used as adulterants (see below). Glyceryl acetate (tri-acetin)
has been found in sophisticated oils. The behaviour on distillation as
compared with normal samples affords the surest indication of such
adulteration. The following table represents a normal distillation of
pure oil:—
PURE OIL.
(Specific Gravity, O911; Eefractive Index, 1-4645).
Quantity. Specific Gravity. Rotation. Refractive Index.
Per Cent.
12$ 0-898 - 10° 1-4660
12$ 0-903 - 14° 1-4635
12$ 0-907 - 16° 1-4645
1-4640
12$ 0-910 - 20°
12$ 0-912 - 23° 1-4615
12$ 0-912 - 23° 1 4615
12$ 0-915 - 34° 1-4630
12$ 0-962 — 1-4790
An oil containing tri-acetin gave the following results (Bennett) :—
Fractions. Quantity. Specific Rotation. Refractive

Gravity. Index.
Per Cent.
1 12$ 0-900 - 15° 1-4645
2 12$ 0-902 - 15° 1-4670 !
3 12$ 0-910 - 14° 1-4650
4 12$ 0-920 - 16° 1-4640
5 12$ 0-926 - 20° 1-4640
6 12$ 0-938 - 22° 1-4640
7 6 1-4640
Residue 19 1-147 — 1-4450
With cedar-wood and copaiba oils, the high boiling fractions are
found to have very high refractive indices (up to 1*4900 or even 1-500),
and in the case of African copaiba, cadinene is found in the fraction 255°
to 270°, and in the case of cedar oils, the corresponding fraction may be
laevo-rotary to the extent of - 45°.
As indicating the behaviour of African copaiba oil, which has been
used to a considerable extent for adulterating this oil, the following
figures for the pure copaiba oil are of interest. A sample of the balsam
itself was distilled by the author and Bennett and the oil collected in
four equal fractions.
The figures obtained were :—
LABIATE 237
Specific Gravity. Rotation. Refractive Index.
1 0-917 + 17° 30' 1-5030

2 0-918 + 28° 30' 1-5043
3 0-921 + 46° 1-5061
4 0-927 + 55° 1-5082
Other samples of African copaiba oil had the following characters :—

Rotation + 30° „ + 37°
Two of these on fractionation showed the following variations in
optical rotation and refractive index :—
I. II.
Rotation. Refractive Rotation. Refractive

Index. Index.
25 per cent. . + 16° 1-4960 + 24° 1-4975

25 . + 19° 1-4965 + 26° 1-4980
25 . + 24° 1-4980 + 29° 1-4981
20 . + 48° 1-5089 + 43° 1-5090
5 ,, residue — — — —
OIL OF SPEARMINT.
There are several different essential oils known under the name
spearmint oil; the botanical origin of the plant used for distillation
differing with the country in which the plant is grown. In the United
States and in this country several varieties of Mentha viridis (Mentha
spicata), are distilled. In Eussia the plant distilled is Mentha vertieellata,
and in Germany either Mentha spicata, var. crispata, or Mentha longi-
folia.
The principal types of this oil have the following characters :—
American Spearmint Oil.
Specific gravity 0-920 to 0-940 (rarely higher)
Acid value 0 „2
Ester ,, 18 „ 36
Carvone (neutral sulphite method) 35 to 66 per cent.
The oil is soluble in 1 to 1'5 volumes of 80 per cent, alcohol.
English Spearmint Oil.
Carvone 30 to 48 per cent.
Austrian Spearmint Oil.1
Russian Oil.
Optical rotation • - 20° „ - 28°
Carvone . . . . . . . . 5 to 10 per cent.
Linalol 50 „ 60
According to E. K. Nelson, an American oil which he examined had
Refractive index at 25° . 1-4866
Ester value 12-4
,, (after acetylation) 36-4
The oil contained 66 per cent, of carvone, phellandrene, and
Z-limonene, and dihydrocarveol acetate. Esters of acetic, butyric, and
caproic or caprylic acids are also present.
Elze,2 after removing the carvone from a German spearmint oil,
obtained an oil with a more intense spearmint odour than the original
oil. It had a specific gravity 0-917 and optical rotation - 28°. It
contained 18 per cent, of esters and on fractionation yielded the follow-
in g results :—
Boiling-point Percentage. Rotation. Ester-
(4 mm.) rf»°. content.
A 40° to 45° 15-0 0-860 - 27° 30' 2-8 %

B 45° „ 75° 15-0 0-894 - 25°
C 75° „ 80° 24-0 0-930 - 24° 19'0 „
D 80° „ 85° 7-5 0-935 - 30° 50'
E 85° „ 100° 35-0 0-940 - 40° 31-0 „
The author was able to prove the presence, in fraction A, of ^-phel-

landrene, which was identified by its nitrosite (melting-point 105° to
105^°) as well as by its constants (boiling-point 175° to 176° [755 mm.] ;
îso 0'8575°; a - 26° 0'). Fraction E, which possessed a marked odour
of spearmint, was saponified. Acetic acid, together with small propor-
tions of valeric acid (probably isovaleric acid?) were identified. The
alcoholic part consisted to the extent of 15 per cent, of dihydrocuminic
alcohol (d150 0-9539 ; a - 30° 15'), which yielded a naphthyl urethane
melting at 146° to 147°, and also, when oxidised with Beckmann's
mixture, an aldehyde (melting-point of the semi-carbazone 198° bo 199°),
and an acid, melting at 132°. When fraction E was saponified the
typical spearmint odour disappeared; hence, in Size's opinion, the
dihydrocuminic acetate is the carrier of the odorous principle of
the oil.
F. Rabak 3 has carried out an investigation on the influence of the
1
According to3 Schimmel & Co. *Chem. ZeiL, 34 (1910), 1175.
Jour. Ind. Eng. Chem. (1918), 10, 4, 275.
LABIATE 239
time of harvest, drying, and freezing of spearmint, on the yield and
odorous constituents of the oil. He gives the following characters for
typical oils distilled from the plant at different stages of its development.
He finds the oil from the fruiting herb more fragrant than that from
the budding or flowering plant. Oil distilled from the leaves and tops
are richer in esters than the oil from the whole plant. Eabak concludes
that the yield of oil is affected by seasonal conditions, being much higher
in some seasons than in others. The maximum yield is obtained during
the flowering period. Drying the plants results in a lower yield, and
freezing causes the oil to contain more esters and alcohols.
Esters as Total
Year and Description Specific Optical Refractive Acetate of Alcohols
of Material. Gravity. Rotation. Index. C10H180. C]0H180.
1908.
Fresh Herb :
Budding . 0-925 at 22° - 25-1° 1-4874 at 24° 3-8 °/0 9-1 °/0
Flowering 0-929 „ - 24-5° 1-4880 „ 4*6 °/0 8-54 °/0
Fruiting . 0-929 „ - 21-7° 1-4853 „ 8-7 °/D 13-4 °/0
1909.
Fresh Herb :
Budding . 0-931 at 21° - 16-3° 1-4891 at 21° 8-6 °/0 12-0 °/0
Flowering 0-929 - 16-1° 1-4864 7-7 °/0 12-4 °/0
Fruiting . 0-934 - 17-4° 1-4873 7-3 % 10-9 °/0
Dry Herb :
Budding . 0-928 - 17° 1-4888 7-0 °/0 11-7 °/0
Flowering 0-933 - 17-5° 1-4868 10-8 °/0 12-7 °/0
Fruiting . 0-925 - 16-5° 1-4846 Q.I
y L °/
lo 15-6 %
1910.
Fresh Herb :
Budding . 0-931 at 23° - 22-8° 1 -4895 at 23° 7*6 °/ 16 °/0
Flowering 0-925 „ - 20-3° 1-4825 „ 13-4 °/° 18-4 °/0
Fruiting . 0-930 „ — 1-4800 „ 15-9 °/0 21-4 °/0
Dried Herb :
Budding . 0-912 „ - 18-2° 1-4775 „ 10-8 °/0 15-7 °/
Flowering- — 1-4788 ,, 31-8 °/0 28-2 °/0
Fruiting . 0-916 „ —
"~-" 1-4745 „ 22-0 °/0 30-5 °/0
Eussian spearmint oil contains, according to Schimmel & Co.,1 50 to

60 per cent, of Z-linalol. Cineol, Z-limonene, and carvone are also present.
OIL OF MENTHA AQUATICA.
The dried herb, Mentha aquatica, the water mint, yields about 0*4
per cent, of essential oil, having an odour of pennyroyal. The characters
'Of the oil are not well determined. An oil distilled by Schimmel & Co.
had a specific gravity 0*880 and optical rotation - 2° 14', whereas a
sample examined by Tschirch had a specific gravity 0*9553, optical
rotation -f 64° 56', and refractive index 1*4827.
Irk 2 found a Hungarian oil to have a specific gravity 0*9603, optical
rotation + 22*73°, and refractive index 1*4900.
1
Bericht, April, 28. *Pharm. Zentral., 52 (1911), 1113.
240 THE CHEMISTKY OF ESSENTIAL OILS'
OIL OF MENTHA SILVESTRIS.
The dry herb, Mentha silvestris, yields about 1 per cent, of essential'
oil, having the following characters :—
Optical rotation about 4- 30°
Refractive index 1'4954
Acid value 2-4
Ester ,, 20-9
„ ,, (after acetylation) 170 to 175
The oil contains very little menthol, but a considerable amount of
pulegone, with a small amount of a phenol (carvacrol?).
An oil examined by Tschirch was stated by him to have the extra-
ordinary optical rotation - 132° 52' and refractive index 1*46856. The
authenticity of this specimen must be regarded with suspicion.
OlLS OF MONARDA.
The best known oil of the Monarda species is that known as America
horse-mint oil, which is obtained to the extent of about 1 per cent, from
the herb Monarda punctata. The oil has a specific gravity from 0*930
to 0*940, and is either optically inactive or slightly dextro-rotatory.
The plant is of considerable importance, as it may before long be
available as a regular source of thymol, which has hitherto been manu-
factured principally from ajowan seeds. Experiments1 have been carried
out by the United States Department of Agriculture, with this end in
view.
In 1910 seeds obtained from Volusia County were sown, and the first
year's growth yielded 0*20 per cent, of oil, and the second 0*24 per cent.,,
the oils containing 64 per cent, of phenols. The plants were observed
to vary, the variations falling into two classes :—
1. Darker plants with more serrate leaves and a pronounced red
colour in the stems and branches.
2. Plants with larger leaves of a light green colour and little or no
red colour in the stems and branches. The lighter type also produced
more leaves. The average yield of oil from the two types (thirty-four
tests being made) was 0*40 per cent, of oil from the dark plants, contain-
ing 66 per cent, of phenols, and 0*42 per cent, from the light type, con-
taining 69 per cent, of phenols.
By continuing the cultivation of the light green variety, the yield of
oil was increased to 0*44 per cent, in 1914, containing 72 per cent, of
phenols; and in 1915 the yield of phenols was 74 per cent., although
the percentage of oil was only 0*42 per cent.
The oil has the following characters:—
Optical rotation + 1° ,, - 2°
The oil contains about 70 to 80 per cent, of phenols, of which a small
portion consists of carvacrol and the remainder of thymol, the rest of the
oil being chiefly cymene, which boils at 175° to 176° C., whilst thymol
boils at 232° C.
Fractional distillation in a copper retort is therefore resorted to, and
1
Bulletin, No. 372; and P. and E.O.R. (1916), 331.
LABIATE
the portion of the oil coming over below 215° C. is set aside. The next
fraction coming over between 215° and 240° C. is then secured, leaving
a thick tar-like mass in the retort, which, so far as is known at present,
has no value. The first fraction may contain about 25 to 30 per cent,
of thymol, the cymene acting as a solvent of it, and preventing crystal-
lisation. This fraction is, therefore, redistilled, and the fraction redis-
tilling between 215° and 240° C. saved.
This fraction, added to the first which was distilled at the same
temperature, is cooled in a shallow dish, and a crystal of thymol added
to start crystallisation. After standing overnight the crystals are separated
from the mother liquor by means of a centrifuge, and the crystals washed
with water whilst the centrifuge is running at full speed. If there is a
large quantity of mother liquor left, it probably contains a considerable
portion of the lower boiling fraction and should be redistilled, removing
any that comes over between 215° and 240° C.
The oil thus treated gives a commercial yield of 66*3 per cent, of
thymol of a perfectly white crystalline character. Carvacrol is also
probably resent in the oil, as well as cymene, and traces of ^-limonene.
Monarda citriodora.—This plant is known in North America under
the name of Lemon Mint. It yields about 1 per cent, of essential oil
on distil ation, which has the following characters :—
Phenols 65 „ 80 per cent.
Aldehydes . 1-2 ., 4 „
Ths oil contains a considerable amount of carvacrol, with a little
thymol. Thymo-hydroquinone is also present, and probably citral and
cymene.
Monarda myristica.—The oil d;stilled from the seeds of this plant,
known as "Owere*' seeds on the Gold Coast, has been examined at the
Impei ial Ins itute.1
1. 2.
Specific gravity 0-849 0-8592 r
Optical rotation - 44° 40' - 57° Q
Acid value . . . . . . . . 1-2 1*4
Ester l«9 6*4
„ „ (after acetylation) . . . . 52-9 35'5
Monarda didyma.— L'his plant is indigenous to North America.
The dtied herb yie ds about 0*03 per cent, of e sential oil, the twigs and
leaves ibout 0'(M per cent, and the half-open flowers 0*26 to 0*32 per
cent.
The oils have th^ follow ng characters:—
No. From Specific Gravity Rotation. Re'ractive Acid Ester

at 15°. Index. Value. Value.
1 Dry Herb . 0-902 at 20° - 10°

2 Half-drv Herb . 0-8786 - 24° 36' 1-4676
3 Dry Twigs and Leaves 0-8855 - 32 38' 1-4689 5-5 20-4
4 Half open Fiowers 0- 665 - 7° 30' 1-4689 2-i , 4-4
5 n »» 0-8740 - 15° 45 1-4674 46 5-6
l
Bull. Imv. Just., 13 1915), 346.
VOL. I. 16
Sample No. 1 was examined by Brandel,1 the remainder by Schim-
mel & Co.2 Neither thymol nor carvacrol are present in the oil.
Monarda fistulosa.—This plant is known in North America as the
wild bergamot. The fresh herb yields from O3 to 1 per cent, of essen-
tial oil, and the dried herb, about 2-7 per cent.
The oil has a specific gravity varying from 0*915 to 0'959, according
to the part of the plant distilled, and is slightly laevo-rotatory. Its
phenol-content is about 50 to 70 per cent.
The oil has been exhaustively examined by E. B. Miller,3 who finds
the following substances present therein: 5-a-pinene, Z-a-pinene, p-
cymene, one or two unidentified terpenes, butyric aldehyde, iso-valeric
aldehyde, a third aldehyde, possibly piperonal, carvacrol, thymoquinone,
hydro-thymoquinone, dihydroxy-thymoquinone, dihydrocuminic alcohol,
an unidentified alcohol, acetic acid, butyric acid, valeric acid, caproic
acid, basic substances, and (in the aqueous distillate) acetone, form-
aldehyde, methyl alcohol, formic acid, and acetic acid.
OIL OF PENNYROYAL.
The leaves and other parts of the plant Mentha pulegium yield the
ordinary pennyroyal oil. This plant is a native of most parts of Europe,
the Caucasus, Chili, Teneriffe, etc. The volatile oil is of a yellow or
greenish-yellow colour, and possesses a strong odour of the plant.
E. M. Holmes* gives the following account of this herb :—
" Two forms of the plant are met with in this country, the commonest
form having weak, prostrate stems, which root at the joints and form a
dense green turf. This is named var. decumbens. The flowering stems
are sparingly produced, and often lie prostrate on the leafy cushions of
the plant.
" The other form, known as var. erecta, has stouter upright flowering
stems, which end off lateral stolons or prostrate branches near the
base. These root sparingly, forming new plants, which gives rise to
upright flowering stems during the ensuing year. This is much rarer
as a wild plant, but is the best for cultivation, as it can be reaped
and tied up into bundles more readily. The stems are usually 6 to 9
ins. long, but under favourable conditions, such as moist soil and a
warm climate like that of Devon and Cornwall, will grow to 15 or 18
ins. There are several other varieties of this plant found on the Con-
tinent. One variety, eriantha, with hairy flowers, occurs at Biarritz,
and a similar form has been found near Falmouth, in this country.
Another, in which the whole plant is hairy, is found in Sicily, and is
named var. tomentosa, and a third, covered with rather stiff hairs, named
var. tomentella, is found near Montpelier and in Hungary. A fourth,
with small leaves, occurring in Eastern Europe is named var. thymifolia,
and on the steppes of Southern Russia a hairless variety with smaller
leaves and flowers, has been described as a variety, but as it is an an-
nual plant it has probably the right to specific raak, and should be
called Mentha micrantha. It has been called Pulegium micranthum.
"Of these varieties it is uncertain which are used on the Continent
as sources of the oil, but the plant used in Spain, so far as can be judged
l
a
Pharm. Rev., 21 (1903), 109.
3
Bericht,October, 1904, 101; October, 1908, 89 ;4 October, 1909, 78.
Circular 4 (1918), University of Wisconsin. P. and E.O.R. (1911), 254.
LABIATE 243
"belongs to the variety eriantha. The Bussian oil is stated to be derived
from the Mentha micrantha."
Specific gravity . . 0-930 to 0'955
Optical rotation . . + 15° ,, + 25°
Refractive index . . 1'4810 „ 1-4865
Pulegone . . . . not less than 80 per cent, (sulphite method)
The oil is soluble in 1/5 to 2*5 volumes of 70 per cent, alcohol. On
'fractional distillation not more than 5 per cent, distils below 212°, and
from 212° to 216° at least 80 per cent, will come over.
The principal constituent of the oil is the ketone pulegone, which,
in very fine specimens, may be present to the extent of over 90 per cent.
According to Tetry l there are also present Z-limonene, dipentene, men-
thol, and menthone.
A Eussian pennyroyal oil, distilled from Pulegium micranthum has
been examined by Butlerow 2 many years ago. It had a specific gravity
Q'934. It commenced to boil at 202° and distilled principally at about
227°. He stated that the principal constituent had the formula G10H160,
so that it was probably pulegone.
American pennyroyal oil is distilled from a herb indigenous to North
America, Hedeoma pulegoides. The oil is principally distilled in North
Carolina, Ohio, and Tennessee. The dried leaves yield about 3 per cent.,
.and the leaves and stalks together about 1/5 per cent, of essential oil.
The oil contains pulegone, up to the extent of about 30 per cent.
According to Kremers 3 the oil contains two other ketones, one of which
is apparently menthone, and the other he has termed hedeomol, which
boils at 168° to 171° and forms an oxime melting at 41° to 43°. He
also identified formic acid, acetic acid and isoheptylic acid in traces.
Barrowcliff4 has recently examined this oil. The oil used in this
investigation possessed the following characters: ^150/1500 = 0'9297;
ao + 25° 44' in a 1-dcm. tube; soluble in twice its volume of 70 per
cent, alcohol. It was found to consist of: (1) an undetermined phenol,
in very small amount; (2) Z-pinene; (3) Z-limonene; (4) dipentene, all
of these terpenes being present in only small amount; (5) l-methyl-3-
cycZohexanone about 8 per cent.; (6) pulegone, about 30 per cent.;
>(7) Z-menthone, and (8) d-isomenthone, identical with the dextro-rota-
tory constituent of Beckmann's " inverted menthone "; the amount of
these two menthones constituting about 50 per cent, of the oil; (9) a
sesquiterpene alcohol, about 2 per cent.; (10) esters of formic, acetic,
octoic, decylic, and salicylic acids, and the ester of a dibasic acid of the
probable formula C8H14O4, together with formic, butyric, octoic, and
•decyclic acids in the free state; all these esters and acids being present
only in small amount.
Barrowcliff does not appear to confirm the presence of any ketone
-corresponding with Kremer's hedeomol.
1
Bull. Soc. Chim., iii. 27 (1902), 186. *Jahr. d. Chem, (1854), 594.
*Amer. Jour. Pharm., 59 (1887», 535. *Jour. Chem. Soc., 91 (1907), 875.
OIL OF THYME.
French oil of thyme, which is the most esteeme 1 variety of the oil
known, is distilled from the fresh herb, Thymus vulgaris. A consider-
able quantity of thyme oil is also distilled in Spain, but probably from
mixed species of thyme, and a certain amount is also distilled in Al-
geria from Thymus algeriensis.
Two commercial varieties are recognised, the " red" and " white""
oils. The former is the crude distillate, and probably owes its red
colour to the action of the phenols present on the iron of the crude
stills and condensers frequently used. The red oil when properly
rectified forms the colourless or "white" oil of commerce. The yield
of oil is very variable—sometimes being as low as 0*2 per cent., often
rising to 1 per cent, in the fresh and 2-5 per cent, in the dried herb.
The French oil contains from 20 to 35 per cent, of phenols, chiefly thy-
mjl, upon which the value of the oil chiefly depends. The Spanish oil
contains a much higher percentage of phenols (50 to 70 per cent.) of
varying composition. A few years ago carvacrol was generally the pre-
ponderating phenol, but to-day careful selection of the species or varieties
distilled has enabled a Spanish oil to be produced, so rich in thymol that
this body is actually manufactured from it.
E. M. Holmes has recently shown that there are two Spanish species
of thyme now known to yield thymol as the principal phenol. These,
are Thymus vulgaris and Thymus Zygis.1
French oil of thyme has the following characters:—
Specific gravity . . 0-905 to 0'935 (rarely 0'900)
Optical rotation . - 0° 30' to - 4°
R .-fract.ve index . . 1-430J „ 1'4'J50
Phenols (mostly thymol) 20 to 40 per cent, (rarely below 25 per cent.)
Spanish thyme oil has the following characters :—
Specific gravity . ' 0'928 to 0'958
Optical rotation + 2° „ - 4°
Refractive index 1-5025 ., 1-5110
Phenols . . . 50 to 75 per cent.
It is soluble in 3 volumes of 70 per cent, alcohol. The phenols of
Spanish thyme oil consist principally of carvacrol, but sometimes a.
fairly large proportion of tnymol is present.
J. C. Umney 2 has examined three samples of thyme oil distilled hi
British East Africa.
The three samples of thyme oil were distilled respectively from
plants grown from seeds obtained through Sutton & Co., of Beading,
from young plants from the same source, and from French seeds of
Thymus vulgaris. The following are the characters of the oils :—
No. Yield. Specific Phenols. Refractive Remarks.

Gravity. Index.
Per Cent. Per Cent.

1 0-50 0-901 32 1-4900 Phenols solidify.
2 0'70 0-905 32 1-4768 ,, liquid.
3 0-38 0-905 40 1-4908 „ partly crystallise.
2
. cmd E.O.R. (1920), 339. Ibid. (1914), 423.
LABIATE 245
No. 1 was distilled from English thyme grown from Sutton's seeds.
No. 2 was distilled from English thyme grown from young plants.
No. 3 was distilled from French thyme grown from seeds.
It will be seen from the above that the percentage of phenols is
highest in the case of the oil distilled from the plant grown from the
French seed, and the phenols partially crystallised. In the other cases
it is noteworthy that the phenols in the oils distilled from plants grown
from English seeds consisted chiefly of thymol, whilst the phenols of
the oil distilled from the English plants could not be induced to crys-
tallise, and therefore appear to consist chiefly of carvacrol.
The phenols are the principal constituents of thyme oil, thymol be-
ing the most valuable for medicinal purposes, but carvacrol, an isomeric
phenol, preponderating in some oils. Cymene and Z-a-pinene are pre-
sent in the oil, as well as a li tie menthone. Borneol and linalol have
been detected in the high boiling fractions of the oil, and a crysta line
body melting at 169° and having the formula C10H22O3. It is probably
identical with a similar body isolated from Juniper berry oil.
Admixture with the oil of Thymus serpyllum does not alter the
specific gravity, but increases the rotation, as this oil * rotates up to
- 12°. Oils adulterated with French turpentine have a high laevo-
rotation. A very large amount of the French " white " oil contains
a considerable quantity of turpentine. The percentage of phenols is
indicated by the decrease in volume on shaking with a 5 per cent,
aqueous solution of potash in a cassia oil flask, and also by the
amount of oil distilling above 220°, which should not fall below 25
per cent. Kremers recommends the following method of estimating the
thymol:—
Five c.c. of the oil to be examined is weighed and brought into a
glass-stoppered burette graduated to y1^ c.c. and is diluted with about
an equal volume of petroleum ether ; a 5 per cent, potassium hydroxide
solution is added, and the mixture shaken for a short time, then the
liquid is left standing until separation is complete. Then the alkaline
solution is allowed to run into a 100 c.c. graduated flask. This opera-
tion is repeated until no further decrease in the volume of the oil takes
place.
The alkaline solution of thymol is made up to 100 or 200 c.c. as the
•case may require, using a 5 per cent, soda solution. To 10 c.c. of this
solution in a graduated 500 c.c. flask is added a —$ normal iodine solu-
tion in slight excess, whereupon the thymol is precipitated as a dark
reddish-brown iodine compound. In order to ascertain whether a suf-
ficient quantity of iodine has been added, a few drops are transferred
into a test tube and a few drops of dilute hodrochloric acid are added.
When enough iodine is present, the brown cplour of the solution indi-
cates the presence of iodine, otherwise the liquid appears milky by the
separation of thymol. If an excess of iodine is present, the solution is
slightly acidified with dilute hydrochloric acid and diluted to 500 c.c.
From this 100 c.c. are filtered off, and the excess of iodine determined by
titration with ^ normal solution of sodium thiosulphate. For calcula-
tion, the number of cubic centimetres required is deducted from the
number of cubic centimetres of ^ normal iodine solution added and
the resultant figure multiplied by 5, which gives the number of cubic
oentimetres of iodine required by ihe thymol.
Every cubic centimetre of ^ normal iodine solution equals 0*003753
grm. of thymol. Knowing the quantity of thymol in the alkaline solu-
tion, the percentage in the original oil is readily found.
The reaction taking place is represented by the equation :—
C H
io i4° + 41 + 2NaOH = C10H12I2O + 2NaI + 2H2O.
In the estimation of carvacrol a slight modification of this'method
must be made, because carvacrol is thrown down as a finely divided
white precipitate, giving the solution a milky appearance. In order to
form a precipitate the liquid is vigorously shaken after the addition of
iodine solution, and is subsequently filtered. Then the liquid is acidu-
lated with hydrochloric acid, and subsequently the same procedure is
followed as was described for thymol. The calculation is also the same.
Labbe 1 has examined an authentic sample of thyme oil and found it
to contain 30 per cent, of thymol, 17 per cent, of a terpene which he
could not identify, 15 per cent, of menthene, 21 per cent, of cymene,
5 per cent, of linalol, 8 per cent, of borneol, and traces of carvacrol.
Thymus capitatus also yields an oil of specific gravity about *900,
and closely resembling the above-described oils. It contains pinene,
cymene, dipentene, thymol, carvacrol, and bornyl acetate. Its phenol-
content is about 6 per cent. A similar oil is obtained from Thymus
camphoratus. A somewhat different oil is obtained from a variety of
Thymus serpyllum (citratus or citriodorus). This oil has an odour re-
calling thyme, lemon, and geranium. Its specific gravity is 0*890 to
0*920 and its optical rotation - 10° to - 20°. It contains only a very
small amount of phenols, but cymene and a sesquiterpene have been
isolated from it.
The value of this oil depends so much upon the phenols it contains
that it is important that these should be estimated, as the abstraction of
thymol, a valuable commercial product, is by no means uncommon.
Thymus Mastichina, the so-called Spanish wood marjoram, yields an
oil of thyme which has been examined recently by Dorronsoro.2 It
has a bright yellow colour, turning darker with age, and a camphorace-
20°
ous odour reminding of thyme. Its constants are as follows : dô 0*907
-LO
to 0*945; CID - 0° 50' to + 4° 40'; n^0 1*4630 to 1*4654 ; saponifica-
tion value 12*7 to 18*5 ; ester-content 4*44 to 6-47 per cent, (calculated
as linalyl acetate) ; ester value after acetylation 29*2 to 49*3 = 8*2 to
14*09 per cent, alcohol C10H18O.
The oil is soluble in any proportion in 94 per cent., in one-half to its
own volume in 90 per cent., and in 1 to 3 volumes of 80 per cent,
alcohol. It does not always dissolve readily in 70 per cent, alcohol, 30
volumes of this strength being occasionally required to make a solution.
The oil was split up into 8 fractions by distillation under reduced
pressure.
Temperature (98 to ICO mm.). Per Cent. 7iD220. aDao°.
Up to 100° 2-65 1-4600 + 3° 41'
100° 110° 43*00 1-4620 + 4°
110° 120° 28-53 1-4605 + 1° 58'
120° 125 6-25 1-4617 ±0°
125° 145° 10-25 1-4657 - 3°
145° 160° 3-75 1-4718 - 4° 10'
160° 175° 3-05 1-4781 - 1° 55'
l
a
Bull Soc. Chim. iii. 19, 1009.
Paper read before the Soc. Espan. Fisic. y Quimica, October, 1910.
LABIATE 247
The oil has the following composition :—
d-a-pinene 7 to 8 per cent.
Cineol 64 „ 72 „
Phenols . traces
Ketones . »»
Esters 4 to 6-5 per cent, (linalyl acetate)
Free alcohols 8 to 14 per cent.
OILS OF MARJORAM AND ORIGANUM.

Some confusion has existed in regard to the botanical origin of the
various origanum or marjoram oils of commerce. This confusion is well
cleared up by Holmes,1 who gives the following details concerning the
plants.
The oil known as oil of sweet marjoram is derived from Origanum
major ana:—
"The plant is known in this country as sweet, knotted, or garden
marjoram, to distinguish it from the wild marjoram, Origanum vulgare,
which differs from it both in appearance and odour. In France
Origanum majorana is known to botanists and florists as * Marjolaine
douce/ the wild marjoram being called ' Marjolaine sauvage'. In
Germany it is known as ' Meiran '. It is supposed to be a native of
Mediterranean countries, and has been cultivated as a pot herb from the
earliest times, being used for this purpose by the ancient Egyptians. It
was introduced into this country from North Africa in A.D. 1573, but it
is hardly known in a truly wild state in Europe, and its native country
must be regarded as doubtful. Other species were, however, and are
still, used in southern Europe.
"Although still cultivated at the present day in almost all countries
for culinary purposes, the oil is chiefly distilled in and imported from
Spain.
" The plant is a small bushy herb, usually about 12 or 18 ins. high,
with small ovate, stalked, greyish-green, entire, somewhat hairy leaves,
and small, rounded, stalkless heads of flowers forming greenish clusters
at the top of the stems and upper branches, the small white blossoms
being rather inconspicuous, and almost hidden among the crowded
green bracts. There is a variety of the plant with woody perennial
stems which was cultivated by herbalists in this country in the eighteenth
century, and was distinguished by the botanist Willdenow as Origanum
majorancides. This is the plant that yields the oil distilled in Cyprus."
" Holmes points out that, it is generally recognised that the oil of
marjoram coming from a definite port or place of manufacture, is not
always identical in composition or constituents. Origanum oil from
Trieste sometimes yields carvacrol and sometimes thymol, in different
samples, and the same occurs in oils imported from Smyrna and from
Cyprus. It would appear, therefore, that more than one species is em-
ployed in the manufacture of the oil in each district.
" The oils have been attributed to various species of Origanum, but the
statements do not afford any definite information in cases in which
the botanical authority for the name is not given. Thus there are three
different species of Origanum bearing the name of Origanum Creticum,
and two bearing that of Origanum Smyrnceum, and two bearing that of
Origanum hirtum, so that the use of either of these names is of no
i P. and E.O.R. (1912), 322 ; (1913), 741.
service for identifying the plant unless the name of the botanical
authority follows the name of the plant, e.g. Origanum Creticum Lin-
naeus ; Origanum Creticum Schousboe; or Origanum Creticum Sieber.
" When these are given it is possible for any botanist to understand
which species is meant, and so far the course is clear. But the matter
is further complicated when two different plants are used in the same
locality, at different times, or are mixed before distillation. Failure of
the crop, or the exhaustion of the wild plant from careless collection,
may lead at any time to substitution of the nearest plant having a some-
what similar odour or similar appearance, and then the identification of
the botanical sourca of the oil can only be settled by the botanical ex-
amination of a specimen of the plant actually employed for distillation.
"I, is now known that the character and percentage of the phenols
carvacrol and thymols differ in different species, and may possibly do
so in the same species under different conditions, and that as a rule they
do not both occur in the same species. But with the aid of botanical
descriptions and illustrations it should be possible to select and cultivate
experimentally those species which give the highest yield, and to
determine the conditions of soil, or the use of particular manure under
which the largest yield may be obtained. Until this is done there is
little hope of obtaining anything approaching a uniform oil in commerce.
" The principal species from which the oil has actually been distilled
and examined are the following:—
Origanum majoranoides Willd.
Origanum onites Linn.
Origanum maru Linn.
Origanum hirtum Link."
The oil of Origanum majorana, or sweet marjoram, is produced
principally in Spain, where the fresh herb yields 0*3 to 0*4 per cent, of
oil. This oil has the following characters :—
Specific gravity . . 0*895 to 0 910
Optical rotation + 15° M + 20°
Ester „ 10 „ 30
These properties may vary somewhat, and three samples, two dis-
tilled in Cyprus and one in London from material obtained from
Cyprus, were found to have the following characters :—l
Cyprus. Cyprus. London.
Specific gravity . . . . 0-899 0*912 0-888
Optical rotation . . . . + 14° 2' +3° 45' + 13° 15'
Saponification value . . . 6-4 8'25 12-8
Solubility in 80 per cent, alcohol . 1 in 1-3 1 in 1 1 in 8 to 9
This oil contains about 40 per cent, of terpenes, principally terpinene,
terpineol, terpinenol-4, and small quantities of esters. Possibly borneol
and camphor are present in traces.
The oil from Origanum majoranoides from Cyprus has been ex-
amined by Pickles 2 who gives the following results :—
Carvacrol, about 84*0 per cent.; another phenol with a creosote-like
odour, 0*2 per cent.; a hydrocarbon origanene C10H16, about 2*5 per
cent.; cymene and terpenes, boiling-point 170° to 180°, about 8 per
1 a
Bull. Imp. Inst., 11 (1913), 50. Trans. Chem. Soc. (1908), 876.
LABIATE 249
cent.; terpene alcohols, boiling-point 100° to 125° C., about 3'5 per cent.;
and a residue boiling above 125° C. The origanene, oxidised by per-
-oxide of hydrogen, yielded succinic acid.
This Cyprus oil has the following characters:—
Specific gravity . 0*960 to 0'970
Phenols (mostly carvacrol) . . . . 70 to 85 per cent.
The terpene origanene isolated by Pickles has the following char-
acters :—
Optical rotation . . . . + 1° 50'
Melting-point of nitrosochloride 91° to 94°
,, ,, nitrol benzylamine 104° „ 105°
Smyrna origanum oil is piincipally the product of Origanum onites
Linn. The yield of oil is about 1*5 to 2*5 per cent, of the dried herb.
'The oil has the following characters :—
Optical rotation - 1° ,, - 15°
Phenols . . . . 16 to 75 per cent, (usually 25 to 50 per cent.)
The oil contains carvacrol, some thymol, linalol, cymene, an olepinic
terpene, and probably a-pinene and camphor. Cedrol has been found
by Schimmel & Co. in a sample of the oil, but this may have been an
•oil adulterated with cedar-wood oil.
Syrian origanum oil is principally derived from Origanum maru
Linn. This oil has the following characters:—
Specific gravity 0-930 to 0-960 (rarely higher)
Optical rotation - 0° 50' to + 1° 35'
Phenols 55 to 75 per cent.
It is usually soluble in 3 volumes of 70 per cent, alcohol.
The phenols consist principally of carvacrol.
The principal species used in the distillation of Trieste origanum
-oil is Origanum hirtum Link. The dried herb yields from 2 to & per
•cent, of oil having the following characters :—
Specific gravity 0'940 to 0*980
The oil is soluble in 3 volumes of 70 per cent, alcohols. The
phenols consist almost entirely of carvacrol, and there are also present
oymene and terpenes.
Origanum vulgare yields from 0*1 to 0*5 per cent, of oil having a
specific gravity 0*870 to 0-910, and optical rotation about - 35°. It
contains phenols which have not been carefully investigated.
Origanum Creticum yields an oil having the following characters :—
Phenols 44 per cent., mostly carvacrol
It is soluble in 2 volumes of 80 per cent, alcohol. This oil was dis-
tilled in Sicily, and examined by Umney and Bennett.1
l
Pha'rm. Jour., 75 (1905), 860.
A Greek origanum oil l of unknown botanical origin has been found
to have the following characters :—
Phenols , . . . 6 3 per cent.
It was soluble in 4 volumes of 70 per cent, alcohol.
The Imperial Institute has examined the oil from a species of
origanum from Cyprus found near Lapithos, locally known as " rikha-
non ". The plant was described by E. M. Holmes as a new species
under the name .of 0. Bevani* In August, 1916, 49 Ib. of the dried
flowering plants without roots were obtained and examined at the
Institute. The material, which contained 9*8 per cent, moisture, yielded
1*9 per cent, of volatile oil, which is only about half the yield of the
ordinary Cyprus Origanum. The oil when first distilled was pale yellow,
but soon acquired a reddish-brown colour; it had the characteristic thyme
odour. It had the following characters :—
Specific gravity a c 1 5 ° . . . . 0*951
Refractive index at 23° C. . . . . 1-51
Phenols p e r cent. . . . . . 75
Solubility in 70 per cent, alcohol at 15° 0. . In 2-7 vols.
PATCHOULI OIL.
Patchouli oil is distilled from the dried leaves of several types of the
patchouli8 plant, of which the principal is Pogostemon patchouli. E. M.
Holmes gives the following interesting information as to its botanical
source and origin :—
Patchouli has long been known and cultivated in India and the Straits
Settlements and various islands of the Indian Ocean, so long indeed, that
its original country was lost sight of until quite recently. The first notice
of its appearance in European commerce appears to be that given by Mr.
J. J. Virey in 1826,4 who describes it as having been brought from the
Isle of Bourbon, where it was evidently cultivated; the flowers being un-
known, and it was doubtfully referred to as Plectranthus graveolens, a
native of New Holland. It was spoken of by Mr. Virey as an insectifuge
for clothes and shawls.
The first notice of a sale of the leaves in this country is an account
given by Dr. J. Pereira 6 of forty-six cases put up for sale at Garraway's
Coffee House on 27 June, 1844, by Mr. Ellis, a drug broker of Fenchurch
Street. It was packed in cases of two sizes, containing respectively 50 Ib.
and 100 Ib.; 6s. per Ib. was asked for it, but no bids were made. It is
rather remarkable that this lot was said to have come from New York,
where it was reported to have been carried from China. The dried plant
as imported consisted of the leafy tops, 1 ft. or more in length, the stems
being round and woody and the branches obtusely quadrangular and the
leaves serrate, or crenate-serrate. But it was recognised by Dr. Pereira
as an East Indian product, for he says that it had been introduced into
the Botanic Gardens at Calcutta from Penang, but that up to 1841 it had
not flowered there.
1
2
Evans' Analytical Notes, 1910.
8
4
P. and E.O.R. (1915), 6, 19. 6
Ibid. (1913), 369.
Jour, de Pharm. (1826), xii. 61. Pharm. Jour. (1), iv. 808.
LABIATE 251
Its introduction into Europe is accounted for by a writer in the
Gardener's Chroniclel by the fact that a few years previously real Indian
shawls bore an extravagant price, and purchasers could always distin-
guish them by their odour of patchouli. The French manufacturers,
having discovered the secret of the odour, imported the dried leaves to
perfume articles of their own make, and thus palm off their homespun
shawls for real Indian.
The true patchouli plant was first described and illustrated in 1845
by Dr. 'Pelletier-Sautelet, in the Mem. de la Soc. Boy. des Sciences
d'Orleans, torn, v., No. 6, the plant having flowered at Orleans in
February of that year, and the description and figure of the plant were
copied into the Pharmaceutical Journal.2 In the spring of 1849 the
plant flowered at Kew, and another illustration of the plant, but not
quite so characteristic, was published in Hooker's Journal of Botany*
The obtuse character of the apex of the leaf, and the crenato-lobate
margins of the leaf, with the base wedge-shaped and not toothed, are
well shown in both.
The plant was supposed by Dr. Pelletier-Sautelet to be hitherto un-
described, in consequence of its not having previously been seen in
flower, and he named it Pogostemon patchouli. Its native country re-
mained unknown until March, 1896, when Holmes was able to identify
it as a wild plant of the Philippine Islands, which had been described
by Blanco under the name of Mentha cablin in the Flore de Filipinos
in 1837. This botanical source explains why the plant was known to
the Chinese, and why the first importation into this country may have
gone to New York from China. One of the uses of the plant appears
to be to give its characteristic odour to Chinese and Indian ink.
The true patchouli is known in the Straits Settlements as Tilam
wangi or Dhelum wangi (" sweet patchouli"). A wild patchouli, known
as Tilam outan, is sometimes added to the genuine patchouli on distilla-
tion, but its botanical origin is uncertain.
The oil distilled from Java patchouli leaves has for some years past
been a commercial article, and is usually known as Dilem oil, in order
to distinguish it from the oil from Pogostemon patchouli. Java pat-
chouli is clearly recognised as Pogostemon Heyneanus, a species distinct
from the true Pogostemon patchouli, and the following notes by E. M.
Holmes 4 are sufficient to clear up any difficulties resulting from the con-
fusion existing between the various names employed prior to 1896 :—
The typical form of this species has long been cultivated in gardens
in India, from the Concan southwards to Coimbatore, under the name
of patchouli, and was referred to Pogostemon Heyneanus by botanists,
but when, in 1843, the origin of the non-flowering cultivated patchouli
of the Straits Settlements was shown to be a different plant, and re-
ceived the name of Pogostemon patchouli Pellet., the authors of the
Flora of British India considered that in consequence of the similarity
of odour, the Indian plant Pogostemon Heyneanus Wall, must belong to
the same species, and altered its name to Pogostemon patchouli Dalz.
and Gibbs, and that of the Straits Settlements non-flowering plant into-
Pogostemon patchouli, var. suavis, hence the Pogostemon Heyneanus be-
came known in botanic gardens as Pogostemon patchouli Dalz. and
1 2
1849, 645. 1849
4
(1), viii. 574. »1849, 329, pi. xi.
P. and E.O.R. (1913), 418.
1
Gibbs, 2
and the genuine patchouli, as its var. suavis, and it was not until
1896 that it was shown that the true patchouli (Pogostemon patchouli
Pellet.) was a distinct species and a native of the Philippine Islands.
The native Indian patchouli was then referred back again to Pogostemon
Heyneanus Wall.
It is practically certain that some other leaves from closely allied
species are from time to time to be found in " Java patchouli leaves''.
Distillation of the leaves in the Straits Settlements is carried out in
stills with false-bottom cylinders, usually with steam at a pressure of
about 1*3 atmospheres, when a yield of about 1*5 per cent, is obtained.
By using higher pressure a larger yield of oil results, but the quality is
inferior. By very prolonged distillation up to 2*6 per cent, has been
obtained in the native distilleries, but in Europe, where most of the
leaves are distilled for perfumery purposes, a yield of 4 per cent, is ob-
tained from the true patchouli leaves, and of about 1 to 1*5 per cent,
from the Java leaves. There appears to be no doubt that the question
of fermentation of the leaves has an important bearing on the yield
of oil.
A. W. K. de Jong 3 has carried out an investigation in regard to the
oil obtained from plants during various stages of their development. As
>tate of Acid Ester Solubility in 90 per

No. the Leaves. Colour. Odour. dlf.0. aDt ^200. No. No Cent. AlcohoL
I. Singapore Oils.
1 Fresh 0-9655 1 - 51° 18' 1-50820 1-5 2-0 Soluble in 0'8 vol. if
1-5 to 5 vols. are
added, the solution
faint becomes cloudy
bright and afterwards
yellow patchouli
odour 0-9587 -50° 58' 1-50766 again clear.
2 Dried 1-1 Soluble in 6 to 7
and more vols.
3 Fermented 0-9628 - 52° 33' 1-50784 0-9 1-5 Soluble in 7 and
more vols.
II. Java Oils.

4 Fresh terpene- 0-9344 - 15° 20' 1-50050 0-8 9*9 Soluble in 0'3 and
like more vols. (soluble
in about 10 and
more vcls. 85 per
cent, alcohol).
5 Fresh faint 0-9450 - 15° 20' 1-50483 5-8 Soluble in 0*6 and
patchouli more vols. (insolu-
bright odour ble in 10 vols. 85
yellow per cent, alcohol).
6 Dried calamus- 0-9168 + 3° 15' 1-50030 6-1 Soluble in about 10
like — and more vols.
7 Slightly calamus- 0-9229 -f 2° 32' 1-50058 0-8 4-9 Soluble in about 10
fermented like vols. with separa-
tion of paraffin.
8 Strongly faint 0-9210 - 0°26' 1-50207 — 5-0 Soluble in 8 and
fermented patchouli more vols.
odour
1 2 3
Pharm. Jour. (4), xxvi. 349. Ibid. (4), ii. 223. Teysmannia (1906), No. 6.
LABIATE 253
a result he came to the conclusion that the best results are to be obtained
by c -tting the plants when they have five pairs of leaves, and to distil
only the leaves, as the leaf-stalks contain so little oil that they do not
pay to distil.
The table on opposite page shows the variation in oil distilled from
leaves which were either fresh, dried, or fermented before distillation.
The oil from fresh leaves appears to be practically valueless.
The above considerations indicate the difficulty in fixing standards
for an oil, which varies so much by alterations in the conditions of culti-
vation, preparation of the leaves, and distillation.
Oils distilled locally from the dried Singapore leaves (" imported
oils") will usually have characters falling within the following limits :—
Specific gravity at 15° . 0-955 to 0'980
Optiral rotation - 44° „ - 62°
Refractive index at 20° 1-5065 ,, 1-5130
Ester 1-5 „ 8
Soluble in 3 to 10 volumes of 90 per cent, alcohol.
The oil is sometimes less soluble than this, but any marked devia-
tion from these figures should be regarded with suspicion, and the oil
should be subjected to minute examination.
Oils distilled in Europe from imported Singapore leaves, which are of
much finer odour than most of the native distilled oil, have in general,
Specific gravity at 15° . . . . . . . 0-965 to 0 995
Acid value 1„ 5
Ester „ 2 „ 12
Most samples are soluble in 1 to 2 volumes of 90 per cent, alcohol,
although some samples require 4 to 6 volumes for solution.
Dilem oil, or patchouli oil distilled irom Java leaves, has an odour
distinctly, recalling that of calamus oil, and has characters differing con-
siderably from those of the patchouli oil fi om Singapore leaves. This
oil usually has characters falling within the following limits:—
Specific gravity at 15° 0*920 to 0*940
Acid value . . . . . . . . . 1 , ,5
Ester , 6 ,, 20
It is soluble, sometimes with turbidity, in 6 to 10 volumes of 90 per
cent, alcohol. Oils are, however, from time to time found with values
much outside these limits, but how far this is due to the addition of
other species of patchouli leaves to the distillation material is not known^
Schimmel & Co. have recorded an oil* from Java leaves having a specific
gravity 0*9659 and an optical rotation -51° 16'.
A sample of patchouli oil distilled from 1 aves from Perak has been
reported upon by the Imperial Institute, having the following char-
acters :—
Specific gravity at 15° . 0*9595
Soluble in 7*4 volumes of 90 per cent, alcohol.
254 THE CHEM1STKY OF ESSENTIAL OILS
Lehmann l has drawn attention to the fact that oils of recent distilla-
tion have frequently had a lower specific gravity and optical rotation than
usual, and also showed a marked decrease of solubility in 90 per cent,
alcohol. The amount of oil obtainable from the herb is also decidedly
smaller, seldom being above 2 per cent. Two of the typically abnormal
oils showed the following constants :—
Specific gravity . 0-935 to 0'937
Saponification value 4-5 „ 6-5
Both were soluble in 4 to 5 volumes of 90 per cent, alcohol. The
odour of the oil was especially fine and strong. The suspicion that the
leaves had been adulterated proved to be unfounded. The marked re-
duction in the yield of the oil and the change in the nature of the con-
stants is probably attributable to atmospheric conditions existing during
the time of the growth of the herb.
Patchouli oil is adulterated to a certain extent with the oil from other
leaves which are fraudulently packed with patchouli leaves, such as basil
leaves and the leaves of a Malayan plant, known as " purpulut " (Urena
lobatd). The leaves of Hyptis suaveolens are also used as an adulterant.
Sassafras (or heavy camphor oil) is sometimes found as an adulterant,
as well as cubeb oil, cedar-wood oil, and—rarely—petroleum.
The earliest chemical examination of this oil was made by Dr. Glad-
stone in 1864, who stated that it contained a hydrocarbon analogous to
that from oil of cubebs, together with a small quantity of2 an intensely
blue colouring matter which he termed cserulein. Gal and Mont-
golfier3 have shown that the oil contains a solid body, which they
termed patchouli camphor, and which Wallach has shown to be a ses-
quiterpene alcohol C15H26O. This body is probably the oxidation pro-
duct of other substances in the oil, and appears to have little or no
odoriferous value. It is deposited when the oil stands for long in a
cold place. When recrystallised it melts at 56°. It is laevo-rotary,
the specific rotation in the melted condition being - 118°, or in chloro-
form solution - 97° 42'. Dehydration gives rise to a hydrocarbon
G15H24 patchoulene. This hydrocarbon has an odour of cedar-wood
oil, boils at 254° to 256°, and has a specific gravity 0*9334 and optical
rotation - 36° 52'.
Wallach claimed to have isolated cadinene from the oil, but later
researches have shown that this sesquiterpene is absent from the oil,
so that the oil examined by4 Wallach was probably adulterated.
Von Soden and Eojahn have examined samples of patchouli oil of
known purity, and have separated it into two main fractions by distilla-
tion under reduced pressure. The earlier fractions of specific gravity
0*984 to 1-002 were found to consist chiefly of patchouli alcohol, whilst
two other fractions of specific gravity 0*946 and 0*964 were found to
consist of high-boiling sesquiterpenes. A series of refractionations suc-
ceeded in separating a fraction of specific gravity 0*930 to 0*940 and of
optical rotation - 50°, and one of the same specific gravity but of rather
higher boiling-point. From the former, after hydrolysis, a sesquiterpene
was obtained in a state of purity which boiled at 264° to 265° at 750 mm.,
1 2
Chem. Zeit. (1913), 37, 1589. Comptes rendus, 68 (1869), 406.
* Ibid., 84 (1877), 88. * Bericlite, 37 (1904), 3353.
LABIAT-ZE 255
and had a specific gravity O9335 and an optical rotation - 58° 45'.
This latter fraction yielded a sesquiterpene of specific gravity 0*930,
optical rotation + 0° 45', and boiling-point 273° to 274° at 760 mm.
According to Schimmel & Co.1 about 97 per cent, of patchouli oil
consists of bodies of no value for odour purposes. They have detected
the following constituents in patchouli oil: benzaldehyde; eugenol;
cinnamic aldehyde; a terpenic alcohol of rose-like odour and of un-
determined constitution; a ketone of caraway odour forming a semi-
carbazone melting at 134° to 135°; and a base of stupefying odour not
yet identified. But as all these bodies are present in traces only it
•cannot be said that our knowledge of the odour bearers present in
patchouli oil 2is complete.
Simmons records two samples of commercial oil to which some
artificial ester, or oil containing a high proportion of esters, had been
added. These two samples had the following characters:—
1. 2.
Specific gravity 0-9948 0'9937
Rotation - 38° 30' - 49" 30'
Acidity trace trace
Ester value 58 18-5
Solubility in 90 per cent, alcohol . . 1 in 0'75 1 in 0'5
MELISSA OIL.
True melissa oil, or oil of balm, is the distillate of the herb Melissa
cfficinalis, a plant indigenous to the Northern Mediterranean littoral and
Western Asia. It is also cultivated in North America. The leaves have
an odour recalling that of a mixture of lemon grass and citronella. The
yield of oil is, however, so small that the melissa oil of commerce is
practically invariably the result of the distillation of lemon oil with a
little citronella oil (or3 citronella 1) over the leaves of the plant.
Schimmel & Co. have examined the pure oil, distilled from the
fresh herb, and found two oils to have the following characters :—
From Fresh Herb ™ ,, , _ ,
at Commencement ^mom , ft*h Herb
Ful1 Flower
of Flowering. -
Yield 0-014 per cent. 0*104 per cent.
Rotation + 0° 30' +0°
The oil contains citral, and probably a little citronellal. Flatau and
Labbe 4 state that a sample examined by them contained the following :
Geraniol 20 per cent.
Linalol 12 „
Oitronellol 6 ,,
OIL OF SAGE.
Sage oil is obtained from the herb Salvia officinalis, a plant indi-
genous to the Northern Mediterranean littoral. The oil is distilled to a
considerable extent in Dalmatia, and recently a fair amount of oil has
been manufactured in Spain but from a different species of Salvia. The
leaves and twigs of the plant yield from 1 to 3 per cent, of oil. A cer-
tain amount of oil is also distilled in Germany.
1
:
Report, April, 1904, 68. *4 Chemist and Druggist (1904), 815.
<Bericht, October, 1894, 37. Bull. Soc. Chim. (1898), ii. 636.
The oil distilled in Dalmatia and in Germany is of typically sage-
odour and is used for flavouring purposes, whilst that distilled in Spain
is distilled from Salvia trilobia, with possibly other species as well, and
more resembles spike lavender in odour than the ordinary sage of the
garden.
Pure Dalmatian or German sage oil has the following characters :—
Refractive index 1 4575 „ 1-4690
Esters as linalyl acetate . . . . . . 2 to 6 per cent.
Total alcohols as borneol 20 „ 25
Spanish sage oil has the following characters:—
Specific gravity . . . . 0*912 t o 0-932
Optical rotation . + 10° to -f 20° (rarely laevo-rotatory)
Esters as linalyl acetate . 5 to 20 per cent.
Total alcohols as borneol . 20 „ 29 „
It is soluble in 6 volumes of 70 per cent, alcohol. x
On fractionating German oil of sage H. Seyler obtained 1 to 2 per
cent, of a first fraction boiling below 155°, which could be separated inta
three portions by repeated distillation over sodium. The fraction first
passing over, of the boiling-point 142° to 145° (d20<> = 0'80; nD = T4438;
aD = +1° 40'), gave analyses corresponding to C10H18. This hydro-
carbon, called " salvene," when oxidised with potassium permanganate,
yielded an acid, whose semicarbazone C10H16O2CON3H3 melted at 204°,
and which possibly is identical with /3-tanacetoketonic acid (/3-thuja-
ketonic acid).
Salvene has probably the following constitutional formula :—
CH(CH3)2
H2C; /
HC'/
CH.CH 3
From the first runnings of a Spanish oil of sage no salvene could be
isolated.
Pinene and cineol are probably present in sage oil in small amount,
together with borneol, a small quantity of esters, and the ketone thujone.
Muir and Sugiura isolated a body which they named salviol, which is
now known to be identical with the body which has been named thujone.
Dextro-camphor is also present in traces. English distilled sage oil has
been said to contain cedrene, but the authenticity of the sample examined
is doubtful.
Salvia cypria, a native of the Island of Cyprus, yields an essential
oil having a camphoraceous odour. Two samples 2 gave the following:
characters:—
2
*Berichte, 35 (1902), 550. Bull. Imp. Inst. 11 (1913), 429.
LABIATE 257
1. 2.
Specific gravity 0-9263 0'926
Saponification value 13*9 8
„ (after acetylation) . . 38-9 36
The oil contains about 75 per cent, of eucalyptol.
Salvia sclarea also yields an oil with a highly aromatic odour, re-
calling that of ambergris. It is known commercially as clary oil or
muscatel sage.
French oil of clary has the following characters :—
Ester value 110 „ 206
Esters as linalyl acetate 38 to 73 per cent.
It is soluble, in 2 volumes of 90 per cent, alcohol.
German clary oil has the following characters :—
Optical rotation - 25° „ - 48a
Pinene, cineol, and linalol have been isolated from this oil.
Salvia mellifera (Eamona stachyoides) is a labiate plant found in
Southern California, and known as black sage. Eabak * first examined
the oil which he obtained to the extent of 0*75 per cent, of the green
flowering plant. He found the oil to have the following characters :—
Acid value 2
Ester „ 2-5
Eabak detected ^-camphor, cineol, pinene, theyone, and borneol in
the oil, as well as traces of free formic acid, and formic and acetic acids
in the form of esters.
Burke and Scalione2 have also examined the oil, obtaining 0'9 per
cent, from the leaves and twigs. The oil had the following characters :—
Specific gravity at 15° 0'8979
Optical rotation 4-24-4°
Acid value 2-2
Ester „ 1-6
These chemists identified the following bodies in the oil: a-pinene,
cineol, thujone, camphor, and inactive terpenes, probably consisting of a
mixture of dipentene and terpinene.
SATUBEJA OILS.
Savon/ Oil.—The oil distilled from the green herb, winter savory,
Satureja montana, has been examined by Haller,3 who states that it is
an orange-yellow oil of aromatic taste, somewhat resembling true ori-
ganum oil, of specific gravity 0*9394 at 17° and optical rotation - 3° 25'.
1
U.S. Dept. Agric. Bur. Plant Industry, 235, 14.
*Jour. Jnd. Encj. Chem., 6 (1914), 804. " Comptes rendus, 94 (1882), 132.
VOL I. 17
258 THE CHEMISTRY OF ESSENTIAL OIL3
He found in it from 30 to 40 per cent, of carvacrol, and traces of another
phenol. Two hydrocarbons at least are present, probably cymene and
a terpene. A sample examined by Schimmel & Co. had a specific gravity
•939 and optical rotation — 2° 35'. It was soluble in 4*5 volumes of 70
per cent, alcohol, and contained 65 per cent, of phenols. Two samples
distilled in the South of France, and examined by Schimmel & Co., had
1. 2.
Refractive index 1-4949 —
The oil of the summer savory, S&tureja hortensis, does not differ
greatly from that of the winter savory. It has the following char-
acters :—
Optical rotation + 0° 4' „ - 1°
Phenols - 35 to 45 per cent.
An oil examined by Jahns, having a specific gravity 0-898, was found
to contain 30 per cent, of carvacrol, with traces of a second phenol,
cymene, and one or more terpenes.
Sottureja. cuneifolia, a plant grown on the Dalmatian Islands, yields
an oil which has been examined by Schimmel & Co.1 Four samples had
Spesific gravity. Rotation. Refractive Index. Phenols.
0-9182 - 4° 45' 1-4382 23 psr cent.
* 0*9190 - 5° 15' 1-4982 34
0-9444 - 2° 15' 1-4053 59
0-9444 - 1°50' 1-4056 59
Carvacrol and cymene are the principal constituents of the oil.
Saturejoi thymbra yields an essential oil having the following char-
acters :—
Thymol about 20 per cent.
Pinene, cymene, dipentene, and bornyl acetate are also present in
the oil.
Szturjja Gal&minthi (Cal&mintha nepeta).—-A number of oils have
been described under this name, but in most cases the botanical source
was not traced with certainty. A sample2 of absolute authenticity has
been examined by Boure-Bertrand Fils, who reported on the oil as
, follows: the plants yielded 0*14:26 per cent, of essential oil, and were
grown in Sicily. The odour of the oil, which is brownish in colour, re-
cills that of pennyroyal. The oil had the following characters :—
Specific gravity at 15° G 0-9249
,, „ of the acetylated oil . . . . + 9° 40'
Acid value 1-4
Coefficient of saponification 12-6
Esters (as menthol acetate) 4-4 per cent.
Coefficient of saponification of the acetylated oil . . 48*5
Total alcohols (as menthol) 14-0 per cent.
Soluble in 0'5 volume and over of 80 per cent, alcohol
„ ,,2 volumes of 75 per cent, alcohol, then slight opalescence
,,3 ., ,,70 „ „ „ cloudy
1
Bericht, October, 1911, 108. * Bulletin, October, 1912, 68.
LABIATE 259
The estimation of the pulegone, carried out by means of neutral
sodium sulphite, shows 20 per cent, of this ketone.
Two Dalmatian oils examined by Schimmel & Co, had the following
values:—
1. 2.
Specific gravity 0*9305 0-9395
Optical rotation ; + 2° 60' + 6° 28'
Acid value 0*9 —
Ester „ 5-4 14*6
The oil contained about 45 per cent, of pulegone.
A French distilled oil had characters very similar to those of the
Dalmatian oil.
Umney & Bennett1 have reported on an alleged Sicilian oil, which
contained only a very small amount of ketones. The characters of the
oil were as follows :—
Optical rotation + 14°
Total alcohols 18'2 per cent, as menthol
Ketones 10*8 per cent.
Satureja hortensis.—This plant yields about Ol per cent, of essential
oil, which has the following characters :—
Optical rotation + 0° 4' „ - 0° 56'
The oil contains carvacrol, cymene, and a terpene.
Satureja calamintha subsp. silvatica.—This plant is known in middle
Europe as Mountain Balm. It yields an essential oil having the follow-
ing characters:—2
Optical rotation 17° „ - 28°
Refractive index 1*4911 „ 1*4951
Acid value . 0
Ester 4*5 to 8*3
Its constituents have not been investigated.
OID OF BASIL.
Sweet Basil Oil.—This oil is distilled from the fresh herb Ocimum
basilicum, which yields about 0*05 per cent, of essential oil. This oil
has a most excellent fragrance, and is used in the preparation of mignon-
ette extract and similar perfumes.
A certain amount of Basil oil is distilled in Germany, France, Spain,
and Algeria, but a fair quantity is also now distilled in Keunion, Java,
and Mayotte.
E. G. and C. Camus 3 have recently investigated the botanical re-
lations of the cultivated species of Basilicum. There are several
varieties of Ocimum basilicum L. The variety purpurascens Benth.,
which is regarded by several authors as a distinct species, is cultivated
under the name of violet-red basil.
1
2
Chetn. and Drug., 67, 970.
3
!Schiimnel, Bericht, April, 1901,
61; October, 1905, 11.
Boure-Bertrand Fils, Bulletin, October, 1910, 23.
The var. thyrsiflorum Benth. is known as the common white basil.
The var. album Benth. (Ocimum album L.; 0. laxum, 0. americanum)
is cultivated under the name of lettuce-leaf basil, while the var. crispum
(Ocimum crispum Thunb. ?) is grown under the name of curly-leaved
basil.
The authors treat in detail of the morphological and anatomical
conditions of the various degenerate species, and in conclusion describe
the different essential oils, of which the properties are summarised in
the table below.
The variety most suitable for cultivation is Ocimum crispum (curly-
leaved basil), because it yields the highest percentage of oil, while so far
as its odour is concerned the essential oil from this variety is not in-
ferior to the ordinary commercial product.
The oil from the lettuce-leaved basil (var. album) gives a slightly
cloudy solution with 70 per cent, alcohol; all the other oils give clear
solutions when mixed with from 2 to 3 times their volume and more of
70 per cent, alcohol. The methylchavicol (estragol) content of all the
oils (acertained by the determination of the methoxyl-group) was about
55 per cent.
Ocimum Basilicum.
!
Constants. Var. Thyrsiflorum. Var. Crispum. Var. Album. Var. Purpurascens.
Crop 1910. Crop 1909. Crop 1910. Crop 1910. Crop 1910. Crop 1909.
0-9168 0-9125 0-9123 0-8975 0-8959 0-9100

aD - 10° 52' - 11° 28' - 10° 30' - 12° 54' - 13° 52' - 10° 14'
OD of the Acety
lated Oil + 1° 36' + 1° 34' + 0° 30' + 0°2' + 1° 52' + 3°2S'
Daoo . 1-488 1-484 1-484 1-479 ! 1-477 1-477
Acid Value 2-8 1-4 2-1 0-7 3-5 2-1
Ester Value 5-6 3-5 4-9 7-0 9-8 7-7
E 81 e r-c o n t e n t
calc. as Linalyl
Acetate 1-96 p. c. 1-22 p. c. 1-71 p. c. 2-45 p. c. 3-43 p. c. 2-68 p. o.
Ester Value after
Acetylation 116-9 114-8 116-9 130-2 126-7 117-6
Alcohol - content i
calc. as Linalol 35-19 p. c. 34-50 p. c. 35-19 p. c. 39-66 p. c. 38 '46 p. c. 35-43 p.o.
Yield . 0-0855 p. c. 0-1285 p. c. 0-0780 p. c. 0 0370 p. c. ~~~
——
Normal samples of German or French distilled Basil oil have the

Specific gravity . . . . . 0-900 to 0-930
Optical rotation . . . . - 6° „ - 20°
Refractive index . . . . . . 1-4800 „ 1-4950
Acid value 1 „ 4
Ester „ 2 „ 12
Eeunion oil, which is derived from an unknown variety, has the
Optical rotation '. + 1° „ + 12°
Refractive index . . . . . 1-5150 „ 1-5175
Acid value 1 „3
Ester ,, 8 „ 25
LABIATE 261
It is soluble in 8. volumes of 80 per cent, alcohol, sometimes with
slight turbidity.
Two samples of Mayotte oil examined by Eoure-Bertrand Fils l had
the following values :—
1. 2.
Specific gravity at 15° C. . 0'9677 0-9630
Optical rotation . + 0° 58' + 0° 56'
Solubility in 80 per cent, alcohol 3 volumes and over 3'2 volumes and over
Acid value 1-4 0-7
Coefficient of saponification 5-6 6-3
Esters (as linalyl acetate) . 1*9 per cent. 2-2 per cent.
Two varieties of Java oil have been examined in the laboratories at
Buitenzorg. One is that from a large-leaved variety known as " Selasih
Mekah ". The oil had a specific gravity 0*900 at 26° and an optical
rotation of - 15° to — 18°. It contained about 30 to 40 per cent, of
phenols, of which eugenol is stated to be the principal.
A sample of the oil distilled in the Seychelles2 had the following
characters :—
Befractive index at 21° 1-5140
Acid value 0-8
Ester „ 2-5
Another variety of the plant yielded an oil of specific gravity 0*948
at 25° and containing much methyl-chavicol. This plant is known as
Selasih hidjan.
Dupont and Guerlain 3 have identified methyl-chavicol (estragol) and
/-linalol in the oil. Bertram and Walbaum 4 isolated cineol, d-u-pinene,
and ^-camphor.
The Java oil contains cineol, estragol, pinene, an olefinic terpene
(ocimene?), and eugenol.
Koure-Bertrand Fils 6 have examined the oils of Ocimum canum and
Ocimum gratissimum, distilled at Dakalba (Ivory Coast).
The essential oil of Ocimum canum Sims (0. americanum L.) con-
sists, when slightly heated in the hand, of a mobile liquid, highly re-
fractive, slightly yellowish. Its odour is peculiar and rather pleasant.
At the time of its preparation it collects at the bottom of the receiver.
At the ordinary temperature it soon gives a deposit of large acicular
crystals. The separation of crystals is sufficiently abundant to cause
the whole product to become semi-solid.
Specific gravity at 32° C. 1*0330
Optical rotation at 30° C - 2° 80'
Acid value 0
Coefficient of saponification 301-4
Soluble in all proportions in 80 per cent, alcohol.
,, ,, 2J volumes and over of 75 „ „
Solution slightly cloudy in 5J volumes and over of 70 per cent, alcohol.
It was found to contain about 87 per cent, of methyl cinnamate, of
which ester the crystals above mentioned consist.
The oil from Ocimum gratissimum has a specific gravity 0*9105 and
an optical rotation + 0° 58'. It contains thymol and carvacrol.
1 2
3
Bulletin,
October, 1912, 71. 4
Bull. Imp. Inst., xvi., I, 30.
Comptes rendus, 124 (1897),
8
300. Arch. Pharm., 235 (1897), 176.
Bulletin, October, 1913, 18.
A sample of oil from Ocimum gratissimum distilled in the Seychelles l
had a specific gravity 0'995, optical rotation - 14-1°, and refractive
index 1-5260 at 21°.
The essential oil from the leaves of Ocimum viride from Sierra Leone
has been examined by Goulding and Pelly.2 The oil had a specific gravity
0-9115 and optical rotation + 1° 30'. By distillation at atmospheric
pressure the following fractions were obtained :—
Boiling-point. Per Cent. Specific Gravity. Rotation.
165° to 180° 25 0-8614 + 0° 33'
180° „ 200° 20 0-8804 + 1° 40'
200° „ 220° 20 0-9164 + 2° 38'
220° „ 235° 20 0'9548 + 3° 38'
235° ,, 250° 10 0*9565 + 5° 14'
It is obvious, however, from an examination of the average optical
rotations of the fractions as compared with that of the original oil, that
decomposition had gone on during the distillation. The authors found
present 32 to 65 per cent, of phenols, 40 per cent, of alcohols, 2 per cent, of
esters, and one or more terpenes. Two samples from the Seychelles
had specific gravities 0*924 and 0*942; and contained 52 per cent, and
62 per cent, of phenols, mostly thymol.
Bacon 3 has examined the oil from Ocimum sanctum, which he ob-
tained to the extent of 0*6 per cent, from the leaves, and which had the
onO
Specific gravity ^0 0'952
Saponincation value . . . . . . . . . 2'8
Methyl-chavicol, cineol, and linalol are present in the oil.
Bhaduri4 has examined the oil of Ocimum pilosum. The whole
plant when fresh is fragrant, but quickly loses its odour when dried.
The seeds form a gelatinous mass when steeped in water; this mucilage
is employed medicinally in India. The green seeds contain more
essential oil than the leaves, but the whole plant was distilled. The oil
obtained was pale yellow in colour and very mobile. Its characters were
as follows:—
Befractive index 1-4843 at 24-5°
It contains limonene, citral, citronellal, cineol, and a little thymolr
as well as other undetermined phenolic constituents. Unlike other
Indian basil oils, it contained no methyl-chavicol.
OILS OF MOSLA.
The Japanese plant Mosla Japonica yields about 2 per cent, of
essential oil containing 44 per cent, of thymol. Its specific gravity ia
about 0*920. Muryama 5 has identified thymol, carvacrol, and pinene
in the oil. 6
Hoshino states that although thymol and carvacrol are constituents
of the oil, they are never found together in the same oil. A thymol
containing oil had the following characters :—
2
^ 9
i Bull. Imp. Inst., xvi., I, 30.1 . 4
Ibid.,
6 (1908), 209.
Philipp. Jour. Sci., 5 (1910), 261. • J. Amer. Chem. Soc. (1914), 36, 1772.
6
Pharm. Zentral. 51 (1910), 35. • J. Chem. 2nd. Tokyo (1919), 22, 557.
LABIATE 263
Specific gravity . 0*9154

Ester value . 4-5
Thymol 50 per cent.
He identified phellandrene, ^-cymene, y-terpinene, caryophyllene,

cadinene, and probably sabinene in the oil.
Mosla punctata yields about 1 per cent, of oil, calculated on the air-
dried herb, of a fragrant odour, having the following characters:—
Ester value 16
It does not contain any phenols, but owes its odour to a ketone, which
has been named a-mujone. It also contains a sesquiterpene, not yet
identified, having a specific gravity 0*9259, optical rotation + 2*16°, and
refractive index 1-51615.
The herb, Mosla grosserata, yields an oil which appears to be very
variable in character. It is known in Japan as oil1 of Himeshiso. The
fresh herb, according to Furukawa and Tomizawa, yields 0'24 per cent,
of an oil containing 25 per cent, of carvacrol, some thymoquinone and
some thymohydroquinone. It also contains ^-cymene, phellandrene,
and terpinene. Murayama, however, has examined four samples,
three from wild and one from cultivated plants.2 These oils had the
Wild Plants. Cultivated

Plants.
1. 2. 3 4.
Specific gravity 0-998 0*954 1-0488 0-9006
Optical rotation -3-75° -3-2° -11-75° -4-5°
Saponification value 33 23 — 37
„ ,, (after acetylation) 66-6 ! 54-5 49-2
Phenols 20 per cent. | — — 13 per cent.
In the oils from the wild plants the following constituents were
identified: thymol, methyl-eugenol, _p-cymol, thymohydroquinone,
myristicin, a terpene and a sesquiterpene. Thymol, thymohydro-
quinone and a terpene were identified in the oil from the cultivated
plants.
OIL OF HYPTIS.
Hyptis suaveolens is found in South America, the Philippines, Java,
and China. Bacon 3 has obtained from it 0*0135 per cent, of essential
oil, having a powerful odour of peppermint. The oil distilled in Java
has the following characters :—
Acid value 0*7
Ester „ 14
,, (after acetylation) 31'7
1
J. Chem. Ind. Tokyoz (1919), 22, 382. *Pharm. Jour. Japan (1920), 459, 389.
Philipp. Jour. Sci., 4 (1909), 130.
PERILLA OILS.
The leaves of Perilla arguta, known in Japan as Shiso, yield an
essential oil of a pale yellow to greenish colour, of a peculiar hay-like
odour, and having the following characters :—1
Specific gravity . . . . 0*9265 t o 0*939
Optical rotation . . . - 90° to- 93°
Refractive index . . . 1-4983
Aldehydes 50 per cent, (neutral sulphite method)
The aldehyde present in the oil has been examined by Semmler and
Zaar 2 who find it to be a dihydrocumic aldehyde, Ci0H14O, and which
has been named perillic aldehyde. It has the following characters :—
Specific rotation - 146°
Eeiractive index 1*50746
Gattefosse considers that geraniol is present in the oil in the form
of esters. The saponification value is very high, due partially to the
presence of esters and partially to the action of alkali on the aldehyde
present.
The dry leaves of Perilla citriodora yield from 2 to 3 per cent, of
an oil of specific gravity 0*911 to 0'913, containing about 60 per cent,
of citral. From the lower boiling fractions Kondo and Yamaguchi 3
have isolated a body which they term perillene, of the formula C10HUO,
and having the following characters :—
Specific gravity a t 2 0 ° . . . . . . . . 0*9017
Optical rotation . . . . . . . . . . +0°
Refractive index at 21° 1*4705
It is a complex body containing a furane nucleus. The oil also contains
a sesquiterpene boiling at 251°.
OIL OF HYSSOP.
Hyssopus officinalis is a plant indigenous to the Mediterranean
countries and Central Asia. The fresh plant yields, on distillation, up
to 0*3 per cent, of essential oil having the following characters :—
Specific gravity 0*925 to 9'945
Optical rotation + 1° , - 25°
Refractive index 1*4730 1*4860
Acid value 0'8 2
Ester „ 3 15
„ ,, (after acetylation) 37 70
An elaborate investigation of hyssop oil has been made by Schimmel
& Co.4 ê following oils have been distilled by themselves :—
I. Oil from blossoming dry herb: d15o 0*9377 ; aD - 22° 3C'; acid
number 1*8 ; ester number 5'8 ; ester number after acetylation 44*0. Not
soluble in 10 volumes 70 per cent, alcohol; soluble in about 6 and
more volumes 80 per cent, alcohol, with separation of paraffin.
II. Oil from blossoming withered herb : dl5o 0*9322 ; aD - 22° 23';
acid number 1*3 ; ester number 3'6 ; ester number after acetylation 37*3 ;
1 2
3
Schimmel's Report, October, 1910, 146. 4
Bericht, 44 (1911), 52.
J. Pharm. Soc. Japan (1919), 446, 263. Report, April, 1908, 57.
LABIATE 265
1*48315; not soluble in 10 volumes 70 per cent, alcohol; soluble
in about 8 volumes and more 80 per cent, alcohol with slight tur-
bidity (separation of paraffin) ; soluble in every proportion in 90 per cent,
alcohol.
III. Oil from highly faded herb which had ceased blossoming:
dl6Q 0-9336 ; aD - 20° 26'; nD20o 1-48441; acid number 1-8 ; ester number
S'l; soluble in about 7 and more volumes 80 per cent, alcohol, with
slight turbidity (separation of paraffin).
For the following investigation they used oil III. After repeated
fractional distillation, the lowest-boiling fractions were combined and
distilled several times over sodium. The portions obtained at a pres-
sure of 758 mm. showed the following properties :—
B.-p. 164° to 166°, 3-1 per cent, of the oil, d^ 0-8650, aD - 19° 29', nD Q 1-47548
„ 166° „ 168°, 5-6 „ „ „ dig0 0-8645, OD - 20° 16', n^ 1-47705
„ 168° „ 170°, 2-6 „ „ „ d 0-8632, aD - 20° 15', nD 1-47753
All three fractions had a turpentine-like odour, and on oxidation
with permanganate in the presence of free sodium hydroxide, yielded
sodium nopinate. They consequently contained /2-pinene (nopinene),
which was thus for the first time detected in large quantity in an es-
sential oil. The fraction of the boiling-point 164° to 166° contained the
largest quantity of /3-pinene, so that the constants for this fraction pos-
sibly approach those of the hydrocarbon most closely. The free nopinic
.acid obtained from the sodium salt crystallised from benzene in long
needles with a silken lustre, of the melting-point 126° to 127'5°.
The principal constituent of the oil is a saturated ketone of the
formula CIOH16O, which is the active variety of pino-camphone, which
has been prepared in the inactive form synthetically, by Wallach, by
the reduction of nitrosopinene. The characters of the two bodies are
as follows :—
i Pinocamphone (Wallach) : Z-Pinocamphone from hyssop oil:
Boiling-point 211° to 213°. Boiling-point 211° to 212°.
daio 0-959. duo 0-9662.
"D 1-47273. "D20o 1-47421.
Mol. refr. 44-44. Mol. refr. 44-40.
Optical rotation 0°. Optical rotation - 13° 42'.
OIL OF ELSHOLTZIA CRISTATA.

The dry herb, EUJioUzia cristata, yields 2 per cent, of an oil which
is esteemed in Japan as an antipyretic and diuretic. The oil has a
golden-yellow colour and has the following characters :—
Acid value 0
Ester ,, 1-8
The oil contains a ketone, which has been examined by Asahina and
Murayama,1 and which has the following constants :—
Boiling-point at 10 mm. . . 87° to 88°
„ 760 210°
1
Schimmel's Report.
It has the formula C10H14O2, and forms a semicarbazone melting at
171° and an oxime melting at 54°.
SPANISH VERBENA OIL.
The so-called Spanish Verbena oil was, until recently, believed to be
derived from a verbena species. E. M. Holmes,1 however, has defi-
nitely identified it as a Labiate plant, Thymus hyemalis. He has shown
that the plant, although called Verbena, does not belong to the Verbena
family, but to the Labiate plants, and is nearly allied to the Lemon
Thyme cultivated in gardens in this country. In habit, however, it is
quite different to Lemon Thyme, having a stiff, rigid, erect growth with
woody stems, and small, short, linear leaves, in small axillary tufts
along the whole length of the stem, giving it quite a heath-like appear-
ance. Until quite recently much confusion has existed between the
different species of thyme found wild on the Continent, the species
either hybridising or varying according to the environment, so that
there has been considerable difficulty in discriminating between species-
and varieties. The full description of the plant is as follows}:—
Thymus hyemalis J. Lange : An undershrub, •£ to 1 ft. high, flexu-
osely branched from the base, with erect branchlets, the younger twigs
hoary with white hairs, the leaves short and linear with revolute mar-
gins, crowded into small tufts in the axils of the leaves, the flowers
forming small crowded heads at the tips of the branchlets. The calyx
is purplish and two-lipped, the upper lip consisting of two subulate
teeth, the lower with three short ovate acuminate teeth, the corolla of a
deep rose colour, and nearly twice as long as the calyx.
This species is related to Thymus hirtus W. and Thymus vulgar is
L., and has been placed by Boissier under Thymus mastichina L., and
by Pourret under Thymus sparsifolius, var. hyemalis, but by J. Lange it
is considered to be a distinct species. Its heath-like habit of growth is,
at all events, very distinctive, as well as the small heads of flowers, each
of which is nearly stalkless.
The oil is frequently known as Spanish Thyme-Lemon oil. The
author and Bennett,2 have examined a sample, which had the following
characters :—
The oil is of a yellow colour, and has an odour recalling that of
thyme, but with a strong flavour of lemon, differing in this respect from
the oil derived from Thymus serpyllum (wild thyme). The latter oil
also differs in being laevo-rotatory. The following are the chief char-
acters of the sample examined :—
Specific gravity at 15° C 0-901
Optical rotation in 100 mm. tube + 18° 30'
Aldehydes (principally citral) 20 per cent.
Proportion absorbed by 5 per cent, potash solution 10
Refractive index at 19° 0 1-4808
,, „ of first 80 per cent, distilled 1-4779
„ ,, of 20 per cent, residue 1-4980
The portion absorbed by potash solution on separation proved to be
somewhat resinous, and gave only a feeble phenol reaction with ferria
chloride. A small portion of the oil was fractionated in order to give-
some idea of its possible constituents. The results were as follows :—
2
*P. and E.OM. (1912), 212. Chemist and Druggist, 69 (1906), 481.
LABIATE 267
Below 175° 0. Nothing distilled
JLJVU nrocu Jit u u> LIU JLOU 10 per cent, was collected
180° , 190° . 13
190° , 200° . 11
200° , 210° . 12
210° , 220° . 18
220° , 230° . 18
Above 280° . 18 , residue
Pinene and limonene are probably present. The high boiling-point
of the residual fraction, which has a refractive index of about 1*500,
points to the presence of a sesquiterpene. The oil is not soluble in 70
per cent, alcohol (10 volumes), but dissolves in 2 volumes of 80 per cent,
alcohol.
Other samples of this oil examined had specific gravities up to 0*924
and optical rotations from - 6° to + 10°.
Charabot and Fillet have prepared two samples of Spanish vervain
oil, the one distilled from the dried leaves, the other from the flowers,
the respective yield being 0*184 per cent, and 0*878 per cent. The oil
from the leaves had a rotatory power of - 10° 30', that from the flowers
-h 6° 50'. This latter appeared to be more rich in citral than the
former, containing 70 per cent, and about 10 per cent, of alcohols.
OlL OF LOPHANTHUS BUGOSUS.
This plant is found wild in North America and in Eastern Asia.

The oil has been examined by Vilmorin and Levallois.1 It is an amber-
yellow liquid, soluble in all proportions of 95 per cent., and in 5 volumes
of 85 per cent, alcohol. It has the following characters :—
Ester value . . . . 3-7
„ ,, (after acetylation) 7.4
The principal constituent is methyl-chavicol, and it also contains
limonene.
OlL OF LOPHANTHUS ANISATUS.
The herb, Lophanthus anisatus, yields about 0*1 per cent, of essential
oil having an odour t resembling that of tarragon. It has the following
characters :—
Acid value 2-8
Ester „ 14-0
The principal constituent is methyl-chavicol.
OIL OF NEPETA.
2
Umney and Bennett have examined the oil distilled in Sicily from
the catmint, Nepeta Cataria. It has the following characters :—
2
* Bull. Soc. Chim. (1914), 342. Pharm. Jour., 75 (1905), 861.
It contains 22 per cent, of menthol of which about 3 per cent, is
present in the form of esters. A small amount of a ketone is also
present.
The oil of Nepeta Nepetella has an odour of peppermint and has the
Acid value 45*5
Ester „ 245-7
,, ,, (after acetylation) 314'5
It consists largely of the caprylic and valerianic esters of menthol or
an allied alcohol.
OIL OF PBOSTANTHBBA CINEOLIFEEA.
Baker and Smith l have examined the oil distilled from the leaves
and stalks of this Labiate plant. The yield was 0*71 per cent, and the
oil had an odour of eucalyptol, with the following characters :—
The oil contains about 3 per cent, of geranyl acetate, pinene, cymene,
free geraniol, eucalyptol, traces of phenol (carvacrol ?), and an aldehyde
which is probably cuminic aldehyde.
OIL OF BYSTBOPOGON MOLLIS.
Bystropogon mollis, known as Argentine mint, yields about 0*4 per
cent, of essential oil, which has been examined by Doering.2 It is a
clear liquid of specific gravity 0*918 to 0'920, which on cooling to 12°
does not separate any menthol. It boils principally at 210°. The oil
contains 2*5 per cent, of furfurol, but no other constituent has been
identified.
OIL OF MERIANDBA.
The oil of Meriandra benghalensis (M. dianthera) has been distilled
in the Italian Colony of Eritrea, and3 is described as " sage-oil ". It has
been examined by Schimmel & Co. A sample distilled from the herb
by these chemists (yield 1-5 per cent.) had the following characters:—
Acid value 3*7
Ester „ 14-8
On freezing, camphor separates from the oil.
The two oils distilled in Eritrea had the following characters: —
1. d15o 0-9464; aD - 0° 30'; nD20» 1-47176; acid value 1-0 ; ester
value 11*8 ; soluble in 2 volumes 70 per cent, alcohol.
2. d16o 0-9526 ;.a D - 1°; wD20o 1-47548; acid value 5'6; ester value
9-3 ; soluble in T8 volumes 70 per cent, alcohol.
Neither sample possessed its full camphor-content, for in the pre-
paration of No. 1 part of the camphor had separated out during distilla-
1
Jour, and Proc. Roy. Soc. N.S.W., xlvi. (1912), 103.
*Bol. Acad. Nac. Cienc. Cordoha, 19 (1913), 379.
3 Bericht, October, 1911, 106.
LABIAT^B 269
tion in the condensing worm, while from No. 2 it had been partly
extracted by freezing out.
OIL OF COLEUS AMBOINICUS.
Weehuizen l has obtained 25 c.c. of essential oil by distilling 120 kilos
of this Labiate plant, using the fresh herb for the purpose. The prin-
cipal constituent was identified as carvacrol.
OlL OF MlCROMEBIA.
Micromeria Chamissonis is a plant found wild on the Western

Coast of the United States, where it is known as Yerba Buena. The
oil has been examined by Power and Salway.2
The air-dried herb yielded 0*16 per cent, of essential oil having the
By extraction of the plant with hot alcohol, and steam distilling the
extract, an oil was obtained having the following characters :—
OIL OF AMARACUS DICTAMNUS.

An oil resembling oil of pennyroyal, and probably derived from
Amaracus Dictamnus, has been examined by Schimmel & Co.3 The oil
Optical rotation . . + 3° „ -f- 6°
Acid value 2*3
Ester „ 20-9
„ „ (after acetylation) 80
It contains from 66 to 85 per cent, of pulegone, and some menthol
and borneol.
OIL OF PYCNANTHEMUM.
Pycnanthemum lanceolatum yields an essential oil resembling
American pennyroyal oil in odour. It has been examined by Correll 4
who found it to have the following characters:—
Optical rotation - - 0 5 „ - 11*1°
It has more recently been examined by E. E. Miller,5 prior to whose-
work Correll had identified carvacrol in the oil, and Alden 6 had shown
that pulegone was also present. The oil examined by Miller had a
specific gravity 0*9017 at 25°, optical rotation - 4'6°, and refractive
index 1*4881 at 16°. He showed that in addition to the two bodies above
l
2
Rec. Trav. Chim. Pays-Bas., 37 (1918), 355. 3
4
Jour. Ainer. Ghem. Soc., 30 (1908), 251. Bericht, October, 1906, 84.
§
Pharm. Rev., 14 (1896), 32.
6
Circular 2, April, 1918, Pharm. Expt. Station, University of Wisconsin.
Pharm. Review, 16, 414 (1898).
named, the oil contains geraniol, dipentene, one or more terpenes not
identified, and a ketone which is probably thujone. The oil from young
plants contains as much carvacrol as, but less ketones than the oil from
matured plants. The following table gives the character of a number of
oils distilled during 1913-1916.
OILS DISTILLED IN 1913.
Yield Specific Optical Rota- Index of Per Per Saponifi-

No. of of Oil Gravity tion in Refraction Cent, Cent, Acid Ester cation No.
Sample. Per of Oil 100 mm. at 18 -9°. of of No. No. of Acetyl-
Cent. at 25°. Tube. Phenol. Ketone. atedOiL
1 0-314 0-9087 - 5-95 1-4962 41-4 3-0 1-49 4-32 166-5

2 0-270 0-8960 - 3-10 1-4915 34-2
3 0-276 0-9140 - 4-28 1-4850 21-7 —
7-0 —
3-44 —
17-02 —
193-7
4 0*442 0-9033 - 3-85 1-4905 31-0 4-0 2-15 11-31 173-8
5 0-376 0-9026 - 3-95 1-4930 38-0 8-0 1-23 5-85 160-4
6 0-431 0-9089 - 2-75 1-4911 32-0 3-0 1-85 7-61 167-1
7 0-426 0-9166 + 0-25 1-4894 24-0 7-5 3-57 11-00 148-7
8 0-425 0-9239 4- 3-38 1-4893 19-0 40-0 4-13 11-88 118-2
9 0-510 0-9292 + 0-60 1 1-4980 38-0 8-0 7-42 15-34 165-8
10 0-432 0-9355 + 5-20 1-4913 23-0 20-0 30-85 19-20 175-2
11 0-444 0-9284 + 4-00 1-4905 22-0 20*0 4-85 14-34 142-3
12 0-490 0-9440 + 4-64 1-4958 29-6 12*0 41-66 27-28 158-8
13 0-522 C-9246 + 3-70 j 1-4910 25-0 26-0 10-99 6-09 127-0
14 0-555 0-9290 + 2-30 1-4910 26-0 12-0 20-95 18-00 171-5
15 0627 09140 + 12-25 i 1-4840 14-5 30-0 1-38 6-92 85-8
16 0-720 0-9465 4- 10-05 1-4940 28-0 24-0 22-86 15-46 1467
17 0-674 0-9239 + 1-60 1-4902 27-4 12-0 18-60 3-64 184-3
18 0-694 0-9034 - 4-22 1-4888 28-0 5-0 0-54 7-94 180-4
19 0-540 0-9200 - 2-35 1-4995 53-0 5-0 0-60 5-04 193-1
20 0-557 0-9340 + 11-20 1-4850 20-0 24-4 45-17 33-27 185-2
21 0-402 0-9220 -0-80 1-4974 42-0 3-0 5-25 1765 195-8
Too highly
22 0-555 0-8998 coloured 1-4831 15-0 3-0 6-01 21-21 190-7
Oil of
1914
—
0-9180 + 0-05 — 32-0 10-0 1-88 4-75 138-8
1915 0-578 0-9087 + 8-05 1-4901 at 14-5° 23-0 15-0 0-55 3-80 110-1
1916 0-318 0-9230 - 1-10 1-5025 at 15° 49-0 5-0 0-72 3-75 111-6
VERBENACEÊ.
OIL OF VERBENA.
Most of the commercial so-called verbena oils and verbena extracts
are in reality composed of lemon-grass oil, which has almost entirely
superseded the older and true vervain oil. The genuine oil closely re-
sembles lemon-grass oil in general characteristics, but is of more deli-
cate odour. It contains a large quantity of citral, which, of course,
accounts for its similarity to lemon-grass oil. The plant yielding this oil
appears to be Lippia citriodora (Verbena triphylla : Aloysia citriodora).
The exact character of true verbena oil is somewhat obscure on account
of the almost universal use of lemon-grass oil under this name.
VEKBENACEJE 271
The so-called Spanish verbena oil is derived from a Labiate plant.
The yield of oil from the leaves varies from 0*07 to 0*2 per cent.
Optical rotation . . . - 10° „ - 17°
Aldehydes . . . . 20 to 40 per cent, (rarely to 50 per cent.)
Australian verbena oil, of uncertain origin, but possibly distilled
from the same plant, has a specific gravity about 0*890 and an optical
rotation - 6° to - 16°.
Verbena oil is rarely soluble in either 70 or 80 per cent, alcohol.
The principal odorous constituent of the oil is citral. Theulier1 has
identified geraniol, Z-limonene, a sesquiterpene, and a paraffin hydro-
carbon melting at 62*5°. Myrcene has been reported as present, but
the oil examined was probably lemon-grass and not true verbena oil.
Kerschbaum2 has made an exhaustive examination of the genuine oil
and has isolated therefrom an aldehyde C10H16O, which he has named
verbenone, and which had the following characters:—
Specific gravity . . . . . 0*974 a t 1 7 °
Melting-point of semicarbazone 208° to 209°
The following results were obtained by Messrs. Eoure-Bertrand
from oils distilled in Grasse at the time of early flowering:—
From From
Leaves. Inflorescence.
Percentage yield from the fresh plant 0*195 0'132
«D - 14° 16' - 8° 24'
Esters . 3-5 per cent. 3*2 per cent.
Combined alcohols 2-8 „ 2-5
Free alcohols 16-5 „ 13-8
Citral . 35-4 „ 29-6
The root yielded 0*014 per cent, and the stems 0'007 per cent, of
essence.
LANTANA OILS.
Lantana Gamara is a tropical plant, common in Java, Farther
India, the Philippines and New Caledonia. Bacon 3 has examined the
oil distilled from the leaves, and found it to have the following char-
acters :—
Ofi°
Specific gravity at ^L 0-9132
Optical rotation at 30° + 11-5°
A Java oil has been examined, which had a specific gravity 0*952
and optical4 rotation - 0° 24'.
Kanga has examined samples distilled from the flowers and leaves
of plants grown in Farther India, and found them to have the following
characters:—
1 2
1
Bull.
Soc. GMm., iii. 27 (1902), 1113. 4
Bericht, 33 (1900), 886.
Philip. Jour. 8ci.t 4 (1909), 12. Arch. der. Pharm., 252 (1914), 1.
From Dried From Fresh From
Flowers. Flowers. Leaves.
Specific gravity . . 0-915 afc 26° — 0-921 at 24°
Optical rotation . . + 23-9° — + 1'96°
Refractive index . . 1-4987 at 26° 1-5031 at 26° 1-4893 at 27°
An oil distilled in the West Indies, from Lantana odorata was found
to have an odour recalling that of amber and hyssop, and had the fol-
Specific gravity . . ' 0*9149
Ester value 4-7
CONVOLVULACE/E,
OIL OF EOSEWOOD.
Eosewood oil or rhodium oil as met with in commerce is almost, if
not quite, invariably an artificial mixture of several essential oils in
which true oil of roses and oil of geranium or Indian geranium are re-
sponsible for the rose or rose-geranium odour. The true oil of rhodium
is distilled from the wood, either of the stem or the root, of Convolvulus
scoparius and Convolvulus floridus, two species indigenous to the Canary
Islands. It is a thick, viscid, pale yellow oil, darkening on keeping.
It has an agreeable rose-like odour and sharp aromatic taste. An oil
examined by Gladstone, but whose authenticity is uncertain, had a
specific gravity 0*906 and an optical rotation - 16°. According to
Gladstone, it contains 80 per cent, of a terpene; but the authenticity
of the sample examined by this chemist is not guaranteed. It is more
probable that a large quantity of sesquiterpene is present. According
to Schimmel & Co. the oil solidifies at low temperatures to a mass of
acicular crystals melting at 11° to 12°. An oil, also of uncertain origin,
examined by these chemists had the following characters :—
Acid value . . . . . . . . . . 0
Ester „ (after acetylation) 151-3
The oil is chiefly used in soap perfumery. The Bois de rose femelle
is the wood of the so-called Brazilian lign-aloe, and yields the corre-
sponding linaloe oil. It is one of the Burseracea, and has no connection
with the above-described rosewood.
PRIMULACE>E,
OIL OF COWSLIP.
The fresh roots of Primula officinalis, when strongly bruised, develop
more or less rapidly, but always very distinctly, a marked odour. This
odour recalls at first that of anise, but that of methyl or amyl salicylate
finally predominates.
Further, if the roots thus bruised be treated with ether, a residue is
left on evaporation of the ether which, when dissolved in a little water,
gives a violet-blue coloration on the addition of dilute ferric chloride.
KUBIACEÊ 273
Since the odour of the essential oil does not pre-exist, it may be in-
ferred that in this root two substances are present, normally separated,
which are capable of yielding an essential oil by their reciprocal action.
Two glucosides have been separated from the roots by Goris, Mascre,
and Vischniac,1 which have been termed primeverin and primulaverin,
and which are both hydrolysed, yielding the two constituents of the
essential oil.
Primaveria has the formula C20H28O13 and melts at 206°, and on
hydrolysis yields sugars and the methyl ester of /3-methoxyresorcylic
acid, of the formula.
C . CO . 0 . CH3
H . C/\C . OH
H . Cv^yCH
C . O . CH3
This is the solid constituent of the essential oil, melting at 49*.
It has been described by Mutschler 2 as primulla camphor.
Primulaverin, C20H28O13, melts at 163°, and on hydrolysis yields the
liquid portion of the essential oil, which is the methyl ester of m-meth-
oxysalicytic acid, of the formula
C . CO . O . CH3
H . C/\C . OH
CH, . O . C
The essential oil from the flowers is practically identical with that
from the roots.
RUBIACEÊ.
OIL OF GARDENIA.
The flowers of Gardenia florid a and Gardenia grandiflora yield, on
maceration with petroleum, and distillation of the extract, about 0*07
per cent, of an essential oil having a specific gravity T009 and a specific
rotation + 1-47°.
According to Parone,3 the oil contains benzyl acetate, stryroyl
acetate, linalol, linalyl acetate, terpeneol and methyl anthraniiate.
OIL OP CHIONE GLABRA.
The bark of this tree, which is found in Grenada, yields 1*5 per cent,
of essential oil, which has been examined by Dunstan and Henry.4 It
is a liquid, depositing crystals on being cooled to - 20°. The principal
constituent is a substance of the formula C8H8O2, of specific gravity
0*850, and crystallising at low temperatures.
It forms an oxime melting at 112° and a phenylhydrazone melting
at 108°. It appears to be ortho-oxyacetophenone, C6H4 . OH . CO . CH3.
Traces of indol or a similar nitrogenous compound are also present.
iRou re-Bert rand Fils, Bulletin, October, 1912, 3. *Annalen, 185 (1877), 222.
* Bull. Chim. Farm., 41 (1902), 489. *Jour. Chem. Soc., 75 (1899), 66.
VOL. I. 18
OIL OF NUANUA LEAVES.
This oil is distilled from the leaves of one of the Nelitris species,
belonging to the Rubiacece. The plant is found in Samoa, and the oil
has been examined by Schimmel & Co. and found to have the following
characters:—
Kefractive index . 1-4849
Acid value 2-2
Ester „ 7-4
OLEACE/E.
OIL OF JASMINE.
The perfume of the Jasmine flower is principally marketed in the
form of enfleurage products or similar preparations, but the oil is of the
highest importance, an 1 its examination has led to the preparation of a
synthetic jasmine oil of considerable commercial value. The jasmine
perfume of commerce is almost entirely prepared from the flowers of
Jasminum grandiflorum, but as there are many closely allied species
the tollowing details1 of them are of considerable interest.
There are about 100 species and varieties, mostly natives of India,
Arabia, China, and tropical regions of the Old World, where this jasmine
is found in the wild state. A few occur in Africa and one in South
America.
The species commonly found in this country is Jasminum officinale,
the white jasmine, but it is not known when it was introduced into
England. It may be propagated by cuttings or by layering. The
flowers only develop on the young shoots, and to secure a good crop
the plant should be pruned in the autumn. Three varieties of this
species are known, the golden and the silver-edged leaf varieties, and a
double-flowered variety.
Jasminum grandiflorum, the Spanish or Catalonian jasmine, is the
species generally cultivated in the south of France, where it is grafted
on cuttings of the white jasmine. It resembles the latter, but the
branches are shorter and thicker, and the flowers much larger and
reddish underneath, forming at the extremities of the branches.
The white jasmine cuttings are planted in rows and trenched. Level
ground is best, but if rising ground only is available, it is formed into
a series of terraces. As soon as the young stem is strong enough shoots
of Jasminum grandiflorum are grafted upon it. It is then left until the
second year, when the long slender branches are trained along light
poles, supported horizontally and running the whole length of the rows,
the branches being entwined and interlaced between them. At the end
of the autumn ihe plants are banked up with earth to half their height,
when the exposed parts die off. The earth is removed in the spring,
when the plant begins to grow rapidly, and the flowers appear about
July, the flowering period continuing until the middle of October.
Jasminum sambac, var. trifoliatum, known in India as " kudda mulla,"
differs from the other varieties in having solitary flowers, the calyx
of which is divided into a large number of segments, and the leaves
*P. and E.O.R. (1916), 36.
o
FIG. 31.—Manufacture of flower pomades.

\_Lautier Fils.
occur in threes at the extremity of the flowering branches and in other
parts indifferently. This variety is called the " Tuscan jasmine," as it
was first imported into India by the Grand Duke of Tuscany about
1691. The flowers are greatly esteemed in India by the native women,
who string them into necklaces.
Two species are found in Madeira. Jasminum odoratissimum bears
yellow flowers, which retain when dry the natural perfume suggestive
of a mixture of jasmine, jonquil, and orange blossom.
Jasminum odoratissimum is also cultivated in Formosa, on account
of its fragrant flowers, which are known as shuei flowers. According to
Tsuchihashi and Tasaki1 these yield on extraction with petroleum ether
a concrete extract consisting of equal parts of " flower wax" and essential
oil. The latter amounted to O116 per cent, of the weight of the fresh
flowers extracted. It is a reddish-brown oil of specific gravity 0*9309,
FIG. 32.—Extracting jasmin by volatile solvents.

Rollet.] [Gattefossf.
refractive index 1'4845, optical rotation + 5'64, acid value 5*85, saponifica-
tion value 92*25, acetyl value 186'2. On fractionation under 4 mm.
pressure it was separable into eleven fractions, in which the following con-
stituents were isolated: dextrolinalol, 6 per cent.; dextrolinalyl acetate,
(5 per cent.; benzyl alcohol, 1*6 per cent. ; benzyl acetate, 6 per cent. ;
indole and methyl anthranilate, 10 per cent.; acid high boiling con-
stituents, sesquiterpene or diterpene alcohol, 57 per cent.
Jasminum azonicum is also a native of Madeira. It bears white
flowers almost all the year round, and has long been cultivated in
English greenhouses.
Jasminum hirsutum is a native of China and India. It bears large
white flowers, and the leaves and stems are hairy, as the botanical name
indicates. The young plants are more hairy than older plants. The
flowers occur in bunches, sometimes as many as thirty in a bunch.
1
J. Chem. Ind. Tokyo (1918), 21, 17.
OLEACE^ 277
Jasminum paniculatum is a white-flowered species, used in China

for scenting tea.
Jasminum revolutum is also a native of China, and bears yellow
flowers with a very fragrant odour.
Jasmin oil prepared from the pomade has the following characters :—
Optical rotation - 1° to + 4° 15'
Esters as benzyl acetate 41 to 73 per cent.
Differences of opinion have been expressed as to the composition of

this .oil. Verley l extracted the pomade with acetone and obtained, after
evaporation of this solvent in vacua, 40 grms. of oil, which on distilla-
tion in vacua left 40 per cent, of resin and yielded 60 per cent, of
essential oil. Verley concluded that the oil was approximately com-
posed of 10 per cent, of linalol and 90 per cent, of phenyl-glycol-
methylene-acetal (C9H10O2), which he termed jasmal. These researches
led to the granting of a French patent for the production of this body
synthetically, as an artificial jasmin oil. The specification states that
50 grms. of phenol-glycol, 30 grms. of sulphuric acid, diluted with 125
grms. of water, and 100 grms. of formic aldehyde are to be heated on a
water-bath. The resulting body when purified boils at 218°, and is said2
to have a strong jasmin odour. On the other hand, Hesse and Miiller,
who have examined a very large number of samples of this oil, state
that they have most carefully examined the oil, and assert that there is
not a trace of this body present, but that the main constituent is benzyl
acetate. The following are the figures they give for ten samples of oil
prepared by themselves from the pomade :—
Esters—
calculated as
No. Yield Specific Rotation
per Cent. Gravity.
Linalyl Benzyl
Acetate. Acetate.
1
Per Cent. Per Cent.

1 •427 1-015 + 2° 30' 95-4 73-0
2 •457 1-018 4- 2° 30' 91-5 70*0
3 •429 1-011 + 2° 30' 95-0 72-9
4 •473 1-009 + 3° 30' 92-0 70-4
5 •409 1-006 + 3° 15' 90-3 69'1
6 •395 1-007 + 3° 10' 90-9 70-7
7 •595 1-014 + 3° 20' 92-8 71-0
8 •490 1-012 + 3° 10' 94-1 72-0
9 •526 1-009 + 3° 30' 95-4 73-0
10 •480 1-015 + 3° 20' 93-3 71-4
They have made a very careful and exhaustive examination of the

oil, and have studied quantitative methods for estimating its com-
ponents, which led them to the conclusion that the average composi-
tion of the oil is as follows :—
1 2
Comptes rendus, 128 (1899), 314. Bericht, 32 (1899), 565, 765.
Per Cent,
Benzyl acetate 65
Linalyl „ 7'5
Benzyl alcohol 6
Linalol 15'5
Indol 2-5
Jasmone . . . . . . . . . . . . 3
Methyl anthranilate 0*5
Schimmel & Co. could find no jasmal in the oil, and more recently
Hesse l has found small quantities of indol, methyl anthranilate, and a
ketone which he terms jasmone, a sweet-smelling oil of specific gravity
0-945 and boiling at 257° to 258°.
Jasmone forms an oxime melting at 45° and a semicarbazone melt-
ing at 201° to 204°. Elze 2 has also isolated geraniol and para-cresol
from jasmin oil. •*-•-
There is another compound which can easily be prepared artificially
which has a distinct jasmin odour. The styrolene compounds are, as a
group, remarkable in taat they often possess floral odours. Thus, the
alpha-substitution products of styrolene C6H5 . CH : CH2, such as brom-
styrolene C6H5. CH : CHBr, have usually a distinct hyacinth-like odour.
Styrolene alcohol C6H5 . CH(OH)CH2OH is identical with phenyl-
glycol, the basis of the above-mentioned French patent; whilst second-
ary styrolyl acetate C6H5 . CH(O . CO . CH3)CH3 has itself a marked
odour of jasmin. This body can be prepared by the action of bromine
on boiling ethyl-benzene. The resulting bromide is heated with silver
acetate and glacial acetic acid, yielding styrolyl acetate.
Artificial oil of jasmin compounded on the lines of the above-
mentioned facts is now a regular article of commerce. It closely
resembles the natural perfume, except that it is less delicate, and is
well adapted for high-class toilet perfumery.
ERICACEAE.
OlL OF WINTERGREEN.
This oil is one of those which is so closely imitated by other oils

that the commercial article is very seldom the true oil at all. Genuine
wintergreen oil is the product of distillation of the leaves of Gaultheria
procumbens; " commercial" wintergreen oil is almost invariably the
product of distillation of the bark of Betula lenta, one of the Betulacea;:
or an artificial synthetic oil, methyl salicylate. Gaultheria procumbens
is a plant of North America, known as the tea berry or partridge berry.
The leaves are gathered and distilled in primitive apparatus, either
ordinary whisky stills, or stills composed of wooden tubs with copper
bottoms. The resulting oil, which is yielded to the extent of -5 to 1
per cent., has a specific gravity 1*180 to 1*193, and is faintly laevo-
rotary (under - 1°). It distils between 218° to 221°. Its refractive
index is about 1*5350. The bark of Betula lenta, the sweet birch, yields-
about the same quantity of an oil of so exactly similar a nature that it is
now sold as oil of wintergreen to the almost entire exclusion of the true
Gaultheria oil. The oil is the product of decomposition of the glucoside
1
Bericht, 32 (1899), 2611; 33 (1900), 1585; 34 (1901), 291, 2916 ; 37 (1904), 1457.
2
Chem. Zeit., 34 (1910), 912.
ERICACEAE 279
gaultherine. The only physical difference between the two oils is that
of sweet birch quite inactive optically, both oils being almost pure methyl
salicylate C6H4 . OH . CO2CH3. Cahours l was the earliest reliable in-
vestigator of wintergreen oil, but his work has been shown to be only
partially correct. According to him the oil consisted of about 90 per
cent, of methyl salicylate and 10 per cent, of a terpene, which he named
gaultheriline. Probably he examined an adulterated oil. Trimble and
Schroeter 2 stated that both oil o_LjEmtea?green and oil of birch contained
traces of benzoic acid and ethyl alcohol, togetherwith "under 0*5 per
cent, of a hydrocarborf (different in the two oils). Power and Kleber,3
however, have examined a very large number of samples, and give as
the result of their work the following summary:—
" Oil of Gaultheria.—Contains about 99 per cent, of methyl salicylate,
together with a small amount of a paraffin, probably triacontane C30H62,
an aldehyde or ketone, an apparently secondary alcohol C8H16O, and an
ester C14H24O2. To the latter body is possibly due the optical aclivity_
of the oil, whereas in the oil of birch it may be assumed that this body
has suffered inversion through the process of fermentation by which the
latter oil is formed.
"A pure fresh oil of gaultheria should show an optical rotation of
not less than - 0° 25' in a tube of 100 mm.
" Oil of Sweet Birch.—This oil consists to the extent of about 99*8
per cent, of methyl salicylate, and, in its unrectified state, contains also
a very small amount of the above-mentioned paraffin C30H62, and the
ester C14H24O2, but does not contain the alcohol C8H16O which is found
in gaultheria oil.
—" The oil of sweet birch is always optically inactive. —-
"Both of these oils have a specific gravity ranging usually from
1-180 to 1-187 at 15° C. Both of them, as well as the synthetic methyl
salicylate, form a perfectly clear solution with five (5) times their volume
of 70 per cent, alcohol at about 20° C., which, in connection with other
distinctive characters, is an excellent practical test for their purity.
" Neither the oil of gaultheria nor the oil of sweet birch contains any
trace of benzoic acid or its esters, nor does either of them contain any
terpene or sesquiterpene."
The above facts easily explain the appearance on the market of
artificial methyl salicylate, which is easily prepared by a condensation
of methyl alcohol and salicylic acid. It has been objected that the
odour of the artificial oil is not so fragrant as that of the natural oil,
but so long as the salicylic acid used in its manufacture is pure, no ex-
ception can be taken to it. As the synthetic oil is worth less than half
the value of the natural product of Betula lenta, and mixtures of the
two are impossible to detect, it is easy to understand how the producing
districts in America started importing the artificial oil, which returns to
commerce as natural oil. The purchase of this oil, so far as its origin
is concerned, must therefore be largely a matter of trust in the seller.
With the exception of the fact that the true oil of Gaultheria is faintly
laevo-rotary whilst the oil of Betula and the synthetic oil are optically
inactive, the limits as regards physical and chemical characters are
identical for the three oils. The specific gravity should never vary
outside the limits 1-180 to 1-193. The oil should give a clear solution
with five times its volume of 70 per cent, alcohol. On saponification
2
*Annalen, lii. 331. Jour. Amer. Chem. Soc. (1889), 398.
*Pharm. Rundschau, 13 (1895), 228.
with alcoholic solution of potash, the oil should give a result equivalent
to at least 98 per cent, of methyl salicylate. The salicylic acid result-
ing from the addition of acid to the saponification product, after a single
recrystallisation from alcohol, should melt at 155° to 157°. This will
guard against the use of impure salicylic acid in the preparation of the
artificial oil.
This oil is sometimes adulterated with petroleum or light camphor
oils, both quite easy of detection; also with sassafras oil, which, in spite
of its high specific gravity, is easily detected by its lowering the saponi-
fication number, and its characteristic odour remaining after the winter-
green odour has been destroyed by saponification. The oil is used to a
certain extent in pharmacy, either as a drug or to cover the nauseous
taste of other drugs, but more extensively as a flavouring in the manu-
facture of such confections as the American chewing gums.
Power and Kleber l have made an exhaustive examination of winter-
green and birch oils, and consider that they can be discriminated by
their odour, as would be indicated from the following results of their
work:—
In previous investigations the oils had been saponified by heating
with a solution of caustic alkali, and the alkaline solution subsequently
distilled, or shaken with a solution of either petroleum benzine or ether.
In order, however, that none of the constituents should become decom-
posed or altered by this treatment, they took advantage of the fact that
methyl salicylate combines with cold dilute solutions of the alkalies to
form salts of the ester. These are quite unstable, but the potassium
compound is readily soluble in water. The oils were, therefore, shaken
with successive portions of a cold dilute solution of potassium hydrate,
and when the oil had become reduced to about one-third of its original
volume an equal volume of ether was added, and the extraction with
alkali continued until nothing more was taken up by the latter from the
ether solution. After distilling off most of the ether, and the dissipation
of the last traces of the latter by heating for a short time on a water-
bath, the residues were weighed. The amounts were as follows:—
From 1500 grms. of Gaultheria oil, 15'7 grms. of residue, or 1-05 per cent.
„ 5000 „ Birch oil, , . 9-8 „ „ 0-196
The portion of both oils which was soluble in alkali consisted of
pure methyl salicylate. The acid separated therefrom had a melting-
point of precisely 155*5° C., which is that of pure salicylic acid, and it
did not contain a trace of benzoic acid.
The ether residues formed at ordinary temperatures a semi-solid
mass, from which, by distillation with steam, a nearly colourless oil was
obtained which no longer solidified in the cold. The amount of this
was as follows :—
From Gaulfcheria oil, 6-3 grms. or CK2 per cent.
„ Birch oil, 2'9 ,, 0'058
From the residue remaining after distillation with steam there was
obtained a substance crystallising in colourless, odourless laminae, ot a
r rly lustre, and having an apparently constant melting-point of 65*5°
The behaviour of this substance towards reagents proved quite con-
clusively that it is a paraffin, and most probably triacontane C30H62.
Its analysis gave the following result:—
1
Schimmel's Report, October, 1895, 50.
EEICACBÊ 281
C. 85-2 per cent. H. 15'2 per cent.
Calculated for C^H^.
C. 85-3 ,, H. 14-7
The oil, separated as above-mentioned from the paraffin, was readily
soluble in 80 per cent, alcohol, and therefore could have contained no
hydrocarbon, and especially no sesquiterpene as stated by Trimble.
Any benzoic acid contained in the original oil would also have been
found in this liquid, as the esters of benzoic acid are very resistant
toward a cold solution of potash. Upon saponification of a small por-
tion with a hot alcoholic solution of potash a somewhat oily acid was
obtained, but no trace of benzoic acid could be detected.
The oil separated from the paraffin was then subjected to fractional
distillation, at first under ordinary pressure and finally in a vacuum.
The lower boiling portion formed a crystalline compound with sodium
bisulphite, and when isolated in this manner was found to have an
odour resembling cenanthol. By oxidation it yielded an acid having
the odour of the higher fatty acids. An analysis of its silver salt gave
figures corresponding approximately to the formula C6H10O2.
After the separation of the body which yielded a compound with
sodium bisulphite, the oily liquid from the gaultheria was resolved by
fractional distillation into essentially two parts, the one distilling at
160° to 165° G. under ordinary pressure, the other at about 135° C.
under a pressure of 25 mm. or at 230° to 235° under ordinary pressure.
Both of these fractions possessed a highly penetrating and characteristic
odour, differing from each other, but which was so intense that a single
drop added to 5 c.c. of synthetic methyl salicylate almost completely
concealed the odour of the latter.
An analysis of the fraction boiling at 160° to 165° C. gave figures
agreeing with the formula C8H160.
Calculated for C8H16O:— Found :—
1. 2.
C. 75-0 per cent. 7*49 per cent. 74'9 per cent.
H. 12-5 „ 12-3 „ 12-4
By treatment of this body with benzoyl chloride and a dilute solution
of sodium hydrate a benzoic ester was obtained. An attempt to obtain
a phenylurethane by treating the substance with phenylisocyanate was
not successful. On the other hand, by the reaction with the latter,
diphenylurea (melting-point 235° C.) was obtained, due to the elimina-
tion of a molecule of water. This indicated that the body in question
is a secondary alcohol. The above-mentioned body which combines
with sodium bisulphite may thus perhaps be regarded as the correspond-
ing ketone of this alcohol, which could then be readily converted into
an acid of the composition C6H10O2.
The purification of the fraction boiling between 230° and 235° C.
was attended with great difficulty, as by distillation a slight elimination
of water constantly took place, and the liquid acquired a yellow colour.
Several analyses were made of it, without obtaining perfectly constant
results. The body was, however, characterised as an ester, and in fact,
according to the odour developed after saponification, as the ester of the
previously mentioned alcohol C8H14O. The acid obtained from it by
saponification was of an oily nature, and had a peculiar unpleasant
odour, similar to that obtained from the previously mentioned aldehyde
or ketone. The analysis of its silver salt, which is readily decomposed
with the loss of acid, also gave a corresponding result. It is therefore
282 THE CHEMISTEY OF ESSENTIAL! OILS
probable that this ester is formed from the alcohol C8H16O and the acid
C6H10O2, and that it possesses the formula C14H24O2, which would require
G. 75 per cent., H. 1O7 per cent., whereas the carbon found varied
from 75'7 per cent, to 78*4 per cent, and the hydrogen from 8'88 per
cent, to 1040 per cent. The excess of carbon and the deficiency-of
hydrogen would result from the splitting-off of water.
With regard to the small amount of volatile substance associated
with the paraffin in birch oil, it may be said that independently of the
aldehyde or ketone, which is also present, it appears to consist chiefly
of the above-mentioned ester, and not to contain the body of alcoholic
nature which is present in the oil of gaultheria. The presence, therefore,
of this intensely odorous alcohol, C8H16O, in the latter oil, imparts to it
a specific character, so that by the odour alone it is possible to distin-
guish it from the oil of birch.
A sesquiterpene alcohol, betulol, C15H24O, and its acetic ester have
been found in the oil of Betula lenta.
Many colour reactions have been suggested for differentiating be-
tween the oils of gaultheria and sweet birch and artificial methyl
salicylate. Most of these are unsatisfactory, the only one which yields
useful results in the author's opinion being that of Umney,1 which is as
follows:—
To five drops of the oil in a test tube add five drops of a 5 per cent.
alcoholic solution of vanillin and 1 c.c. of alcohol. Shake well, and add
2 c.c. of concentrated sulphuric acid and mix thoroughly. When this
test is applied, pure gaultheria oil produces an intense crimson colour, and
pure Betula oil a deep blood-red, while synthetic esters give a yellow colour.
Methyl salicylate has been detected in the following amongst other
plants:—
BETULACEJE. Discoverer. Year of
Discovery.
Betula lenta L . . . . . . Wm. Procter, jr. . 1844
Betula lutea Mich, probably, but
not yet determined.
LAUBACE^:.
Lindera Benzoin Meissner Schimmel & Co. 1885
ROSACES.
Spircea ulmaria L . . . . . Schneegans & Gerock 1892
ERYTHBOXYLACE.E.
Erythroxylon coca Lam. Iv. Romburgh . 1894
,, bolivianum (?) .
POLYQALACE^.
Polygala senega L . . . . . Langbeek . 1881
,, var. latif. Torr. and Gray L. Reuter . 1889
baldwinii Nuttall . J. Maisch . 1890
variab. H. B. K. albifl. D. C.
javana D C . . I v. Romburgh 1894
oleifera Heckel
serpyllacea Weihe .
(depressa Warden). VBourquelot 1894
calcarea F. Schultz
vulgaris L.
PYBOLACEÊ.
Hypopitys multiflora Scop. Bourquelot 1894
(Monotropa Hypop. L.).
TERNSTBOSMIACE^:.
Thea chinensis . . . . . Schimmel & Co. . 189T
1
P. and E.O.R., 5 (1914), 60. •
EEICACE^l
Andromeda Leschenaultii . . Broughton . . —

Gaultheria procumbens L. Cahours . . . 1843
„ fragrantissima Wall . Broughton . . 1867
(Gaultheria punctata Blume .
,, Leschenaultii, D. 0.) VKoehler . . . 1879
Gaultheria leucocarpa Blume
Numerous other plants are mentioned in Schimmel's Report, 1900

(April).
The author has also detected traces of it in some plants of the
natural order Violacece.
OIL OF GAULTHEKIA PUNCTATA.
Gaultheria punctata, a plant growing in British India, and also in
the Dutch Indies, yields, according to De Vrij, from 0*75 to 1*15 per
cent, of essential oil. The oil has the following characters:—
Methyl salicylate 97-9 to 99 per cent.
It is practically identical with ordinary wintergreen oil.
OIL OF MARSH TEA.

Ledum palustre, also known as "wild Kosemary," a plant of this
natural order, yields from •£ to 2 per cent, of an essential oil. The plant
is one flourishing in marshy places in the northern parts of North
America, Asia, and Europe. The leaves and flowering twigs are used
for distillation, and the oil obtained is of a reddish-yellow colour and
sharp taste and odour, having a specific gravity from 0'930 to 0*960.
The oil appears to consist almost entirely of a sesquiterpene alcohol
G16H26O, which has been termed ledum camphor, and a sesquiterpene
possibly identical with that obtained by treating the camphor with de-
hydrating agents, and which has been named ledene. Ledum camphor
forms long white needles, melting at 104° and boiling at 282°, and having
a specific rotation of + 8° in alcoholic solution. A ketone of the formula
C15H240 is also present in the oil. The oil possesses strongly narcotic
properties, and is said to be occasionally illicitly added to beer to render
it more intoxicating. This, however, is very doubtful. The oil from
the leaves has a specific gravity of "925 to *935, and that from the
flowering twigs about '960.
A sample distilled by Schimmel & Co. a had the following charac-
ters :—
Acid value 0-9
Ester value 27
No crystals of ledum camphor separated on standing at - 30°.
1
Bericht., 1919, ±6.
OIL OF BHODODENDRON.
Several species of Rhododendron contain essential oils, a distillate
(from mixed species) having been examined by Haensel.1 The yield
of oil was 0*123 per cent., which had the following characters :—
The oil contains a small quantity of aldehydes.
Bertrand-Fils2 have examined a specimen of this oil and found it to
have a specific gravity O840, and an ester value 63*5.
APOCYNACE>E.
OIL OF APOCYNUM ANDEOS^BMIFOLIUM.
The rhizome of Apocynum androsc&mifoliuin yields about 0*016 per
cent, of essential oil having the following characters :—
The oil distils between 130° and 250°. It contains furfurol, and
aceto-vanillone CH30 : CgHÔH) . CO . CH?, which results from the
decomposition of a glucoside, named androsin.
VALERIANACE/E.
OIL OF VALERIAN.
Oil of valerian is obtained by the distillation of the roots of Valeri-
ana officinalis, a plant growing wild, and also cultivated, in Northern
and Middle Europe and in Asia. This is the Dutch and Thuringian
root usually distilled in Europe, but a much larger yield of a very
similar oil is obtained from the Japanese plant Valeriana officinalis,
var. angustifolia.
European roots yield from 0*5 to 1 per cent, of oil, whilst the
Japanese roots yield up to 8 per cent.
The characters of the two oils are as follows :—
European. Japanese.
Specific gravity . . . 0-920 to 0-960 0-965 to 1-000
Rotation - 8° „ - 15° - 20° ,, - 35°
Refractive index 1-4840 „ 1-4868 1-4775 „ 1-4875
Acid value . 12 „ 55 1 „ 20
Ester „ 55 „ 100 90 „ 135
The oils from the two varieties are similar, and may be used indis-
criminately.
Pierlot investigated this oil some years ago, but his results cannot
be accepted in the light of our present knowledge of essential oils.
Oliviero3 has carefully examined some European oils which had ab-
normally low specific gravities—*875 to '900, and isolated the terpenes
pinene, camphene, and limonene; borneol and its formic, acetic, and
iso-valerianic esters, terpineol, and probably a sesquiterpene, a sesqui-
terpene alcohol C15H26O, and a crystalline bivalent alcohol of the
1
Chem. Zentral.s (1906), ii. 1495 1. * Bulletin, 4 (1920), 1.
Comptes rendus, 117 (1893), 1096.
COMPOSITE 285
formula C10H20O2, melting at 132°. Bertram and Gildemeisterl have
examined the Japanese or " kesso" oil and found in it the terpenes
pinene, camphene, and dipentene, terpineol, borneol, bornyl acetate, and
bornyl iso-valerianate, a sesquiterpene, a blue oil not identified, and
kessyl acetate C14H23O . CO2CH3. This body is the acetic ester of
kessyl alcohol C14H24O2. It is a liquid boiling at 300°. Kessyl alcohol
forms rhombic crystals melting at 85°.
Valerian oil is employed to a considerable extent on the continent as
a popular remedy for cholera, in the form of cholera drops, and also to
a certain extent in soap perfumery.
An oil is also obtained from Valeriana Celtica, a native of the Swiss
Alps and the Tyrol. Between 1 and 2 per cent, of oil is obtained
having an odour recalling that of a mixture of patchouli and chamo-
miles. Its specific gravity is2 from 0-960 to 0*970.
Messrs. Schimmel & Co. have distilled a parcel of Mexican root
which was probably Valeriana Mexicana, known locally as cuittapatti.
The oil had a disagreeable odour of valerianic acid; its specific gravity
was '949, and it was optically inactive. It appears to consist almcs*
entirely of hydrated valerianic acid.
OIL OF SPIKENARD.
This oil, which is the true spikenard or Indian spikenard, has been
described as being obtained from various plants, but there now appears
to be no doubt that it is obtained from Nardostachys Jatamansi, a plant
flourishing in the Alpine Himalayas and district. Kemp 3 distilled
56 Ib. of the root and obtained 3 oz. of oil, whilst another parcel of
100 Ib. yielded 15 oz. It is a pale yellow oil of specific gravity -975,
and optical rotation about — 20°.
Asahina 4 has examined a Japanese distilled oil, which he found had
Specific gravity O9536
Acid value . . . . . . . . . . 0
Ester „ 45-7
He isolated from the oil a sesquiterpene of specific gravity 0*932,
boiling at 250° to 254°.
Although its odour may be considered disagreeable by many, it is
highly esteemed in the East as a perfume. Its use is practically re-
placed in Western countries by that of oil ot valerian.
COMPOSITE.
CHAMOMILE OIL.
There are two varieties of this oil, the Eoman chamomile oil, dis-
tilled from the flowers of Anthemis nobilis, a plant indigenous to the
southern and western parts of Europe, and cultivated in Germany,
Great Britain, France, and Belgium; and the German chamomile oil
distilled from the flowers of Matricaria chamomilla.
1 2
3
Arch. d. Pharm., 228 (1890), 483. 4
Bericht,
April, 1897, 47.
Pharmacographia Indica, ii. 237. Jour. Pharm. Japan (1907), 355.
Eoman chamomile oil, which is the oil official in the British
Pharmacopoeia, is obtained to the extent of 1 per cent, from the re-
cently dried flowers. It is distilled in England, especially at Mitcham,
Sutton, and Long Melford. When first distilled it is of a blue colour,
but usually turns to a greenish or greenish-yellow colour on keeping.
It has a characteristic flavour and odour, but not of the nature to
justify its use in perfumery. Its characters are as follows :—
Optical rotation - 3° „ + 3C
Ester „ 220 „ 320
It is chiefly composed of esters of angelic and tiglic acids, two
isomeîc acids of the formula C5H8O2. The following esters have been
identified: isobutyl isobutyrate, isobutyl angelate, isoamyl angelate,
amyl tiglate, hexyl angelate, hexyl tiglate, and possibly esters of an
alcohol anthemol, C10H16OH. Traces of the free alcohols and acids,
probably due to1 decomposition of the esters during distillation, also
exist. Naudin obtained from the flowers, by extraction with light
petroleum, two crystalline substances not included in the above list.
One of these he terms anthemene, and considers it to be a hydrocarbon
C18H36 of the ethylene series. It forms microscopic needles melting at
63°. According to Klobb,2 however, its formula is probably C30H62.
German chamomile oil from Matricaria chamomilla has a specific
gravity about 0*940. Its colour is intensely blue, often turning greenish-
blue on keeping. It is a thick fluid becoming semi-solid on cooling,
commencing to thicken at about 14° and congealing at 1°. The oil has
.the following characters :—
Specific gravity 0-920 to 0-U55
Befractive index T3G40
Acid value 9 to 50
Ester 5 „ 35
It is freely soluble in 90 per cent, alcohol. According to older
researches, which are not reliable, the oil consists of chamomillol
C10H16O, a terpene, and trichamomillol C30H48O3 (the blue portion of
the oil). As a matter of fact, the only constituents whose identity have
been definitely proved are esters of caproic and nonylic acids, with
traces of their decomposition products, together with a solid hydro-
carbon or mixture of hydrocarbons, which is probably responsible for
the solidification of the oil at low temperatures. This body (or mixture)
melts at 53° to 54°, and when perfectly pure is quite white. Messrs.
Schimmel & Co. consider it to be a hydrocarbon or hydrocarbons of the
paraffin series. Possibly it contains the bodies previously isolated
from Eoman chamomile oil by Naudin (vide supra). The exact nature
of the blue constituent of the oil is not known, but it is probably identi-
cal with that found in other oils, and has been named azulene. It
appears to have the formula C15H18.
Power and Browning 3 have, in the course of an investigation of the
constituents of the flowers of Matricaria chamomilla, examined the
small amount (23 grms.) of essential oil obtained. The oil distilled
1
Bull. Soc. Chim.,
8
Ixi. (1884), 483. *Ibid., vii. (1910), 940.
Jour. Ghem. Soc. (1914), 2280.
COMPOSITE 287
over a wide range of temperature, the whole of the distillate being blue
in colour, with the exception of a small fraction boiling at 250° to 270°
at 15 mm., which was a viscous liquid of green colour. The blue oil
contained furfuraldehyde, and deposited, on standing, a small amount
of a crystalline substance which was found to be umbelliferone methyl
ether. A portion of the essential oil, in ethereal solution, was shaken
with aqueous potassium carbonate solution, and a trace of a free fatty
acid obtained. No other constituent was identified.
Ghamomile oil is often adulterated with cedar and turpentine oils,
sometimes with copaiba oil, and, according to some authorities, with
milfoil oil. Some of the commercial oil is merely turpentine or lemon
oil or a mixture of these oils, distilled over chamomiles. This repre-
hensible custom of selling low-priced rubbish under unjustifiable names
is countenanced by even some reputable firms, who offer in their price
lists " chamomile oil" and " chamomile oil with lemon," the latter at
about one-fifth of the price of the former.
OIL OF FEVERFEW.
The common feverfew, Pyrethrum parthenium (Matricaria par-
thenium), yields a small amount of essential oil of strong, characteristic
odour. The green flowering herb yields about -07 to -4 per cent, of an
oil of specific gravity -900 to '960. The dried herb yields rather less
oil than the fresh plant. Dessaignes and Chautard 1 investigated this
oil and stated that it contained a terpene and an oxygenated body
resembling camphor. In all probability this oxygenated body is a
mixture of camphor and borneol. Schimmel & Co. obtained *068 per
cent, of oil from the herbs, which had a specific gravity *960. Even at
the ordinary temperature it contained a considerable number of hexa-
gonal crystals, which appear to be borneol. Bornyl esters are also
present, but no camphor could be detected.
OILS OF ARTEMISIA.
The principal essential oil of this group is that of Artemisia Absin-
thium, oil of wormwood, or oil of absinthe. It is distilled from the herb,
a plant indigenous to the mountainous regions of Northern Africa,
Southern Europe, and Northern Asia, and cultivated to a considerable
extent in North America, especially in the States of Michigan and
Indiana, and in Wayne County, New York State.
The oil is of a greenish or greenish-blue colour and of intense odour
and taste of the herb itself. It has the following characters :—
Specific gravity . 0-900 to 0-955 (rarely as low as 0-885)
Refractive index . 1-4660 to 1*4750
Ester 12 „ 185
The above figures2 show that this oil is exceedingly variable in characters.
E. B. Miller has examined six typical samples of Wisconsin oils,
and gives the following figures for the ester and acetylation values,
which do not indicate so great a variation as the above figures. In
the ester determination, the results for saponification in thirty minutes
and in sixty minutes are given.
l 2
Jour.prakt. Chem., 45 (1848), 45. Bull. Univ. Wisconsin, 693.
ESTEE DETERMINATIONS.
C.C. N.
C.C. o f - Length of Saponi- Amount Amount
of Ester
Sample Gms. of HoS04 of
'2 Time fi cation
of Oil. Oil Used. alcohol
Required
Heated. for 100 c.c. Number. Thujyl Expressed
KOH used. Alcohol. as Thujyl
Acetate.
of
Solution.
la 4-7976 56-7 half hour 7-94 100-4 27-61 35-U

Ib 5-2484 56-7 one 7-6 99-7 27-42 34-89
2a 5%S329 56-7 half 8-45 75-8 20-84 26-53
26 5-4642 56-7 one 8-46 73-78 20-3 25-83
3a 5-1840 56-7 half 7-63 100-19 27-55 35-07
36 5-3092 56-7 one 7-64 97-56 26-84 34-16
4« 5-2851 56-47 half 7'61 97-58 26-84 34-16
46 4-9747 56-62 one 7-85 97-65 26-85 34-18
5a 5-6123 56-81 half 7-5 96-29 26-48 33-70
56 5-6400 56-81 one 7-56 94-32 25-93 33-00
6a 5-1156 56-81 half , 8-08 89-61 24-64 31-36
66 5-5468 56-81 one , 7-6 94-9 26-10 33-21
ACETYLATION VALUES.
i
Saponifica- Correspond- A Amount of
Sample of
Oil. tion Num-
ber.
ing Amount
of Alcohol.
'±^r ôjissr
Ac-tt &3E& Acetate
present =
Thujyl Acetate.
Per Cent. Per Cent. • Per Cent. Per Ce .

1 157-13 48-97 27-42 21-55 34-89
2 113-93 34-25 20-30 13-95 28-83
3 134-29 41-07 26-84 14-23 34-16
4 118-44 35-74 26-85 ! 8-89 j 34-17
5 | 129-53 39-45 25-93 ! 13-52 33-00
6 125-41 38-06 26-10 11-96 33-12
Roure-Bertrand-Fils l have examined two samples distilled by them-

selves from the wild plants and found them to contain the following :—
1. 2.
Esters . . . . . 9*0 p e r cent. 5-5 p e r cent.
Combined alcohols . . . 7 * 0 „ 4'3 ,,
Free alcohols . . . . 71-9 ,, 76-3
Thujone 8-4 „ 3-0 ,,
Thujyl alcohol appears to be formed at the expense of the thujone
present as2 the growth of the plant proceeds. Two oils examined by
Charabot, which had been distilled at an earlier and a later date from
the same plantation, gave the following results :—
1. 2.
Specific gravity . . . 0'9307 0-9253
Esters 9-7 per cent. 13-1 per cent.
Free thujyl alcohol . . . 7-6 „ 10'3
Combined thujyl alcohol . . 9 - 0 ,, 9'2 „
Total „ ,, . 16-6 ,, 19-5 „
Thujone 43'1 „ 35'0
It contains a considerable proportion of the ketone thujone, varying
1
Bulletin, April (1906), 36. *Comptes rendiis, 130 (1900), 923.
COMPOSITE 289
1
from 30 to 45 per cent. Schimmel & Co. have investigated it, and find
a very small quantity of phellandrene and cadinene and the merest traces
of pinene present. In addition to these bodies, the oil contains free
thujyl alcohol and its acetic, isovaleric, and palmitic esters. The blue
compound present is probably azulene. A pure sample examined by
means of the acetylation and saponification methods gave results
equivalent to 14 per cent, of thujyl alcohol and 15 per cent, of thujyl
acetate. The oil is frequently adulterated, the favourite adulterant being
turpentine. This is best detected by distilling 10 per cent, from the oil.
This fraction should dissolve to a clear solution in twice its volume of
80 per cent, alcohol. The presence of even a very small amount of
turpentine upsets this test. Wormwood oil has a tonic and stimulating
effect on the digestive organs, and is sometimes also used externally. It
is a constituent of the well-known liqueur, absinthe.
Paolini and Lomonaco 2 find that the Italian oil contains 10 per cent,
of a mixture of alpha and beta-thujone, which are identified by means of
their semicarbazones, and about 48 per cent, of thujyl alcohol, which
was separated in the form of its phthalic acid ester. Phellandrene was
also isolated as its nitrosite, melting at 105°, and cadinene was separated in
the form of its hydrochloride. Thujyl alcohol is present in the free state,
and also in the form of acetic, isovalerianic, and palmitic esters. At least
two isomeric thujyl alcohols are present including the deZta-variety.
European wormseed oil (Oleum cina) is the product of distillation
of the unexpanded flower buds of Artemisia maritima, although other
species probably contribute to the commercial oil. (" American worm-
seed " oil is the product of one of the Chenopodiacece, q.v.). The plant
is indigenous to the Orient and Southern Russia, Levant wormseed (as.
the buds are termed) being the most highly valued. The principal
constituent of wormseed is the well-known drug santonin, the well-
known anthelmintic. The greater part, if not the whole, of the oil
found in commerce is obtained from the santonin factories, and is said
to differ slightly from the oil distilled from the seeds without extracting
the santonin ; this, however, is very doubtful. The yield of oil is about,
2 per cent. It is a thick yellow oil having the following characters :—
Specific gravity O915 to 0*940
This oil has been the subject of numerous researches, the results
obtained being extremely variable, no doubt due to difference in the
species 8of Artemisia used, or to the employment of adulterated oil.
Volckel stated that it was a mixture of bodies to which he assigned
the names cinaebene and cinaebene camphor, without giving any very
definite evidence of their purity. Kraut and Wahlforss 4 found the chief
constituent of the oil to be a substance of the formula C10H18O. This
body is clearly cineol, which is definitely settled as the principal con-
stituent of the oil. Faust and Homeyer 6 assigned to the principal
constituent the formula C10H16O. Hell and Stiircke,6 using^ the oil
from Artemisia vahliana, one of the species contributing to the Levant
wormseed, confirmed the presence of cineol C10H18O. The presence of
1 2
Berichte, April (1897), 51. Ckem. Zentral. (1915), i. 607.
4
*Annalen,
5
38 (1841), HO. 6
Ibid., 128 (1864), 293.
Berichte, 5 (1872), 680. Ibid., 17 (1884), 1970.
VOL. I. 19
cineol was again confirmed by Wallach and Brass,1 who also obtained2
a terpene from the oil, which is probably dipentene. Schindelmeiser
has identified *-a-pinene, terpinene, and Z-a-terpineol, and Schimmel & Co.
have found a terpilenol present. A sesquiterpene of specific gravity 0*917
is present in the higher boiling fractions.
Artemisia annua yields an oil which has been examined by Imada and
also by Asahina and Yoshitomi.3 The oil had the following characters : —
Specific gravity at 0-908
Optical rotation ......... - 16-19°
Acid value .......... 1'8
Ester „ .......... 34-6
,, ,, (after acetylation) ....... 63 '5
14°
A ketone, C10H16O, boiling at 182° and of specific gravity at—-^ of 0-8906
was isolated from the oil, and also laevo-camphor. Eucalyptol is also
present. The new ketone, above mentioned, is optically inactive, and
yields a semi-carbazone melting at 95° to 96°. It has been provisionally
named " artemisia ketone ".
Artemisia Barrelieri yields an essential oil of specific gravity about
•920 which contains thujone. Artemisia glacialis, the " mountain worm-
wood," known commercially as " Genepi des Alpes," yields under •£ per
cent, of an oil of specific gravity '964 to %970, which solidifies to a buttery
consistency at 0°. It has been suggested as a suitable ingredient for
making liqueurs to imitate the famous Benedictine and Chartreuse.
Artemisia herba alba, var. genuina, a plant of Algerian origin, yields
an essential oil known by the Arabs 4
as Oil of Scheih or Chih.5 This oil
has been examined by Grimal, by Jeancard and Satie, and by
Bertrand-Fils.6 The oil from7 the variety densiflora has also been ex-
amined by Schimmel & Co. The former oil contains Z-camphene,
•cineol and Z-camphor.
Artemisia campestris, var. odoratissima, is also an Algerian plant,
yielding the so-called Oil of Gouft. It has been examined by Jeancard
and Satie,8 and by Bertrand-Fils.9 The oil contains geraniol, geranyl ace-
tate, Z-a-pinene, and probably nopinene. Its characters are as follows : —
Constants. Jeancard Bertrand.

and Satie.
Density . . . . . . . . . D»-55 0-8720 DH 0-8763

, «i o —15° 20' ai & _i6° 24'
Acid value 1-12 0-94
Saponification value . . . 14 30-81
Ester value . . . . 12-88 29-87
S . V . after acetylation . . . 42 41-07
Total alcohols calculated as C10H18O 11-93 per cent. 11-65 per cent.
Combined alcohols ,, ,, 3-55 8-21
Free alcohols „ „ 8-36 3-44
Soluble in 96° per cent, alcohol t 1/2 vol. 1/2 vol.
The following are the characters recorded by the various

observers:—
1 2
3
Annalen, 225 (1884), 291. Apottteker Zeit., 22 (1907), 876.
5
Jour. Pharm. Soc. Japan (1917), 424, i.
6
*Bull. Soc. Chim. [3], (1904), 31, 694.
7
Ibid., 478. Bulletin (1920), 4, 1, 18.
8
Bericht, April, (1909), 96;October (1909), 19. 9
Bull. Soc. Chim. [3], (1904) 31, 478. Bulletin (1920), 4, 1, 27.
Jeancard Schimmel & Co. Bertrand-Fils.
Characters. and Grimal.
Satie.
I. II. I. II.
Specific gravity . . . . . . D»' 5 0*9540 Djjj 0-9456 DJS 0-9192 Dl 10-8994 DI* 0-9432 Dji 0-958 a
Optical rotation . . . . . . [a]*9 — 15°30' OD —5° 20' a D +14°5' a*77 +2° 6' —6° 12' o
Refractive index . . . . . . w»° 1*47274 n™ 1-45611 n*» 1-46684 w* 1-47120 B
Acid value . . . . . . 8-4 1-5 4-6 3-5
Saponification value .
Ester value . . .
.
.
.
.
66-5
58-1
6-46
95-69
89-23
12'5
11
39-6
35
57-4
53-9
18-2
56-7
38-5
8
QQ
,, after acetylation
Total alcohols calculated as C10H18O
Combined alcohols „ „
.
129-5 135-38 40-7 163-3 147 173-6
39-44 per cent. 37-13 percent. 11*54 per cent. 51-17 per cent. 45*44 per cent. 54-8 per cent.
16-1 24-48 3-03 9-63 14-80 „ 10-6
I
Free
1
alcohols „ „ 23-34 „ 12-65 8-51 41-54 „ 30-64 „ 44-2
Solubility in 70 per cent, alcohol 2 '5 vol. 2 to 2-5 vol. 2-5 vol. 1-8 vol. 1-4 vol.
1
All these samples become opalescent on subsequent addition of alcorjLOl.
CO
Artemisia frigida, submitted in the fresh state to distillation with
steam, yields about 0*4 per cent, of a greenish oil with a cineol-like odour,
and having the following characters :—
Optical rotation - 23° 40' to - 25° 10'
Acid value . . . . . . . . 1to 4
Ester ,, 31 „ 45
„ „ (after acetylation) . . . . 139 „ 143
The dried herb gave on distillation a yield of only 0*07 per cent, oil
of a darker colour; d22o 0'930; acid number, 4*7; ester number, 40;
saponification number, 44*7. From the distillation-water of this second
distillation an oil could still be obtained with petroleum1 ether, which
was also darker than the oil from the fresh herb. Eabak gives for the
extracted oil d22o 0*916 ; acid number 5*3 ; ester number 25 ; saponi-
fication number 30'3. The oil has the following composition :—
Free borneol . . . . . . . . 35-8 p e r cent.
Borneol combined as .heptoic ester . . . . 6-8 ,,
Gineol (eucalyptol) 18 to 20 „
Fenchone . 8 ,, 10 „
From the fresh herb of Artemisia leudoviciana 0*38 per cent, greenish-
yellow oil is obtained, having a strong aromatic odour. Its characters
are as follows :—-
Specific gravity . . . . . . 0'924 t o 0'926
Optical rotation . . . . . . - 13° to - 17° 20'
Acid v a l u e . . . . . . . . 0 t o 4-5
Ester „ . . . . . 10 „ 26
„ , , (after acetylation) . . . . 116
The fresh.herb of Artemisia caudata yielded 0*24 per cent, yellow
oil with a sweetish odour, which points to the presence of methyl
chavicol or anethol. Its characters are as follows :—
Optical rotation . 0° to - 24° 20'
Acid value 0 to 20
Ester ,, 17 „ 73
Artemisia arborescens yields about 0*6 per cent, of a deep blue
essential oil of specific gravity 2about 0*946, acid value 9*8, and ester
value 19*5. According to Jona it contains 13*9 per cent, of alcohols,
of which borneol and thujyl alcohol have been identified, and about 13
per cent, of thujone. As constituents of the esters there were found
formic, acetic, isovalerianic, pelargonic, palmitic, and stearic acids.
Artemisia vulgaris yields an oil which has the following characters :—
Specific gravity . 0-907 to 0*939
Retractive index 1-4776 to 1-4855 (Indian oil 1-4620)
Acid value . 1 to 2
Ester „ . 16 „ 103
The oil contains a-thujone.
Artemisia Dracunculus yields the well-known estragon or tarragon
oil. This is a pale yellowish-green oil of characteristic odour and taste
of the tarragon herb, and having the following characters :—
Optical rotation + 2° , + 10°
Acid value 0 2
Ester „ 1 , 10
1
Pharm Review, 23 (1905), 86. *Ann. Chim. Appl., 1 (1914), ii. 63.
COMPOSITE 293
The oil oxidises on keeping, with the result that the specific gravity
may rise to TOOO, or even over this figure.
; \ (Tarragon oil contains methyl-chavicol (the " estragol " of Grimaux),
ocimene(?), phellandrene, and some unidentified constituents which
influence its odour and flavour.
\*. Artemisia lavandulaefolia, a Javan plant, yields an essential oil con-
taining a crystalline compound of the formula C12H14O2, melting at 32°
to133°. It is probably the methyl ester of an unrecognised acid.
Artemisia glutinosa. Bennett * has examined the oil distilled from
this species in Murcia, Spain. It has the following characters :—
Specific gravity 0*937C
Optical rotation + 24
Total alcohols as borneol . . . . . . 17 '5 per cent.
Esters as bornyl acetate 6-3 per cent.
Phenols 8 per cent.
Aldehydes and ketones 18 per cent.
Terpenes, probably terpinene or dipentene principally, are present.

Methyl-chavicol is probably present in the oil.
OlL OF EUTHAMIA CAROLINIANA.
This plant, a member of the Compositae, is indigenous to Florida and

Texas, and occurs in greatest abundance near the coast. It is rarely
found on new land or in woods, but frequently in moist sandy fields or
lake bottoms. It flowers from September to November, producing an
abundance of small lemon-yellow blossoms. A quantity of the fresh
herb has been distilled at the Florida station of the Office of Drug and
Poisonous Plant Investigations of the Bureau of Plant Industry, the
material being gathered in2 old fields adjacent to the City of Orlando,
in Orange County, Florida. The yield of oil from the fresh herb was
€'693 per cent. The oil was pale yellow in colour and possessed a
pleasant aromatic odour and an acrid, slightly bitter, taste, with a
strong terebinthenous after-taste. The oil has the following char-
acters :—
Optical rotation . 10° 48'
No free acids were present even after storing for fifteen months, and
the saponification value was only 6'35. The saponification value after
acetylation was 25'3, equivalent to 7'01 per cent, of alcohols. No
phenols were present, but a trace of aldehyde was indicated by SchifFs
reagent. The oil consisted mainly of dipentene, with a trace of pinene
and possibly limonene. On fractionation about 10 per cent, of highly
laevo-rotatory fractions was obtained, one with a specific gravity of
0*9056 and optical rotation - 34° 18', and another of specific gravity
0*9286 and optical rotation - 63° 18'. These fractions were not further
investigated. The oil was soluble in 6 volumes of 90 per cent, alcohol
«,nd also in 9 volumes of 70 per cent, with slight cloudiness, but did not
become clear on adding an excess of 50 volumes.
l 2
P.andE.O.R. (1920), 286. Jour. Amer. Cham. Soc. (1916), 1398.
294: THE CHEMISTKY OF ESSENTIAL OILS
OIL OF TANSY.
This oil is distilled from the herb Tanacetum vulgare, a native of
England, but cultivated in France, Germany, the United States, etc.
The yield of oil from the fresh herb is about *1 to *2 per cent., and
from the dried herb about twice this quantity. The oil has the following
characters:—
Acid value 0 1
Ester „ 5 16
„ „ (after acetylation) 24 35
English distilled oil is, however, laevo-rotatory, from - 25° - 35°, and
occasionally foreign oils vary outside the above limits, the optical rota-
tion being as low as - 3~, and the refractive index rising to 1*4750.
It is soluble in 4 volumes of 70 per cent, alcohol. The earliest thorough
examination of this oil was made by Bruylants -1 who stated that it con-
tained an aldehyde C10H16O, which he called tanacetylhydrine. Semmler
examined this body and showed that it was a ketone, and renamed it
tanacetone. Wallach has shown, however, that it is identical with that
ketone of thuja oil which he had already named thujone. Schimmel
& Co. showed that the oil contains traces of borneol and some laevo-
camphor, a fact previously indicated by Persoz.2 The English oil, which
is strongly laevo-rotatory, also contains much more camphor than the
ordinary American oil.
OIL OP TANACETUM BALSAMITA.

Tanacetum balsamita yields about *07 per cent, of essential oil. Th&
oil has the following characters:—
On standing in a cold place crystals of a paraffin-like substance were

deposited. The oil is not soluble in twice its volume of 80 per cent,
alcohol, but is in the same quantity of 90 per cent, alcohol. The oil
distilled completely between 207° and 283°, and gave the following
fractions:—
207' to 220° = 10-4 per cent. 240° to 250° = 12'4 per cent.
220° „ 230° = 16-8 „ 250° „ 283° = 28'2 „
230° „ 240° = 18 „ Besidue = 21'2 „
OIL OF TANACETUM BOREALE.

Tanacetum boreale yields about 0*12 per cent, of essential oil. It
Acid value- 30
Ester „ 40
1 2
Berichte, 11 (1878), 449. Oomptes rendus, 13 (1841), 436,
COMPOSITE 295
OILS OF ACHILLEA.
Achillea millefolium is an aromatic plant known as Millfoil whose
leaves yield about 0*2 per cent, of essential oil, of a deep blue colour. It
has been examined by several chemists, the results recorded differing
according to the locality of origin of the plant. The majority of pure
samples have the following characters :—
SieversJ has recorded American oils whose specific gravity varied
from 0-869 to 0*8935.
The oil has recently been very exhaustively investigated by E. E.
Miller.2 A number of samples distilled from the plant grown near
Madison in various stages of development were found to have the
No. Place of Collection. Yield

Condition. Per Specific Gravity Refractive
Index
Cent. at 25°. at 19-6°.
.
1 Sunset Point Dry 0-164 0-902 1-4740
2 Highlands . Fresh 0-212 0-893 1-4718
3 Hammer sley Farm » 0-125 0-9035 1-4885
4 » »» Dry 0-111 0-908 1-4880
5 >i »» Fresh 0-123 0-9038 1-4855
6 »» »» jj 0-111 0-9098 1-4890
7 Piper Farm . — 0-213 0-8966 1-4765
8 Hammersley Farm (Flower
Heads only) Dry 0-85 0-9055 1-4875
9 Hammersley Farm (Stems
and Leaves of No. 8) » 0-067 — 1-4850
10 — —
— —
11 — 0-9087
12 Med. Herb Garden Dry —
— — — —
13 — — —
14 Sheboygan Co. Dry — 0-8926 —
The results of Miller's investigation may be summarised asfol.ows :—

(1) That a blue oil may be obtained from either the leaves or the
flower heads; most oil is obtained from the latter portion of the plant.
(2) That it would not be profitable to distil the lower two-thirds of
the plant.
(3) That the blue compound may be obtained from very young plants,
though in very small amount.
(4) That drying the plant material apparently produces no change in
either the quantity or the quality of the oil.
(5) That the oil contains the following constituents, Z-a-pinene, d-a
pinene, Mimonene, Z-borneol, bornyl acetate and other esters of borneol,
Z-camphor, cineol, salicylic acid, aldehydes, formic, acetic, butyric (?) and
isovaleric acids, a non-volatile acid or lactone, and a blue constituent of
high boiling-point.
Achillea coronopifolia, according to Willdenow, yields an oil of deep
blue colour and specific gravity -924 with a strong odour of tansy.
l
Pharm. Rev., 25 (1907), 215. '2Bull. Univ. Wisconsin, 785.
Achillea moschata yields the so-called Iva oil, having the following
characters:—
Acid value 5 to 21
Ester „ 18 „ 44
,, „ (after acetylation) 91 „ 115
It contains cineol, valeric aldehyde, Z-camphor, palmitic acid, and a body
C24H40O2, termed ivaol by its discoverer Bichenau.1
Achillea iwbilis also yields an essential oil from the leaves. The oil
has been examined by Echfcermayer,2 who found it to have a specific
gravity 0*936, optical rotation - 10° 41', and to contain 18*2 per cent, of
esters. It contains borneol, camphene, formic, acetic, and caproic acids
in the form of esters, traces of an unidentified phenol, and a hydrocarbon
of the formula (C10H16)n.
Achillea ageratum yields an oil of specific gravity 0*856. Its com-
position is unknown.
OIL OF TAGBTBS PATULA.
The flowers of this plant yield about 0*1 per cent, of essential oil
which has been examined by Schimmel & Co.3 It has the following
characters :—
^Refractive index 1-49714
Acid value 2
Ester . 18-7
(after acetylation) 74-3
OIL OF ARNICA.
Both the flowers and the root of Arnica montana yield essential oils,
the former to the extent of about *1 per cent., the latter up to 1 per cent.
The plant is indigenous to Europe, growing upon the Swiss and German
mountains, and the more northern plains. It is also met with in Northern
Asia and the south-western parts of America. The oils have the follow-
ing characters :—
Flower Oil. Root Oil.
Specific gravity . . . 0-899 to 0'913 0'980 to 1-000
Optical rotation . . . — i -f 1° to - 2°
Refractive index . . . — 1-5070 , , 1-5080
Acid value . . . . 60 to 130 4 „ 10
Ester „ . . . . 22 „ 33 60 ,, 100
The chemistry of this oil has been investigated by Sigel 4 and the follow-
ing bodies have been identified : phlorol isobutyric ether C8H8(OC4Hg)2,
thymohydroquinone dimethyl ether C10H12(OCH3)2, and phlorol dimethyl
ether C8H8(OCH3)2. The flower oil is a blue to bluish-green oil when
fresh, turning yellow or brown on keeping. When exposed to cold it
becomes solid or semi-solid, owing to the presence of a paraffin hydro-
carbon. Esters of lauric and palmitic acid are also present. Thes3 oils
are only used to a small extent in medicine.
1 2
Annalen1 155 (1870), 148. Arch, der Pharm., 243 (1905), 238.
3 4
Bericht, October, 1908, 147. Annalen1fl70 (1873), 345.
COMPOSITE 297
OIL OF CARLINA.
This oil is distilled from the root of the thistle Carlina acaulis,
indigenous to Central Europe. The yield is about 1*5 to 2 per cent.
It is a dark-coloured oil of aromatic taste and odour, having the follow-
ing characters :—
Acid value 1. 2 ,, 3
Ester „ 4 „ 5
This oil has often been examined chemically, but a careful inspection
of the figures obtained shows that the results are not reliable.
The oil has been, however, carefully investigated by Semmler.1 It
•contains about 15 per cent, of a monocyclic sesquiterpene, C15H24, boiling
at 140° at 20 mm., and of specific gravity 0*8733 and refractive index
T4920. An oxide, termed " Carlina oxide," C^HÔ, of specific gravity
1*066 and refractive index 1*5860, forms the principal constituent of the
oil. It is a complex furane derivative of the constitution C6H5 . CH : C :
CH. (C4H3O). Semmler has also isolated a sesquiterpene C15H24 which
he terms carlinene, and a crystalline solid body. Traces of palmitic acid
appear to be present.
OIL OF COSTUS BOOT.
The root of Aplotaxis Lappa, a plant indigenous to Eastern India,
yields about 1 per cent, of an oil with a characteristic odour recalling
that of orris or violets. This plant, named as above by Decaisne, is
identical with Aplotaxis auriculata (De Candolle), Aucklandia Costus
{Falconer), and Saussurea lappa (Clarke). It grows at elevations of
7000 to 12,000 ft. on the north-western Himalayas, being found freely
-as far east as Sikkim and as far west as Kashmir and Lahore. The oil
is of a light yellow colour, having the following characters:—
Specific gravity 0-940 to 0-995 (rarely to 1-010)
Acid value 8 „ 25
Ester 55 „ 115
It commences to boil at 275°, and about half distils over below 315°,
when decomposition takes place. On keeping, the oil develops an
unpleasant odour.
The oil has recently been exhaustively examined by Semmler and
Feldstein,2 who carried out their researches on an oil having the follow-
ing characters :—
Boiling-point at 11 mm from 60° to 215°
From the fraction boiling at 200° to 210° at 11 mm. a lactone of the

formula C15H2002 was obtained, which the authors have named costus
lactone. It boils at 205° to 211° at 13 mm., and has a specific gravity
1 2
Chem. Zeit., 13 (1883), 1158. B&richte, 47 (1914), 2433, 2687.
1'0891 at 21°, optical rotation + 28°, and refractive index 1-53043.
Costic acid, C15H22O2, of specific gravity 1-0501, was also found in the
free state. It is an unsaturated bicyclic acid forming a methyl ester
boiling at 170° to 175° at 11 mm. In the fraction boiling at 190° to 200°
at 11 mm. there was found a lactone of the formula C15H22O2, which
has been named dihydro-costus-lactone. A new sesquiterpene alcohol,.
C16H24O, which the authors have named costol, was also isolated. It
forms a phthalic acid ester, from which it can be prepared in the pure
condition. It was then found to have the following characters :—
Boiling point at 11 mm 169° to 171°
Optical rotation +13
By oxidation with chromic acid it yields an aldehyde. By the action of
phosphorus trichloride it yields costyl chloride, which, by the loss of
HC1, is converted into the sesquiterpene isocostene, C15H24. The authors
have also obtained a hydrocarbon of the formula C17H28, to which they
have assigned the name aplotaxene, belonging to the aliphatic series,,
and two sesquiterpenes which they have named a-costene and 6-costene^
which have the following characters :—
a-Costene. /3-Costene.
Boiling-point . . 122° to 126° (12 mm.) 144° to 149° (18 mm.)
Specific gravity . . 0-9014 at 21° 0-8728 at 22°
Rotation . . . - 12° +6°
Refractive index. . 1-49807 1-4905
The approximate composition of the oil is :—
Camphene about -04 per cent,
Phellandrene ,,0-4
Terpene alcohol ,,0-2
a-Costene , 6 - 0
0-Costene 6-0
Aplotaxene 20-0
Oostol . 7-0
Dihydrocostus lactone 15-0
Costus lactone 11-0
Costic acid 14-0
OlLS OF EUPATOBWM.
Dog fennel oil is distilled from the herb Eupatorium foeniculaceum,.
(E. capillifolium), a plant distributed throughout the northern parts of
America. The oil is of a golden yellow colour and pepper-like odour,
Millerl has recently examined a number of samples distilled in Alabama,
the yield of oil being from 0*8 to 1*35 percent. He found eleven samples
of the oil to have the following characters (see next page), the rota-
tion varying considerably according to season.
An oil distilled in Florida has been described, having an optical
rotation of + 17° 50', and containing much phellandrene. Miller's more
recent work makes the authenticity of this sample doubtful. The oil
contains traces of aldehydes and ketones, and, probably, of salicylic acid.
The principal constituent of the oil is the dimethyl ether of thymo-
hydroquinone. Phellandrene, borneol, bornyl acetate, linalol and
sabinene (?) are present in the oil.
Eupatorium triplinerve, a plant indigenous to tropical America, and
i
Bull. University of Wisconsin, 693 (1914), 7.
Yield Specific Gravity, Saponification Saponification Per Cent, of Thymo-
When Distilled. 25° «D for 100 Per Cent. No after Acid hydroquinone
Per Cent. "Dô. mm. Tube. OCH3. No. No.
25°* Acetylating. Dimethyl Ether.
1 1 May, 1912 0-36 0-93919 1-504479 + 10*27 18-42 5-6 12-94 0-207 57-63
2 13 „ 0-47 0-9326 1-502330 + 7-47 16-87 6-4 13-26 0-206 52-78

3 25 ,, ,, 0-51 0-92378 1-500732 -f 13-82 15-92 5-88 10-61 49-81 o
— o
4 27 June, ,, 0-527 0-91950 1-497808 + 14-29 14-79 9-45 43-72 — 46-02
_
5 30 July, „ 0-567 0-9269 1-49875 + 10-02 16-20 16-68 56-85 50-91
6 8 Sept., 1911 •0960 0-9278 1-499886 - 6-33 — 13-67 — 0-18 ! 52-13
7 13 „ „ 0-99 0-9346 1-501014 - 8-20 16-66 12-26 23-35 — —
8 27 Oct., „ 1-02 0-9472 1-505866 - 13-99 20-16 — — 0-25 63-08
9 16 Nov., ,, 1-11 0-9505 1-506143 - 11-77 20-61 10-53 — 0-10 64-49
10 23 „ 1-03 0-9577 1-506887 - 11-73 21-45 14-43 30-95 — 67-11
11 3 Dec., 1912 0-613 0-96004 1-506422 - 16-70 21-24 10-60 23-83 — 66-46
found wild in other tropical and subtropical countries, yields an essential
According to Semmler,1 the oil contains a sesquiterpene, and the di-
methyl ether of thymohydroquinone. Traces of coumarin are also
present.
OlLS OF SOLIDAGO.
Various species of Solidago yield essential oils, of which the best

known is the " golden rod oil," which is obtained to the extent of about
1 per cent, from Solidago odora, a plant very common in the United
States, east of the Eocky Mountains. The oil has the following
characters :—
According to Miller and Moseley,2 the oil contains about 76 per cent,
of methyl-chavicol. Traces of pinene are possibly present, but this is
doubtful. Borneol is present in small quantity.
Canadian golden rod oil is obtained from Solidago canadensis. It is
a, yellow oil of aromatic odour, of specific gravity 0*859 and optical rota-
tion - 11° 10'. It consists of about 85 per cent, of terpenes, of which
pinene, phellandrene, dipentene, and probably limonene are the con-
stituents. There are also present borneol, bornyl acetate, and cadinene.
Solidago nemoralis is a plant which grows from Quebec to the North-
West Territory, south to Florida and west to Texas and Arizona. A
sample of the oil obtained from this species was examined by Schimmel
& Co.3 It was bright olive-green in colour, and had a peculiar odour,
reminding somewhat of cypress oil. It had a specific gravity 0'8799,
optical rotation - 23° 10', ester number 14'4, ester number after acety-
lation 38*2, and formed a cloudy solution in about seven or more volumes
of 95 per cent, alcohol.
An average of ten samples examined by Miller and Eskew 4 had the
.following characters :—
2*>°
Specific gravity -^0 0»858
„ ,, (after acetylation) . . . . 9-4
It is soluble in about 4 volumes of 90 per cent, alcohol, and in about
24 volumes of 70 per cent, alcohol. On fractionation the oil yielded
/?-pinene and traces of salicylic and acetic acids. The presence of
borneol was considered probable, but no definite proof was obtained.
Phellandrene was not present, and no reactions were obtained for
aldehydes or ketones, phenols or camphor. The chief constituent is
pinene, a mixture of the dextro- and laevo-rotatory varieties.
l 2
9
Berichte, 41 (1908), 509. 4
Ibid. Jour. Amer. Chem. Soc. (1914), 2538.
COMPOSITE 301
Solidago rugosa yields 0*5 per cent, of an oil of the following
characters :—
9 co
Specific gravity fjl 0*862
Jio^
„ „ (after acetylation) . . . . . 11
It contains pinene and limonene.
Solidago Caroliniana yields an oil which has been examined by
Eussell.1 The fresh herb, gathered before flowering, yielded 0*693 per
cent, of oil having the following characters :—
Ester value 6-35
It consists mainly of dipentene. It also contains pinene, limonene, an
aldehyde in traces, and acetic and formic acids in the form of esters.
OIL OF BLUMEA BALSAMIFEBA.

Bltimea Lasamifera is a plant indigenous to India, and is also found
freely in the Malay Archipelago. The essential oil has been examined
by Jonas, 2who found it to have the following characters :—
Acid value 23-4
Ester „ 1
He has identified the following compounds in the oil: cineol,
limonene, palmitic and myristic acid in traces, 5 per cent, of a phenol
not definitely identified, Z-borneol, Z-camphor, and a sesquiterpene and a
sesquiterpene alcohol. The phenolic body present is probably phloro-
glucintrimethyl ether.
OIL OF PLUCHEA FOETIDA.
The fresh herb, Pluchea foetida, which is common in the southern
parts of the United States, yields 0'025 per cent, of an essential oil,
which has been examined by Eabak 3 and found to have the following
characters :—
Optical rotation - 10'8*
Acid value . . . . . . . . . . . 4*1
Ester „ 44
,, „ (after acetylation) 104
It contains cineol.
1
2
Jour. Am&r. Chem. Soc., 38 (1916), 1398.
3
Schimmel's Bericht, April, 1909, 149.
Mid. Drug, and Ph. Rev., 45 (1911), 485.
OIL OF AGEBATUM OONYZOIDBS.
According to Murat, this member of the Composite abounds in
Annam to an extent which makes it a plague to the cultivators. Dis-
tillation takes place at the beginning of February or March; 500 kilos
of this plant yielded only 27 grams of essential oil; the yield, a very
small one, is therefore 0*0054: per cent.
The oil of Ageratum conyzoides from Annam possesses the following
properties :—
Acid No 0*9
Saponification No 12*1
Ester No 11-2
OIL OF HELICHRYSUM ANGKJSTIFOLIUM.

Helichrysum angustifolium yields about 0'08 per cent, of essential
•oil having the following characters :—
Acid value up „ 15
Ester 39 „ 134
(after acetylation) very variable
OIL OF PABTHENIUM.
Parthenium argentatum yields 0*5 per cent, of essential oil which
has been examined by Alexander, who considers that a higher yield
would be obtained if a suitable distilling apparatus were available. The
plant is a native of Mexico, and the oil is of a faint greenish-yellow
colour, slightly laevo-rotatory, and of specific gravity 0*886. On fractional
distillation it behaved as follows :—
67 c.c. distilled at 17 mm. pressure
From 50° to 60° 17 c.c.
„ 60° „ 80° 20-3 „
„ 120° „ 160° 24-8 „
Residue . . . . . . . . . . . 5*5 „
The oil contains Z-a-pinene, and a sesquiterpene (?) of specific gravity
<0-9349, specific rotation - 21° 24', and refractive index 1-4960 at 16°.
OIL OF FLEABANE.
This oil, also known as erigeron oil, is distilled from the fresh-
flowering herb, Erigeron canadensis, a plant widely distributed through
North America, and known locally as horseweed, fleabane, butterweed,
Bolt's tail, etc. Only about 0*5 per cent, of oil is obtained, of a light
yellow colour and aromatic odour. The oil has the following char-
acters :—
Ester „ 34 „ 109
COMPOSITE 303
The known constituents of the oil are the terpene, limonene, terpineol,
and traces of citronellal.
OIL OF ELECAMPANE.
This oil is distilled from the roots of Inula helenium, a plant indi-
genous to Southern Asia and Siberia, and found to a fair extent in
Southern Europe and North America. The oil has the following
characters :—
Optical rotation + 120 to + 123° 45'
Refractive index . . . . . . . 1*5220
Acid value 6 to 8
Ester „ 160 „ 180
,, „ (after acetylation) . . . . 186 ,, 199
The oil is semi-solid, owing to the deposition of crystals of alantolactone,
the above specific gravities being those taken in the superfused condi-
tion. The principal constituent of the oil is alantolactone, with small
quantities of alantic acid, alantol, and helenin (which is probably identical
OH
/
with isoalantolactone). Alantie acid has the formula CUH20 , and
COOH
alantol is isomeric with camphor C10H16O.
OIL OF CHRYSANTHEMUM JAPONICUM.
The leaves and flowers of this plant yield an essential oil which is
known in Japan as kiku oil. It has a specific1 gravity about 0*885 and
boils at 165° to 175°. According to Perrier, the green leaves of the
plant yield an oil of specific gravity 0*932 and refractive index 1*4931.
It contains a paraffin hydrocarbon, and probably angelic acid in the
form of esters.
OIL OP CHRYSANTHEMUM CINBRARIÊFOLIUM.
The flowers of this plant, growing largely in Dalmatia and Monten-
egro, and which, when ground, form the insect powder of commerce,
yield about 0 07 per cent, of essential oil. According to Siedler,2 it con-
tains a paraffin C14H30 melting at 54° to 56° and a substance melting at
62°, probably palmitic acid. It also contains a phenol, and probably
butyric acid.
OIL OP CHRYSANTHEMUM MARGINATUM.
Shinosaki3 has obtained 0*005 per cent, of a greenish blue essential
oil by distilling this plant. The oil has the following characters :—
Optical rotation - 46'58°
Refractive index 1*5020 at 20°
„ „ (after acetylation) . . . . 63-1
1
Butt. Soc. Chim., iii. 23 (1900), 216.
*Ber. d. deutsch. Pharm. Ges., 25 (1915), 297.
*J. Chem. Ind. Tokyo (1919), 22, 455.
Besides esters and alcohols, a small quantity of aldehyde or ketone,
which yields a crystalline compound with sodium bisulphite, is present
in the oil.
OIL OF SANTOLINA.
The herb Santolina Chamcecyparissus, indigenous to Southern
Europe, yields about O5 per cent, of essential oil, which has been in-
vestigated by Francesconi, Scaraffia, and Granata.1
,, rotation - 11-74° at 25°
A sample examined by Schimmel & Co. had the following values :—

Acid value G-G
Ester „ 1G-4
,, , , (after acetylation) . . . . . . . 74'2
A terpene is present in the oil, and two isomeric ketones, which

have been named a-santolinenone and /3-santolinenone, of the formula
C10H16O, both of which are unsaturated. A saturated ketone of the
camphor type of the same formula is also present, a-santolinenone
appears to be an optically inactive, racemic ketone, and /3-santolinenone
is also optically inactive, and probably racemic.
/2-Santolinenone yields a liquid oxime and a crystalline compound
with hydroxylamine melting at 63° to 64°. This compound is obtained by
allowing a solution of hydroxylamine hydrochloride to react with an
ether-alcoholic solution of the oil with the addition of sodium bicarbonate.
UMBELL1FER/E,
OIL OF ANISEED.
On account of the great similarity of the oil distilled from Pin^pinella
Anisum, with the star aniseed oil, which constitutes the greater part of
the aniseed oil of commerce, this oil will be described, together with the
latter, as one of the Magnoliacese (q.v.).
OIL OF CARAWAY.
This oil is distilled from the seed of Car am carui, a plant inhabiting
the low-lying lands in many parts of Northern and Central Europe. It
is cultivated in England, Germany, Holland, Prussia, Morocco, etc. The
Dutch fruit is esteemed very highly, and the oil obtained from it is worth
more than that obtained from any other, except English, which, how-
ever, is a matter of local sentiment. Schimmel & Co. give the following
as the average yields obtained from various fruits :—
]
Gazz. Chim. Hal, 44 (1914), ii. 150, 354, 46 (1916), ii, 251.
UMBELLIFEEÊ 305»
Bavaria, wild 6-5 to 7 per cent.
Finnish 5 to 6
Hessian, wild 6„7
Moravian, cultivated 4
East Frisian 5-5 to 6
Russian, wild 3*2 „ 3-6
Styrian 6
Wurtemburg 5-5 to 6
German, cultivated 3*5 ,, 5
Galician . . . . . . . . . . 4-5
Dutch, cultivated 4 to 6'5
Norwegian, wild 5 ,, 6-5
East Prussian, cultivated 5 ,, 5-5
Swedish, wild 4 „ 6'5
Tyrolese . . . . . . . . . 6*5
Caraway oil has the following characters :—
Specific gravity 0-910 to 0-918 (rarely 0-907>
Optical rotation + 70° to -f 82° 30'
As caraway oil consists almost entirely of carvone, of specific gravity
0*964, and limonene of specific gravity 0*850, the amount of carvone
present can be very approximately deduced from the specific gravity of
the sample.
Various direct methods of determining the carvone have been pro-
posed, based on the preparation of crystalline compounds of this body.
The oxime, the sulphuretted hydrogen compound, and the phenylhydra-
zone have been employed, but only approximate results can be obtained
in all these cases. The following are the details recommended in the
case of the phenylhydrazone :—
When 5 c.c. phenylhydrazine are added to 5 c.c. of caraway oil the
mixture becomes warm owing to chemical combination taking place, and
if the action be accelerated by placing the test tube in boiling water for
a few minutes a copious crystallisation of carvone phenylhydrazone,
C10H14 : N . NH . C6H5, appears, and on cooling the whole solidifies to
a crystalline mass. After heating for one hour the reaction is complete,.
the excess of phenylhydrazine is removed by adding 5 c.c. glacial acetic
acid whilst hot, shaking, and diluting with 20 c.c. water. The contents,
of the test tube are then cooled and filtered through a paper disc by1
means of a pump, and the crystalline mass washed with water until
of a pale yellow colour. By this process not only is the excess of phenyl-
hydrazine removed in aqueous solution as acetate, but nearly all the oily
terpene adherent to the crystals is washed away. On crystallising from
a definite volume of 95 per cent, alcohol the carvone phenylhydrazone is
obtained in long silky pale yellow needles, melting at 106° C., but so-
difficult to dry without decomposition as to render the determination
only approximate.
The sodium sulphite process yields good results. On fractional dis-
tillation not more than 25 per cent, should distil below 185° and at least
55 per cent, to 65 per cent, should distil over 200°, a considerable frac-
tion—40 per cent, to 50 per cent.—being obtained from 220° to 230°.
The valuable constituent of this oil is the carvone, and on this
account, and as it is easy to separate this body in a fairly pure state,
carvone is often used in place of the oil, and is official in the German
Pharmacopoeia. The result is that there is much de-carvonised oil on
VOL. i. 20
the market to be disposed of. A portion of the carvone is abstracted by
fractional distillation, and the misleading name " rectified caraway oil "
often given to the remaining oil, which frequently has a specific gravity
of *890 to '900 and a correspondingly high rotation. When all the car-
vone is abstracted the resulting " carvene " as it is called—in reality
almost pure limonene, with traces of carvone—is sold as " light" oil of
caraway. It is used for perfuming cheap soaps, but it is false economy,
as the same value in pure oil or in carvone has a far higher odour value,
and is cheaper in the end. " Carvene " is comparable to " citrene," the
waste terpenes obtained in preparing terpeneless oil of lemons, and
"auranciene," the corresponding terpenes from orange oil. They are
all practically useless for perfumery purposes, and are either sold under
misleading names or used to adulterate the respective oils from which
they have been obtained. There is also an oil known as caraway chaff
oil, which appears to be distilled from a mixture of the herb itself, and
the chaff obtained on threshing the seeds. "Light" caraway oil ex-
amined by the author had a specific gravity *848 and an optical rotation
4- 103°. Umney gives a sample of "light" caraway or "chaff "oil as
having a specific gravity *8482 and an optical rotation of — 58*5°. At-
tempting to determine the question as to when the carvone was formed
in the plant, Schimmel & Co. distilled the samples described below,
grown by them on their Miltitz fields :—
No. 1 from fresh long-cut, blooming plants with partly ripening
fruits.
No. 2 from fresh plants cut at the same time and in the same way,
from which, however, the umbels bearing both flowers and ripening
fruits had been removed, so that the stalks and the leaves alone were
distilled.
No. 3 from plants in a more advanced stage of ripening, and after
the time of blooming, but before the full ripening of the fruits.
The following were the physical constants of the oils obtained :—
Specific Gravity. Refractive Index. Optical Rotation.
Uo. 1 0-882 1-48306 + 65° 12'
.,, 2 about 0-880 1-5083 + 20° 36'
„ 3 0-9154 1-48825 + 63° 6'
The odour of oil No. 2 hardly resembled that of caraway seeds, nor
did it contain either limonene or carvone, the characteristic constituents
of caraway oil, in any perceptible quantity. The small sample was just
sufficient for ascertaining the boiling-point; it began to boil at 195° C.,
the thermometer then rapidly rose to 230° C., and between 230° and 270°
about 65 to 70 per cent, distilled over; the residue was resinified.
Sample No. 1 evidently contained much more terpene and less
carvone than sample No. 3. Hence it is possible that the latter results
from the oxidation of the former during the ripening of the plant. A
body of high boiling-point, not yet identified, was detected in small
quantity in each of these oils\
The constituents recognised in caraway oil are carvone, d-limonene,
dihydrocarvone, carveol, and dihydrocarveol, and a base having a
narcotic odour which has not been investigated.
OIL OF CORIANDER.
This oil is distilled from the fruit of Coriandriim sativuni, a native
of the Levant and Southern Europe, cultivated in many places all over
UMBELLIFEKÊ 307
the world. The average yield from various fruits is given by Schimmel
& Co. as follows :—
French , •4 per cent. Dutch . •6 per cent.
Italian , •5 .„ Moravian '8 „
Morocco , •2 to -3 per cent. East Indian •15 to -2 per cent.
Russian . •8 >f -1 Thuringian •6 „ -8 „
Thuringia and Eussia have, of late, been the most important pro-
ducers, the crops from these districts sometimes reaching as high a
figure as 450 tons. The oil has an intense odour of the seeds, which is
much impaired if immature fruits have been used in the distillation.
This is explained by the following experiment undertaken by Schimmel
& Co. A portion of a crop was gathered in the early summer, whilst
the herb was in early flower, and the whole herb distilled. Five weeks
later, when half ripe and just starting to seed, another portion was
gathered and distilled. In another month, the fully ripe fruit of a
third portion was distilled. The result of the examination of the oils
obtained is given below in Schimmel & Co.'s own language:—
" 1. Oil from the entire Flowering Plant in the Green State.—Yield
0*12 per cent. Specific gravity 0*853. Insoluble in 70 per cent, alcohol.
Extremely objectionable, bug-like odour. After 2£ months the specific
gravity of the oil had increased to 0*856. The optical rotation (which
had not been determined immediately after distillation) was then
+ 1° 2' in a 100 mm. tube at 18° C. The bug-odour had disappeared
almost entirely. It would therefore seem that in the meantime the
carrier of the odoriferous principle had become polymerised or other-
wise transformed.
" 2. Oil from Green Half-ripe Coriander Herb, with Fruit.—Yield
0-17 per cent. Specific gravity 0*866. Optical rotation + 7° 10' at 18°.
Soluble in three parts of 70 per cent, alcohol. Odour resembling that
of coriander, with a subsidiary odour reminding of bugs. After one
month the specific gravity had increased to 0*869.
" 3. Oil from Ripe Coriander Fruit, distilled immediately after har-
vesting.—Yield 0*83 per cent. Specific gravity 0*876. Optical rotation
-h 10° 48' at 16°. Soluble in three parts of 70 per cent, alcohol. Pure
coriander odour."
Pure coriander oil has the following characters :—
Refractive index 1-4635 „ 1*4760
Acid value . . . . . . . . . 1 , ,5
Ester „ 3 „ 22
On fractional distillation from 45 to 55 per cent, is obtained between
190° and 200°, indicating a due proportion of coriandrol.
The oil is sometimes adulterated with orange oil, which causes a
lowering of the specific gravity and a considerable rise in the optical
rotation, It also interferes with the solubility in 70 per cent, alcohol.
Cedar-wood oil and turpentine have also been met with as adulterants.
Semmler1 isolated the characteristic component of this oil, which
he termed coriandrol, an alcohol of the formula C10H17OH. Barbier2
has, however, shown that this is identical with dextro-lm&lol. The
only other known constituent of the oil is pinene.
2
*Berichte, 24(1891), 206. Comptes rendus, 116 , 1459.
According to Walbaum, the oil contains about 50 per cent, of linalol,.
but his results were obtained by a direct acetylation. If the method of
Boulez be used, which is necessary in the case of linalol, from 65 to 70
per cent, of linalol is indicated. Dextro-a-pineue, i-a-pinene, /2-pinene,
dipentene, cymene, terpinene, ger-aniol, borneol, acetic esters, and decyl
aldehyde are also present in the oil, with, possibly, phellandrene and
terpinolene.
OIL OP DILL.
Dill OH, is obtained by the distillation of the fruit of Anethum grav-
eolens Linnasus (Peticedanum graveolens Bentham). It is indigenous,
to Central and Southern Europe, but is found in many other localities,
such as the Caucasus, Persia, and the north-east of Africa and India.
Slight botanical differences exist between the European plant and that
grown in India, so that the latter has been described as a distinct
species (Anethum Sowa). A difference of opinion exists as to whether
this distinction is justifiable, but the oils obtained from the two plants
are certainly not identical. The yield of oil obtained from the seeds is
about 3 to 4 per cent.
European dill oil is a pale yellow liquid having the following char-
acters :—
Specific gravity . . . 0*895 to 0'918 (rarely below 0-903)
Optical rotation . + 70° to + 82°
Refractive index . . 1-4830 „ 1-4900
Carvone . . . . 30 to 60 per cent, (by the sulphite method)
The oil is soluble in from 4 to 9 volumes of 80 per cent, alcohol.
In spite of the difference in odour between this and caraway oils,
the composition of the two is almost identical, both consisting nearly
entirely of limonene and carvone. Dill oil, however, contains less car-
vone than caraway oil. Hence the tests given under caraway oil apply
here, and stress should be laid on the specific gravity, optical rotation,
and fractionation. Not more than 15 per cent, should distil below 185°,
and not less than 40 per cent, above 220°. English distilled oils usually
have the highest specific gravity, from "910 to -916, and are conse-
quently held in the highest esteem. The following are the average
fractions obtained from English and German oils :—
English. German.
Below 185° . 10 per cent. 10 per cent.
185° to 200° 20 „ 22 ,,
200° „ 220C 20 „ 22
220° ,, 230° 48 „ 42
Above 230° . 2 4
East Indian dill has a much higher specific gravity than European
oil, this figure usually varying from -945 to *970. Its rotation is from
+ 40° to + 50°. This high specific gravity is in all probability due to
the presence of dill apiol, a body isomeric with ordinary parsley apiol,.
discovered by Ciamician and Silber. Indian oil contains much less
carvone than European oil, as does the Japanese oil, which also pos-
sesses a high specific gravity and appears to be nearly identical with
Indian oil. A sample of Japanese oil examined by Umney was found
to have a specific gravity 0'964 and optical rotation + 50° 30'. The
optical rotation of both varies from + 40° to + 50°. Spanish oil is.
UMBELLIFEE.ZB 309
distilled from the herb, with or without the unripe fruits. It has a
specific gravity 0-905 to 0'935, optical rotation + 37° to + 60° and
refractive index 1-4910 to 1-4970. It does not contain more than 20
per cent, of carvone. Schimmel & Co. have found a large amount of
phellandrene in a sample of English, and also in Spanish oil. Apart
from this, the only known constituents are limonene and carvone, with
traces of a solid body, possibly a paraffin hydrocarbon, and, in Indian
oil, dill apiol C12Ht4O4. Spanish oil contains phellandrene, carvone,
iimonene, dill apiol, and dill isoapiol. Pure dill oil is used to a con-
siderable extent in pharmacy as a carminative.
African dill oil has recently been examined by J. C. Umney.1
The African fruits are slightly larger than the English fruits,^ and
a little paler in colour. Their odour closely resembles the English.
They are produced from plants grown from English imported seed,
whilst the Indian variety has been ascribed by some to a different
species, Anethum sowa, which is also the source of the Japanese dill.
The yield to ether of these fruits was 11'6 per cent., comparing
very closely therefore with English fruits, which yielded 10'9 per cent,
to ether.
The essential oil had the following characters, and contained no
fraction heavier than water :—
Optical rotation at 20° C + 77° 3'
Solubility in 80 per cent, alcohol . . . . 1 in 6 to 1 in 6£
As a general rule it is found that the yield of essential oil from
umbelliferous fruits is higher in temperate climates, as for example
from fennel, the Galician and Eoumanian varieties of which yield as
much as 4 per cent, of oil against 0*75 per cent, from the East Indian
fruits, but in this case the difference is not so marked.
If the fruits can be produced in quantity in Cape Colony, they
should form a most useful source of supply.
OIL OF FENNEL.
This oil is distilled from the fruit of several varieties of Foeniculum
vulgare, which is found all over Europe except in the north and north-
east, being especially common on the Mediterranean littoral, and is also
found in Asia Minor, Persia, India, and Japan. Two oils are recognised
in commerce, the " sweet" and <; bitter" oils, the former being more
esteemed. The sweet fennel is distilled from Foeniculum dulce, but
this is probably only a variety of the common wild fennel. The yield
of oil obtained is very variable, according to the fruit distilled. In
general it averages from 4 to 6 per cent. In the ordinary way, Galicia
and Roumania furnish some of the best fennel crops, and from their
fruit a large portion of the oil of commerce is distilled. The great
variability in the fruits of different districts makes it necessary to fix
some limits for the physical characters of the oil, which, however, may
be exceeded in individual cases.
Ordinary sweet fennel oil has the following characters :—
Optical rotation + 6° to + 20° (rarely to + 26°)
Congealing-point + 3° ,, + 10°
1
P. and E.O.R. (1910), 290.
The principal constituent of the oil is anethol, and the oil also con-
tains fenchone, a-phellandrene, dipentene, camphene, d-pinene, and
methyl-chavicol. As anethol is the principal constituent of fennel oil,
the congealing-point may be regarded as a fair criterion of the value.
A good oil will contain as much as 60 per cent, of anethol. If
necessary the crystalline stearoptene may be separated and examined,
but as a rule added solid bodies will alter the other characters of the
oil. The oil is soluble in an equal volume of 90 per cent, alcohol.
The above tests will guard against the abstraction of anethol, or the
addition of the residue of oil from which this body has been abstracted.
One observer gives as the specific gravity and optical rotation of
the oil distilled from French bitter fennel, -910 to -955 and + 22° to-
+ 48° respectively. Tardy,1 however, has examined a sample of this oil,
and states that its specific gravity is 1*007 at 0°, and its optical rotation
+ 18° 20'. In the oil he found pinene, dipentene, cymene, phellan-
drene (?), d-fenchone, methyl-chavicol, and anethol, together with
anise aldehyde and anisic acid, and a ketone of the constitution
OCH3
C6H /
\CH 2 . CO . CH3
Schimmel & Co. have examined a sample of Japanese oil, and give the
specific gravity as *9754, and the optical rotation as 4- 10° 3'. Umney
gives *9754 and + 15° 5' for a sample of the same oil. He found 10'2
per cent, of fenchone in the oil.
Foeniculum piperitum yields an oil (Sicilian fennel oil) of specific
gravity about '950. Spanish fennel oils, when pure, do not differ materi-
ally from other genuine sweet and bitter fennel oils. But much of the
commercial Spanish oil is a mixture distilled from the so-called wild, and
other fennel species.
The sweet Eoman fennel, as it is termed, usually contains much
anethol and little or no fenchone. It has the following characters :—
Optical rotation . . + 5° to + 16° 30'
Congealing-point 10° to 14-5°
Macedonian fennel yields a very similar oil. Wild bitter fennel,
growing in France, Spain, and Algeria, yields an oil of specific gravity
0-905 to 0'925 and an optical rotation up to -f 50°. It is practically
free from anethol. Indian fennel oil has a specific gravity '970 and an
optical rotation +21°.
Tardy has examined an Algerian oil of specific gravity 0*991 and
optical rotation + 62°. He found present: pinene, phellandrene,
fenchone, methyl-chavicol, anethol, a sesquiterpene, and a little thymo-
hydroquinone. Schimmel & Co. find camphene in fennel oil, but are
not able to confirm the presence of cymene. Traces of basic com-
pounds were also detected.
Wild bitter fennel oil differs considerably from the above-described
oils. Its specific gravity varies from 0%£05 to 0*925, and optical rota-
tion + 40° to 4- 65°. Anethol is present only in traces, but a fair
amount of phellandrene is present. Tardy isolated from this oil a
crystalline compound melting at 213°, which is possibly di-para-
1
Bull. Soc. Chim., xvii., 660.
UMBELLIFEEÊ 311
methoxystilbene. A crystalline substance melting at 164° to 165° is
also present in the oil.
Water fennel oil is obtained from the fruit of Oenanthe Phellan-
drium, the fruit of which yields about 2 per cent, of oil. The oil has
Optical rotation -f 12° „ + 20°
Refractive index 1-4840 ,, 1-495O
The oil contains pinene, sabinene, and ^&ztfro-/?-phellandrene.
Schimmel & Co. have also isolated an alcohol which they termed
androl, and which has the following characters :—
Optical rotation . . - 7° 10'
Boiling-point . 197° to 198°
It forms a phenyl-urethane melting at 42° to 43°. Its formula is
C10H20O. They have also isolated an aldehyde, which they named
phellandral, and which is, chemically, a tetrahydrocumic aldehyde of
the constitution
CH.(C 3 H 7 )
H2C
H 9 C,
C . COH
OIL OF CUMIN.
Cumin Oil or Cummin Oil is obtained from the fruit of Cuminum
cyminum, a native of Upper Egypt and Ethiopia, but cultivated in
Arabia, India, China, Malta, Sicily, etc. The bulk of the supply of
commerce is obtained from Sicily, Malta, Mogador, and India. The
yield is from 2*5 per cent, to 4 per cent, of a light yellow oil having
Oil distilled from Cyprus seeds,1 however, was found to have the
Refractive index 1*5100 to 1-5140 at 23°
Aldehydes 47 „ 52 per cent.
Distillates of high gravity dissolve in 3 volumes of 80 per cent,
alcohol, but low gravity oils require 8 to 10 volumes. The oil contains
from 25 to 35 per cent, of aldehydes. Wolpian 2 states that he has
obtained from cumin oil a fraction boiling at 157° to 158°, which was a
terpene which he could not identify with any known terpene. How-
ever, it is doubtful whether he obtained it in a state of purity, and the
proposed name hydrocuminene appears rather premature, as no de-
rivatives were prepared.
1
2
Bull. Imp. Inst., July-September, 1917.
Pharm. Zeit. filr Russland, 1896, p. 97.
The oil has been exhaustively examined by Schimmel & Co.1
After repeated fractionation they succeeded in obtaining 11 grms. of a
body with boiling-point 158° to 168° and an odour of pinene. Treated
with nitrosylchloride a very small quantity of a nitrosochloride was
obtained, of which the benzylamine-combination melted at 120° to 123°.
The presence of a-pinene could be more readily proved by oxidation
into active d-pinonic acid. The acid melted at 68° to 69° and was
identical with d-pinonic acid from Greek oil of turpentine. It follows
that the oil contains i- and d-a-pinene.
The fractions with higher boiling-point contained, besides j9-cymene,
small quantities of terpene hydrocarbons. j0-Cymene was identified by
oxidising with permanganate (hydroxy-^sopropyl benzoic acid, melting-
point 155° to 156°). When the cymene fraction was oxidised it yielded
a small proportion of sodium nopinate. The free nopinic acid melted
at 125° to 126° and was laevo-rotatory. On oxidation with perman-
ganate it yielded nopinone, of which the semicarbazone melted at 187°
to 188°, thus proving the presence of /?-pinene. Wolpian, who had
isolated considerable proportions of hydrocuminene from the oil, was
probably dealing with a sample which was adulterated with turpentine
oil, and his hydrocuminene was certainly only a mixture of a-pinene,
/?-pinene, and ^-cymene,
Although it was the fraction boiling at 178° which showed the
smallest rotation (ao 4- 0° 35'), it absorbed about 10 per cent, of
bromine. With hydrochloric acid it yielded a solid dihydrochloride,
melting at 48°, which, when mixed with dipentene dihydrochloride,
suffered no reduction of the melting-point. From the same fraction a
nitrosochloride was also obtained, but only in very small quantities
and only separated out in the solid form upon the addition of water,
alcohol, and ether. These facts point to the presence of dipentene.
The presence of terpinene could not be proved. No fraction gave
the nitrite reaction, and any considerable quantity of phellandrene is
therefore out of the question. The results of the oxidation with per-
manganate indicate the presence of /3-phellandrene, which proves that
when small quantities of phellandrene are present, identification by the
nitrite reaction is very often a failure.
A small quantity of a-terpineol was isolated, together with a small
amount of cuminic alcohol.
The bisulphite compound, after being purified by washing with
alcohol and ether, was decomposed by boiling it with soda solution
and then distilled by steam. Its constants were as follows: boiling-
point 97° to 99° (7 mm.); d^ 0-9731; aD + 0° 3'. When oxidised with
chromic acid the aldehyde was converted into cuminic acid, melting-
point 113° to 114°. The melting-point of the semicarbazone was 210°
to 211°, of the oxime, 55° to 57°. Cuminic aldehyde (cuminol) which
has long been known as forming the principal constituent of oil of
-cumin, was thus isolated in a state of great purity. It caused some
surprise, however, to find the first fraction of the aldehyde showing a
slight rotation to the right (OLD + 1° 13'), but oxidation always gave
only cuminic acid. In the course of fractional crystallisation of the
semicarbazone they succeeded in obtaining, in addition to cuminic
aldehyde semicarbazone, crystallising in flakelets (melting-point 210°
1
Report, October, 1909, 49.
UMBELLIFEE^ 313
to 211°), another body, melting-point 200° to 201°, crystallising in thin
prisms. This latter semi-carbazone was not found in the other frac-
tions. Further examination failed to confirm the surmise that the two
•semicarbazones of cuminic aldehyde contained cis- and tfrans-modifica-
tions. When oxidised with chromic acid, the aldehyde forming the
basis of the semicarbazone of the melting-point 200° to 201° was also
converted into cuminic acid. The oxime of the aldehyde had a melt-
ing-point 72° to 76° (impure). It is therefore probable that, in addition
to the cuminic aldehyde, tnere is present, in small proportions, a hydro-
genated cuminic aldehyde.
A Persian cummin seed has recently been found on the London
market. This has been examined by Holmes,1 who reported as follows
on the seed:—
" The appearance of a fruit under this name on the London market is
of considerable interest, inasmuch as its botanical source has never been
identified with certainty, and so far as I am aware there is no authenti-
cated specimen of the Persian plant yielding it in any European Herbar-
ium. This fruit has been in the museum of the Pharmaceutical Society
in London for at least thirty years under the name of Carum nigrum.
"The botanical and indeed the geographical source of Persian
'Cummin, which is distinguished at Bombay as * Zeerah Shiah,' i.e. black
•cummin (in contra-distinction from ' Zeerah Suffed,' i.e. white cummin,
the name applied to the cummin fruit, Cuminum cyminum, used in
Europe), is at present not clearly determined, since there are ap-
parently two or three different, but closely allied, fruits having the
cummin flavour, and collected apparently in widely different districts
in or about the 30th parallel of N. latitude, and all bearing the name of
'black cummin.
" The Persian cummin is believed to have come from Mohammerah,
inear the north-west coast of the Persian Gulf, in the Province of
Khuzistan, but of the plant that yields it nothing is known. The
fruit, however, agrees in structure with a fruit from Kunawar, in the
north-east of the Punjab, which is stated by Dr. Koyle (Illustrations of
Himalayan Botany, p. 229) to be collected there under the name of
* Zeerah Shiah/ or black cummin, and he suggests the name of Carum
nigrum for the plant, but gives no description of it. He evidently sent
the plant, however, to Dr. Lindley, who was at that time professor of
botany at the London University, since in the Lindley Herbarium,
which is now in the Botanical Museum of Cambridge University, a
specimen of a Carum received from Dr. Eoyle, occurs, which is named
Carum gracile Lindl. This name, with Lindley's description, occurs
on page 232 of the same work without any reference to Koyle's Carum
nigrum, so that it is evident that Dr. Eoyle sent it to Dr. Lindley un-
named, and Lindley's name for the plant must therefore supersede Dr.
Boyle's Carum nigrum."
The yield of oil from the seeds was 2 per cent., and it has been
êxamined by Umney 2 who found it to have the following characters :—
Persian Cummin Oil.
Yield . 2 p e r cent.
Specific gravity •911
Optical rotation . . . + 7°
Aldehydes by absorption with sodium bisulphite 18 per cent.
1 2
P. and E.O.R. (1913), ±3. Ibid.
Fractionation—
Below 180 2 per <sent-
185 24
190 36
195 - 46
200 50
205 56
210 58
215 63
220 66
225 70
230 76
235 . 86
240 practical] yall
The odour is distinctly sweeter than the normal cummin oil and a>
little more reminiscent of caraway, although, from the figures above
indicated, it does not seem to contain a higher percentage of cumic.
aldehyde. Carvone does not appear to be present. •
OIL OF LOVAGE.
Oil of lovage is obtained by distilling the roots of Levisticum offi-
cinale with steam, the yield being under 1 per cent. The oil is a
somewhat dark brown viscous liquid having an odour of angelica, and
possessing the following characters :—
It is soluble in 3 volumes of 80 per cent, alcohol. Braun l has
investigated it, but he did not succeed in characterising any single
constituent of the oil. Schimmel & Co. have detected terpineol in it,
but, so far, the other constituents are unknown. The fresh herb also
yields from *1 to *2 per cent, of an oil of specific gravity -905 to '940
and optical rotation + 15° to + 45°. The fruit yields 1 to 2 per cent, of
an oil of specific gravity -930 to -940. Lovage oil is chiefly employed
in liqueur and cordial making.
OIL OF CELERY.
All parts of the herb Apium graveolens, the common celery, yield
essential oils, of which that from the seeds is most valued. Schimmel
& Co., however, state that that from the green leaves most exactly re-
produces the natural celery flavour. The oil from the seed is obtained
to the extent of about 3 per cent., as a liquid of strong celery odour
Optical rotation + 60° to + 82° (rarely + 40°)
The constituent present in greatest quantity is dextro-limonene^
Ciamician and Silber2 have recently examined the high boiling frac-
tions of the oil and found therein traces of palmitic acid, guaiacol, and
a crystalline phenol of the formula C16H20O3, melting at 66° to 67°. In
addition, a sesquiterpene was found, and two bodies, both acids, of a.
peculiar constitution, sedanolic and sedanonic acids, together with the
lactone of the former, sedanolide, which appears to be the chief odor-
1
Arch. Pharm., 1897, iii. 1. *Berichte, 30 (1897), 492, 1419.
UMBELLIFEE^] 315
ous constituent of the oil. Sedanonic acid C12H20O3 is a crystalline
body melting at 88° to 89°, and is easily converted into its laetone
sedanolide C12H18O2. Sedanonic acid C12H,8O3 melts at 113°, and
possibly occurs as an anhydride in the oil. These two acids are nearly
related, and Ciamician and Silber consider that sedanolic acid is ortho-
oxyamyl-tetrahydrobenzoic acid, and that sedanonic acid is a related
ketonic acid. The following formulae thus express the relations of
these bodies:—
CH2 CH
/ \ / \
H2C CH.CO.C 4 H 9 H2C C . CH(OH)C4HC
H2C C.COOH , H2C CH.COOH
\ ^ \ /
CH CH2
Sedanonic Acid. Sedanolic Acid.
Sedanolide, the chief odorous constituent, would thus be tetra-
hydrobutyl-phthalide of the formula—
CH
1 i
H2ru r*
\u • rO-tL.
TT o r*4-tig
TT
O
H2C CH. CO
CH2
A closely-related body, phthalylisopropylidene, and its reduction
products, were prepared artificially and found to have an odour much
resembling celery.
Schimmel & Co.1 have also examined the oil and isolated from it a
new sesquiterpene, to which they have given the name selinene. It is-
probably identical with the sesquiterpene discovered by Ciamician and
Silber, but not further investigated by them.
The sesquiterpene fraction was separated into the following two-
portions :—
First fraction. Boiling-point 120° to 121° (6 mm.); di7.5o 0'9197;
a D + 35° 11'; m^ 1*49863.
Second fraction. Boiling-point 121° to 122° (6 mm.); di8° 0-9170;
aD + 38° 12' WDSSIO 1-4956.
The sesquiterpene, or rather mixture of sesquiterpenes, was a yellow
liquid of an agreeable odour, which did not solidify even when cooled
considerably.
By passing hydrochloric acid into the ethereal solution of the hydro-
carbon a solid chloride was obtained, which, after evaporation of the
ether, crystallised out in needles from the reddish-blue residue. The
crystallising process of the chloride was materially facilitated by a
slight addition of alcohol and the application of a freezing mixture.
The product, after being crystallised once, melted at 68° to 70°. The
melting-point of a sample which had been repeatedly recrystallised
from methyl alcohol was found to be 72° to 74°.
1
By splitting off hydrochloric acid with sodium ethylate a hydro-
carbon possessing the following properties was recovered from the
chloride: Boiling-point 268° to 272° (the bulk 268°); di&° 0-9232;
^20° 0-9196; [a]D + 49° 30'; wD2o° 1*50483. The hydrocarbon which
was obtained from the dihydrochloride is again converted by means of
hydrochloric acid in ethereal solution into the dihydrochloride, melting-
point 72° to 74°.
It is therefore possible to obtain the hydrocarbon in the pure state
by means of the dihydrochloride, that is to say, in so far as it is at all
possible, in view of the possible formation of isomerides, to regenerate
a hydrocarbon from a chloride.
Selinene has been investigated by Semmler and Eissel who give
the following details:—
Selinene has a specific gravity 0*919, optical rotation -f 61° 36',
refractive index 1-5092, and boiling-point 128° to 132° at 11 mm. It is
shown to be a bicyclic doubly unsaturated hydrocarbon. On reduction
it yields tetrahydro-selinene, C15H28, of specific gravity 0'8881, rotation
+ 7°, refractive index 1-48259, and boiling at 126° to 128° at 11 mm.
.Selinene yields a dihydrochloride, which, when treated with calcium
hydroxide, yields the alcohol selinenol C16H20O. This body boils at
155° to 163° at 19 mm., and has a specific gravity 0*9627, refractive
index 1-50895, and optical rotation + 52° 36'. If the hydrocarbon be
regenerated the resulting sesquiterpene has a slightly higher optical
rotation, due possibly to isomerisation. The two sesquiterpenes were
oxidised with ozone in order to throw light on their constitutions.
Natural selinene, to which Semmler assigns the name /3-selinene, yields
a large amount of an indifferent body, which yields a disemicarbazone
melting at 228°. From this the diketone was recovered, and found to
have the formula C13H20O2. It boils at 178° to 180° at 11 mm., and has
a specific gravity 1*0566, refractive index 1*49994, and optical rotation
+ 15°. Eegenerated selinene, or orô-a-selinene, boils at 128° to 132°
at 11 mm., and has a specific gravity 0*9190, refractive index 1*5092,
and optical rotation + 61° 36', yields only a small amount of this
diketone, but a large amount of an acid which is termed methyl-
selinene diketo-monocarboxylate C15H24O4, boiling at 185° to 190° at
11 mm., and having a specific gravity 1*0635, refractive index 1*47889,
and rotation + 4° 24'. These facts are accounted for on the hypothesis
that during the elimination of hydrochloric acid from the dihydro-
chloride a double linkage has been displaced into the ring.
An oil from the herb and seed of the wild celery (Ache des marais),
distilled in the South of France, possessed the following constants :—
Optical rotation + 58° 30'.
Acid number . . . . . . . . . . 1-8
Ester „ 41-5
After rectification with steam (in the course of which process a
residue of 7*7 per cent, remained) its properties had undergone con-
siderable change: dl50 0-8541; aD + 70° 55'; n^ 1*47489. Soluble in
6 volumes and more of 90 per cent, alcohol with slight turbidity.
An Algerian oil distilled from wild plants had the following char-
.acters:—
1
Berichte, 45 (1912), 3301.
UMBELLIFEE^ 317
Acid number 0
Ester value 14-7
„ „ (after acetylation) 2O9
The green herb yields '1 per cent, of an oil of the following char-
acters :—
Although it has not been thoroughly examined, it is probable that
its constituents closely resemble those of the seed oil. The oil is
soluble in 10 parts of 90 per cent, alcohol.
OIL OF PARSLEY.
All parts of the common parsley, Petroselinum sativum, yield an
essential oil, of which that from the green herb itself is most esteemed,
although that from the seed is the commoner oil. The yield from the
seeds is from 2 to 6 per cent.
Acid value 2 „ 6
Ester „ . 1„8
It is soluble in 8 volumes of 80 per cent, alcohol, sometimes with
turbidity.
Pinene and apiol are present in the oil. Allyl-tetramethoxybenzene
and one or more unidentified phenol ethers are also present in small
amount, as well as traces of palmitic acid, ketones, and aldehydes.
Myristicin has been identified.
If the oil contains more than a certain quantity of the latter body it
is semi-solid at ordinary temperatures, whilst in any case crystals are
deposited on exposure to cold. German oil is rich in apiol, but French
oil contains very little. Apiol is prepared from the oil either as a thick
liquid, or in the purer crystalline condition, and is used to some extent
in medicine.
The oils from the root l and from the whole herb 2 have also been
examined and found to have the following characters:—
Root Oil. Herb Oil
Specific gravity . 1-049 to 1-012 0-9023 to 1-0157
Optical rotation + 1° 24' + 1° 16' „ + 4° 10'
Refractive index — 1-5090 „ 1*5250
Acid value . — 0„1
Ester — 5 „ 14
(after acetylation) — 19 „ 68
The oil distilled from the herb in flower is similar to the ordinary
herb oil, but is slightly laevo-rotatory.
1 2
Schimmel's Bericht, April, 1894, 55. Ibid., October, 1895, 59.
OIL OF AJOWAN SEED.
This oil is the product of distillation of the fruit of the herb
Ptychotis Ajowan (Carum Ajowan), a plant cultivated in many parts of
Egypt, Persia, Afghanistan, and Bengal. The fruit yields from 3 to 4
per cent, of oil. It has the following characters :—
Optical rotation . + 1° ,, + 5°
Phenols 45 to 60 per cent
The characteristic odour of the oil is due to the presence of thymol.
In addition, cymene, a-pinene, dipentene, and y-terpinene are present.
The oil itself is used to a certain extent in India for medicinal purposes,
but its principal use is for the preparation of thymol. According to
Stohmann, carvacrol is also present, but this statement requires con-
firmation.
Experimental cultivations of ajowan seed have been made in the
West Indies, but, so far, not on a commercial scale. Ajowan seeds
grown in the Seychelles yield about 9 per cent, of oil containing 38 per
cent, of thymol, and seeds grown in Montserrat yield 3 per cent, of oil
containing 54 per cent, of thymol.1
OIL OF ANGELICA.
All parts of the herb Angelica officinalis (Angelica Archangelica)
yield essential oils, of which the best known is that distilled from the
fresh root. The plant is a native of Europe, on mountains or river
sides, especially in Lapland, Sweden, Norway, Germany, etc. It is
cultivated to a considerable extent in Saxony, but is comparatively rare
in Britain. Although the root -oil is that mostly used, and held in high
esteem, according to Schimmel & Co. the seed oil is preferable to this.
Angelica root oil is a light yellow or reddish limpid liquid of strong
aromatic odour and pungent taste. The yield from dried roots grown
in the Saxon Erzgebirge is from 0*5 to 1 per cent, of oil. The specific
gravity varies from -854 to '918, that from the dried root usually having
a higher specific gravity than that from the fresh root.
Optical rotation + 16° , + 41°
Refractive index 1-4770 , 1*4880
Acid value 1,4
Ester „ 12 , 40
,, ,, (after acetylation) 50 75
On long standing crystals are deposited, which according to Gior-
dani have the composition C32H62O6, and melt at 74° to 77°. Beilstein 2
showed that the oil contains one or more terpenes. Naudin 3 confirmed
this, and Schimmel & Co. have shown that amongst the lower boiling
fractions of the oil, dextro-phellandrene exists. Ciamician and Silber4
showed that the crystalline bodies (of which they separated two) exist-
ing in the oil were probably oxyacid anhydrides. Hydrocarbons, prob-
ably sesquiterpenes, were also found, which distilled at 240° to 270°,
1 2
Bull. Imp. Ins*., xvi. 1, 30. 4
Berichte, 15 (1882), 1741.
3 Ibid, 16 (1883), 1382. Ibid., 29 (1896), 1811.
UMBELLIFERaS 319
•and oxypentadecylic acid C15H30O3. They also isolated valerianic and
two methyl-ethyl-acetic acids from the oil. The oil obtained from the
•seeds, which yields about 1 per cent., has a specific gravity *856 to *890,
and an optical rotation of + 10° to 4- 13°. It contains phellandrene,
methyl-ethyl-acetic and oxymyristic acids.
E. Booker and A. Hahn have recently isolated a crystalline lactone
of the formula C16H1gO8 in the last runnings of angelica root oil. From
200 grms. they obtained 10 grms. of a lactone which, when recrystal-
lised from ethyl ether and light petroleum melted at 83°. It boils
without decomposition at 250°. The lactone is an unsaturated body;
when brominated in a glacial acetic acid solution it yields a dibromide,
which, when recrystallised from glacial acetic acid, melts with decom-
position at 143° to 145°.
Schimmel & Co.1 have examined the following samples from various
parts of the plant:—
d15o. Acid Ester Solubility in 90 per cent.

Oil from a
D. W
D200- V. V. Alcohol.
Leaves (Sept.) 0-8550 + 28° 2' 1-47782 0-5 17-6 In 6 vol., with opalescence.
(Oct.) 0-8697 + 22° 8' 1-48044 1-3 22-6 „ 5 „
0-8767 + 20° 11' 1-48316 1-6 21-1 ,, 2-5 vol. a. m.
Boot 0-8733 +' 28° 23' 1-48083 2-5 25-9 ,, 3 vol. a. m.
Seed 0-8623 + 12° 12' 1-48681 1-L 18-1 ,, 6 vol., with opalescence.
The oil distilled from the whole fresh herb has the following char-
acters :—
Acid value . . . 0 „3
Ester „ . , 17 „ 25
,, „ (after acetylation) . . . . . 51
Japanese angelica root, from which an oil is distilled, is from
Angelica anomala (Angelica refracta ?). The oil, which is obtained to
the extent of '1 to *2 per cent, of the root used, has a specific gravity
-910 to '915. At 10° it becomes thick, and at 0° it solidifies to a paste.
The crystalline mass thus deposited consists mainly of a fatty acid
melting at 62° to 63°. The oil distils over between 170° and 310°; the
last fractions have a blue-green colour. This oil has a more acrid
odour than the Saxon oil, but distinctly recalls musk, although this is
to a great extent covered by the other and less pleasant odour of the oil.
The chief employment for angelica oil is in liqueur making.
OIL OF CARROT.
The seed of the carrot Daucus carota, yields from 1 to 1*5 per cent,
of oil, which has the following characters :—
Acid value . . . . . . . . . 1 , ,5
Ester „ 17 „ 55
1
Jour, prakt. Chem., ii. 83 (1911), 243.
According to Landsberg,1 the oil contains pinene and an oxygenated
body of the formula C10H18O. Eichter2 has, more recently, examined
the oil and found present isobutyric and palmitic acids in the form of
esters, and formic and acetic acids in the free state.
From the laevo-rotatory portions of the saponified oil, which boiled
between 150° and 160°, Eichter isolated a fraction boiling at 158° to
166° (d14o 0*8633; aDl5o - 8-45°) in which he proved the presence of
pinene by means of the nitrosochloride and the nitrolbenzylamine^
The latter body possessed the same melting-point as a preparation
obtained from ordinary d-pinene, from which fact Eichter concludes
that the pinene of oil of carrot seed is also d-pinene, an erroneous in-
ference, because, as is well known, d-3 and Z-pinene yield the same
inactive nitrolbenzylamine. Deussen has since shown that pinene
is present in the laevo-rotatory form. In a fraction boiling at from
168° to 176° (duo 0-8624; aDl50 - 5'85°) he discovered Z-limonene,
which he identified from the nitrosochloride and the nitrolpiperidine
(melting-point 103° to 106°). The portions with a high boiling-point
contained a crystalline body C15H26O2, which Eichter calls daucol,
and which he regards as a divalent sesquiterpene alcohol- This body
forms white needle crystals with a silky lustre, melting-point 115° to
116°; [a]Dl4o - 17-15° 17-47°.
The oil obtained at the period of maturity of the seeds by distilla-
tion of the entire plant of the wild4carrot of the Puy-de-D6me, has been
examined by Eoure-Bertrand Fils.
The oil had a bright green colour.
Its constants are :—
Specific gravity at 15° C 0'9016
Soluble in 1 volume of 80 per cent, alcohol, but an opalescence
is formed on the subsequent addition of alcohol.
Acid value 2*7
Saponification number 195*4
„ ,, of the acetylated oil . . . . 226*8
The green colour of the oil is to be attributed to the fact that the
distillation had been carried out in a copper still.
The saponification number indicated above was obtained by boiling
for one hour with semi-normal alcoholic potash; after boiling for half
an hour a value of only about 169 was found.
OIL OF AMMONIACUM.
This oil is usually obtained by distilling the gum resin of Dorema
ammoniacum with water. Persian ammoniacum is derived from this
plant, but a certain amount of ammoniacum from other sources is derived
from Ferula species. The yield of oil is very small, usually about '3 per
cent. The oil has the following characters :—
Refractive index 1*4723 ,, 1*4808
Acid value . . . . . . . . . 1 , ,4
Ester , 40-5
,, ,, (after acetylation) 106*4
It distils between 250° and 290°.
1 2
3
Arch.d. Pharm., 228 (1890), 85. Ibid., 247 (1909), 391.
Berichte, 43 (1910), 523. 'Bulletin, April, 1912, 30.
UMBELLIFER^S 321
A small amount of terpenes distils between 155° and 170°, but the
greater part of the oil distils from 250° to 290°.
Semmler, Jonas, and Eoenischl have examined this oil, and have
identified the following constituents therein: linalyl acetate, eitro-
nellyl acetate, a new dihydro-sesquiterpene which has been named
ferulene, a new sesquiterpene ketone which has been named doremone,
doremyl acetate, cetyl alcohol, and an unidentified terpene boiling be-
tween 65° and 80° at 11 mm. Ferulene C15H26 is a monocyclic dihydro-
sesquiterpene having the follow ing characters :—
Optical rotation . . . . . . +6°
It is probable that this body is not a chemical individual, but is a
mixture of about 75 per cent, of a dihydro sesquiterpene, and 25 per
cent, of a sesquiterpene not yet separated. Doremone C15H26O is an
unsaturated aliphatic sesquiterpene ketone having the following
characters:—
It yields an oxime melting at 88° and a semicarbazone melting at
124°. On reduction with sodium and alcohol, it yields the correspond-
ing alcohol, doremol C16H27OH, which occurs in the oil in the form of
its acetic ester. Doremol has the following characters :—
OlL OF ASAFCETIDA.
The gum resin of certain species of Ferula, chiefly, in all prob-
ability, Ferula Narthex, and Ferula scorodosma, both perennial herbs,
indigenous to Turkestan, Bokhara, Western Afghanistan, and Cashmir,',
yields, when distilled with water, about 3 to 20 per cent, of a some-
what foul-smelling oil. The oil has the following characters:—
Optical rotation + 10° 58' to - 36°
Semmler 2 has investigated this oil, having separated by fractional
distillation under reduced pressure two terpenes, one of which was
probably pinene, and a sesquiterpene, which had a lavender-like odour.
The remainder of the oil consists chiefly of compounds containing
sulphur. According to Brannt, the oil contains allyl sulphide and
ailyl disulphide, but Semmler denies this. Sulphur compounds of the
formulae C7H14S.j, C10H20S2, C8H16S2, and C10H18S2 were found, together
with an oxygenated body of the formula C10H16O, or a multiple of this.
Umney and Bunker 3 have examined the oil from the lump asa-
foetida, and also from the tears, and arrived at the following conclu-
sions :—
l
lnaug. Dissert., Breslau, 1916 ; and Berichte, 1917, 50, 1823.
*Berichte, 23 (1890), 3530; 24 (1891), 78. »P. and E.O.R. (1910), 165.
VOL. I. 21
1. The percentage of volatile oil in the "tears" of asafoetida may
equal that in the " mass " variety, or even be slightly higher in good
specimens, but in general it is slightly lower.
2. In both varieties the actual percentage of volatile oil present is
12 to 16 per cent.
The " tears " themselves, however, and the tinctures prepared from
them are far more pungent in their odour than the " mass " and tinc-
tures from it, despite this approximate equality in the percentage of oil
present. It appeared, therefore, that notwithstanding the greater pro-
portion of oil in the mass the composition of it might be different, and
needed further investigation. They found the following amounts of
sulphur in the two oils :—
Sulphur in oil from mass = 2*06 per cent.
„ „ tears = 10-44 „
It would appear, therefore, that the oil of the mass differs in com-
position from the oil of the tears in containing a far lower proportion
of sulphur compounds,l and is certainly less offensive in smell.
Harrison and Self have examined a number of samples of this oil,
distilled by themselves from the drug as found on the London market,
1
Percentage Sp. Gr. of Oil Ref. Index Rotation Percentage
No. of Oil. at 15 '5°. of Oil at 20°. of Oil. of Sulphur
in Oil.
1 11-0 0-976 1-5200 - 10° 16' 28-2

2 16-4 0-975 1-5152 - 9°0' 21-6
3 9-4 0-917 1-4952 + 6° 58' 19-3
4 5-8 0-981 1-5207 - 9° 30' 29-2
5 10-1 0-915 1-4942 + 9° 39' 17-6
6 7-2 0-993 1-5250 - 35° 55' 37-8
7 11-1 0-918 1-4980 + 0°50' 20-8

8 15-7 0-920 1-4978 + 5° 40' 19-7
9 9-6 0-925 1-4993 + 4° 32' 21-6

10 7-3 0-957 1-5077 - 17° 3' 19-9
11 14-1 0-923 1-4985 _ _

12 16-7 0-927 1-4982 —
13 11-9 0-930 1-4997 —
14-1 0-930 1-4987 — —
14 — —
15 17-1 0-929 1-4999 — —
The sulphur in the oils was determined in the following manner :

About 0*5 grm. of the oil was weighed out into a 150 c.c. flask, fitted
by a ground neck to a vertical condenser ; 5 c.c. of water was then
added through the tube, followed by 5 c.c. of HNO3, and if necessary
the flask was gently warmed to start reaction, which then proceeds
somewhat vigorously; 3 grms. of KBr in powder was then dropped in
through the condenser tube, and the liquid boiled for ten minutes, after
ipharm. Jour. (1912), [4], 34, 205.
UMBELLIFEK^S 323
which it was cooled, and 5 grms. of NaOH, dissolved in a little water,
was added in the same way. The flask was then disconnected and the
contents transferred to a platinum dish and evaporated to dryness and
ignited. The residue was dissolved in water, hydrochloric acid added,
and the liquid evaporated to drive off nitrous and nitric acids, and the
sulphate determined in the usual way. A blank determination must,
of course, be made with all the materials.
It will be observed that high percentage of sulphur in the oil goes
with high specific gravity, high refractive index, and laevo-rotation.
OIL OF GALBANUM.
Galbanum Oil is the product of distillation of the gum-resin Pence-
.danum galbaniflorum and probably other species indigenous to Persia.
From 12 to 24 per cent, of oil is obtained, which has a penetrating
odour and sharp taste.
Galbanum oil has the following characters :—
a-Pinene and cadinene have long been recognised as constituents of
;the oil. Semmler and Jonas x have recently examined an oil having the
Eefractive index 1-4939 at 25°
They detected a-pinene, /?-pinene, myrcene, a sesquiterpene which
is either cadinene, or is easily converted into cadinene hydrochloride,
and a sesquiterpene alcohol, cadinol, of the formula C15H26O. Cadinol
forms a hydrochloride melting at 117° to 118°.
OILS OF HEKACLEUM.
The ordinary heracleum oil is distilled from the fruit of Heradeum
spkondylium, the cow parsnip. The yield is from 0*5 to 3 per cent, of
.an oil having the following characters :—
Optical rotation T 0° ,, 4- 2°
Acid value 4 „ 16
Ester „ 214 „ 276
According to Zincke,2 it contains octyl alcohol C8H17OH and its
acetic 3ester C10H02 and caproic ester C14H28O2. According to Mos-
linger, ethyl butyrate is also present; and also the lauric acid ester of
octyl alcohol, and some hexyl compounds in very small quantities.
The oil of Heracleum giganteum has been examined by Gutzeit, and
found to correspond closely with that just described. Schimmel &
Co. give the following interesting details of this oil:—
It is now well known that this oil is obtained from the fruit or the
entire umbellate heads of Heracleum sphondylium L. A distillate
which we have obtained from the dry umbels from which the fruit had
been removed is for this reason interesting. The yield of oil amounted
3 z
Berichte, 47 (1914), 2068. Annalen, 152 (1869), 1.
*Berichte, 9(1876), 998.
to 0*08 per cent. The odour of the brownish-yellow oil differs distinctly
from that of the fruit. d150 0-9273; a D - 0° 48'; acid number 16-2;
ester number 148'6; ester number after acetylation 195*9; soluble in
1*1 volume 80 per cent, alcohol; when more solvent is added opal-
escence and strong separation of paraffin occur. For comparison we
give below the properties of two oils distilled from the fruit only.
1. Yield (compared with dry material) 0-9 per cent.; d15o 0*8744 ;
aD + 0° 38'; acid number 15'9 ; ester number 215-4 ; ester number
after acetylation 285*3 ; soluble in 0*8 and more volume 80 per cent,
alcohol; not entirely soluble in 70 per cent, alcohol.
2. Yield (calculated on dry material) 1-21 per cent. ; dl5o 0-8798 ;
aD + 1° 6'; acid number 7'3 ; ester number 242*4; ester number after
acetylation 276'3; soluble in 1 and more volume 80 per cent, alcohol.
The oil from the dry, ripe fruit of Heracleum giganteum L. (yield
3*6 per cent.) has the following characters :—
Optical rotation + 1° to + 1° 30'
Kefractive index 1-4230 „ 1-4255
Acid value . . . . . . . . . 1-5 , , 4*0
Ester „ 280 „ 290
„ ,, (after acetylation) 314 ,, 320
It contains the acetic and butyric esters of hexyl and octyl alcohols,
and traces of ethyl butyrate.
The colourless oil had a peculiar odour, similar to that of common
heracleum oil.
OlL OF BUPLEUKUM FBUTICOSUM.
The oil of this umbelliferous plant, which grows wild abundantly in

the island of Sardinia, has been examined by Francesconi and Sanna.1
Rotation + 19° ,, + 47°
Saponification value 5 ,, 14
„ „ (after acetylation) . . . 23 ,, 28*5
The yield varied from 0'5 to 4*4 per cent. The oil consisted chiefly
of hydrocarbons; it contained only small proportions of alcohols and
esters. It was found that the oil-content increases as the plant reaches
maturity, and that the flowers contain more oil than the leaves. Plants
gathered at high altitudes contain more oil than do those from the plains.
The density, optical rotation and index of refraction increase as the plant
develops; they attain their maximum during the flowering period, at
the end of which they diminish again. The ester-content of the leaves
diminishes during the flowering and is greatest in the plants from the
mountains. The leaf-oils contain more ester than do the flower-oils;
plants grown in a moist atmosphere are deficient in ester. The specific
gravity of oils rich in ester is higher, and their rotatory power lower
than that of oils which are deficient in ester. The flowers contain a
larger proportion of free alcohol than the leaves, and during the flower-
ing period the content of free alcohols increases at the expense of that
of the alcohols in combination. The terpene present boils at 167° to»
1
Gazz. Chim. Hal., 41 (1911), i. 395.
UMBELLIFEB^J 325
169° C.; it has the specific gravity 0-8416 at 14° C.; a D + 35-70;
WD 1-4862. It polymerises to a white amorphous mass, melting-point
90° C. Dextro /J-phellandrene is also present.
Francesconi and Sernagiottol have investigated the alcohol bupleurol,
which they isolated recently from the oil. It is best isolated from the
high boiling fractions of the oil by means of phthalic anhydride. It has
the composition C10H20O, and boils at 209° to 210°, and has a specific
gravity 0-8490, refractive index 1-4508, and is optically inactive. It has
a slight but distinct odour of roses. From its general character it is
probably an aliphatic compound. It forms an oily dibromide, and a
crystalline urethane, which forms lustrous needles melting at 45°. On
oxidation with chromic acid it yields (1) an aldehyde yielding a semi-
carbazone melting at 135°; (2) an aldehyde yielding a semi-carbazone
melting at 97°; (3) a ketone boiling at 217° ; and having a refractive
index 1-4419 at 25°; this ketone yields a semi-carbazone melting at 189°
to 190°; (4) a red oil which boils at 207°, and was found to be the ester
of bupleurol and its corresponding acid, which is formed during the
oxidation process. Bupleurol is isomeric with citronellol and with
androl. Its formula is probably OH . (CH^CH^ . C(CH2) . CH 2 .
CH 2 . OH, which would make it a dihydro derivative of the alcohol
nerol. A body, probably an aldehyde, was also isolated at the same
time as bupleurol. This body has the formula C10H16O, and has the
following characters : Specific gravity 0*9264 ; specific rotation + 14-93°;
and refractive index 1-4909.
OIL OF SESELI BOCCONI.
This oil, distilled from Seseli Bocconi (Crithmum siculum) to the
extent of about 0*3 per cent, has a specific gravity of about 0*855.
According to Francesconi and Sernagiotto,2 the essential oil contains,
in addition to laevo-pinene and fota-phellandrene, a di-cyclic aldehyde,
another carbonyl compound accompanying the aldehyde, a di-cyclic
primary alcohol, an unsaturated secondary alcohol, and formic, acetic,
and methyl-butyric acids. The primary alcohol yields, on oxidation
with potassium bichromate and sulphuric acid, an aldehyde apparently
having the formula C10H16O, and being identical with the aldehyde
naturally occuring in the oil. It yields a semi-carbazone melting at
148° to 158°. The primary alcohol has the formula C10H18O.
OIL OF SEA FENNEL.
Crithmum maritinum is a plant growing freely on the French coast.
According to Borde 3 the stems and leaves on the one hand, and the
seeds on the other, yield essential oils, the former to the extent of up
to 0'3 per cent., and the latter to 0*8 per cent. The two oils have the
Stems and Leaves. Seeds.
Specific gravity at 4° . 1-0374 to 1-0492 0-9661 to 0'9809
Optical rotation . . + 6° 42' „ + 8° 15' + 5° 27' „ + 8° 9'
Saponification value . 6-4 4 „ 10
The seed oil contains about 12 to 18 per cent, of d-pinene, 40 to
1 a
Att. E. Accad.s Lincei (1913), 22, 34. Ibid. (1913), 116.
Bull. Soc. Pharm., 16,132, 395.
45 per cent, of other terpenes, and 40 to 50 per cent, of dill-apiol
C6H(OCH3) (O2CH2) (CH 2 . OH : CH2).
Delepine1 has further identified dipentene, cymene, the methyl
ether of thymol, and an alcohol with a rose-like odour but not yet
identified, as constituents of the oil. mnM » mnS.j rbuu
Italian sea fennel oil has been examined by Francesconi and Serna-
giotto,2 who found the oil to have the following characters:—
„ rotation + 3-18°
The principal constituents of the oil were found to be /3-phellandrene,
dill-apiol, and a terpene, which the authors have named crithmene, and
which has the following characters :—
It yields two nitrosochlorides, melting at 101° to 102° and 103° to 104*
respectively.
Sardinian sea-fennel oil has been found to contain _p-cymene.
OIL OF MASTERWORT.
Masterwort Oil is distilled from the root of Imperatoria ostruthium,
a plant indigenous to the mountain regions of Southern and Central
Europe. The root yields about 1 per cent, of oil of characteristic
aromatic odour, which, according to Hirzel, contains bodies resembling
terpene alcohols. Wagner states that angelic aldehyde is present.
Boils at 170° to 190°
Lange 3 has examined an oil distilled from two-year old Tyrolese
plants. The yield was 1 per cent.
The oil had the following characters :—
Acid value . 0-8
Ester 17-9
(after acetylation) 2.V34
The esters of isobutyric, isovalerianic, isopropylidene-acetic, formic
and acetic acids were present, also free palmitic acid ; 95 per cent, of
the oil consisted of terpenes, among which were: dipentene, dextro-
limonene, a-pinene, and dextro-phellandrene. An alcohol C10H20O and
a sesquiterpene yielding a dihydrochloride, melting-point 157° to 157*5°,
are also present. Angelic aldehyde, described by Wagner, could not
be found.
1
2
Comptes rendus, 149 (1909), 215 ; 150 (1910), 1061.
Ait. R. Accad. d. Lincei, Roma (5), 22 (1913), 231, 321, 382.
3
Year Book of Pharmacy (1912), 100.
UMBELLIFEE-ZE 327
OlL OF SUMBUL.
Sumbul Oil or Musk-root Oil is obtained from the dried root of

Ferula sumbul. The yield of oil is only from -2 to 1*1 per cent. The
Acid value 7
Ester „ 20 to 90
On standing for a few days after distillation crystals are deposited,

which melt at 113° to 114°.
It has a distinct musk-like odour, and in India the root of Dorema
ammoniacum is often substituted for it and used under the name of
sumbul root.
OILS OF PARSNIP.
Various parts of Pastinaca sativa yield essential oils. The seed oil
contains the propionic and butyric esters of octyl alcohol. Schimmel &
1
Co. have investigated the oils distilled from the under-mentioned parts
of the plant.
They submitted separately to distillation with water vapour, the
ripe dried seeds, the umbels, and the roots of the plants.
1. Oil from dried seed of Pastinaca sativa.—The bright yellow oil
obtained in a yield of 1-47 per cent, had the following properties :
d16° 0-8736 ; aD - 0° 9'; n^20o 1-43007; acid number 4'4; ester number
240-6; ester number after acetylation 276 ; soluble in 2-J and more
volumes 80 per cent, alcohol.
2. Oil from dry umbels of Pastinaca sativa.—The oil had a dark
brown colour, and had a very remote odour of oil of ambrette seeds.
It was obtained in a yield of 0*3 per cent.; dl5o 1*0168 ; ac - 0° 50';
WDgoo 1-50049; acid number 4'2; ester number 62'9 ; ester number after
acetylation 86-2; soluble in 6*5 volumes 80 per cent, alcohol, with
separation of paraffin.
3. Oil from the dry roots of Pastinaca sativa.—The bright yellowish
oil which in odour reminded somewhat of vetiver oil, was obtained in a
yield of 0*35 per cent., and had the following properties: d150 1*0765 ;
aD - 0° 10'; ?&D20o 1'52502 ; acid number 3'9 ; ester number 12'6 ; ester
number after acetylation 33'7; not completely soluble in 10 volumes 80
per cent, alcohol; soluble in 0*6 and more volumes 90 per cent, alcohol.
The oil from the wild plant seeds has the following characters :—
Optical rotation 0° to + 0° 13'
Acid value 2 „ 10
Ester „ 218 „ 270
„ (after acetylation) 260 „ 296
Two samples of parsnip oil examined by Boure-Bertrand Fils had
the following characters. Sample No. 1 was a German distilled oil from
the seeds only; sample No. 2 was an Italian distilled oil from the stems
with flowers and seeds :—
1
Bericht (1908), 96.
No. 1. No. 2.
Specific gravity at 15° C. . . . 0-8712 0-8970
Optical rotation ±0° + 0° 6'
Solubility in 80 per cent, alcohol . . 1 volume and over 2 volumes and over
Acid value 9-1 5-6
Saponification number . . . . 250-6 228-9
(after acetylation) 293-0 251-1
On dilution with 90 per cent, alcohol the Italian sample deposits a
large quantity of paraffins. When the oil itself is subjected to refrigera-
tion it thickens a little but does not deposit solid matter.
Oil of parsnip contains a considerable amount of esters of octylic
alcohol.
These esters are composed chiefly of normal octyl butyrate.
OILS OF PEUCEDANUM.
The root of Peucedanum officinale and the fruit of Peucedanum
grande yield small quantities of oil, having the following characters:—
P. officinale. P. grande.
Optical rotation + 29° 4' 4-36°
OIL OF ERYNGIUM FCETIDUM.

The oil distilled from this plant, which is known as Walang D&rr in
Java, has the following characters :—
Acid value 29-5
,, ,, (after acetylation) . . . . 327
OlL OF SlUM ClCUTÊFOLIUM.
The fresh herb, Slum cicutcefolium, yields, according to Babak,1 0*5

per cent, of essential oil, having the following characters:—
Specific gravity . . . . ~~ . . . . 0-8447 at 22°
Acid value 0
Ester „ 33
It contains d-limonene and an aldehyde, which has not yet been
identified.
OIL OF CONIUM MACULATUM.
The herb Conium maculatum (deprived of flowers) yields about 0*08
per cent, of essential oil, which, according to Haensel, has the following
characters :—
Acid value 60
Ester ,, 10
The fruit yields 0-018 per cent, of oil of specific gravity 0*895 and
Saponification value 34.
1
Midland Drug and Pharm. Rev., 43 (1909), 5.
MYRTACEJE 329
OIL OF MEUM ATHAMANTHICUM.
The fresh roots of Meum Athamanthicum yield about 0*5 per cent.
• of essential oil which Schimmel & Co. find to have the following char-
acters :—
Acid value 10-3
Ester ., . 151-2
OIL OF CNIDIUM OFFICINALE.

The oil from the roots of this plant has been examined by Sakei.1 He
•obtained 0'82 per cent, of a bitter oil of specific gravity 1*030 to T040.
It contains an unsaturated acid C12H19O3 (?), an alcohol of the formula
C10Hi8O and possibly a lactone of the formula C12H18O2.
MYRTAC^,
MYKTLE OIL.
This oil is distilled from the leaves of Myrtus communis, probably
a native of the south of Europe, although possibly it was introduced
here from Western Asia. It flourishes on the Mediterranean littoral,
especially in Spain, Italy, and the south of France. The leaves yield
.from 0*25 to 0*35 per cent, of essential oil. So long ago as 1867 Glad-
stone examined this oil, but his results are of little value to-day. Jahns
has shown that this oil contains dextro-a-pinene, cineol, and a cam-
phor of the formula C10H16O. Camphene, and probably a terpene not
yet identified at present. Dipentene is present in small quantities.
Under the name " myrtol " the fraction of the oil boiling between 160°
.and 170° has been introduced into commerce. It is not a definite com
pound, and probably possesses little value. Von Soden and Elze 2 have
found in the higher boiling fractions of this oil an alcohol, which they
term myrtenol. It occurs chiefly as its acetic ester.
This alcohol has been examined by Semmler and Bartelt,3 who ob-
tained it by saponifying the higher boiling fractions of the oil and then
fractionating the same. The alcohol has the composition C10H16O and
possesses the following characters :—
Boiling-point at 760 mm. . . . 222° to 224°
j 9 mm. 102-5°
In addition to myrtenol, small quantities of the alcohols gereniol
;and nerol are present.
Myrtle oil has the following characters :—
Specific gravity 0-880 to 0-926C
Optical rotation + 8° + 27
Acid value . . . . 0 2
Ester 13 135
(after acetylation) 30 190
1
2
Schweiz. Apotheker. Zeit., 55 (1917), 226.
3
Chem. Zeit. (1905) 1031. Berichte, 40 (1907), 1363.
The oil varies so much in composition that no solubility values can
be usefully assigned to it. Messrs. Schimmel and Co. have given the
following figures for oils distilled in different countries:—
Specific Gravity. Rotation. Ester Value.
France . 0-890 to 0-904 + 15° to + 25° 19 to 43

Spain . 0-913 „ 0-925 + 22° „ + 25° 20' 68 „ 86
Corsica . 0-883 „ 0-887 + 22° „ + 27° 13 „ 25
Syria . 0-893 „ 0-922 + 11° „ + 26° 18 „ 31
Asia Minor 0-913 + 10° 42' 39-4
Cyprus . 0-917 + 8° 11' 20-9
Algeria . 0-881 to 0-887 + 26° to + 27° 30' 17 to 20-6
Dalmatia 0-925 + 13° 20' 134-8
OIL OF CLOVES.
The clove tree is a beautiful evergreen, indigenous to the Molucca
Islands. It is cultivated in several of the islands to the south of the
Moluccas, and in Sumatra, Penang, Malacca, Madagascar, the Sey-
chelles, Bourbon, Mauritius, the West Indies, Zanzibar, and Pemba,
our chief supply coming from the two last-named islands. The tree
is Eugenia caryophyllata (Caryophyllus aromaticus Linn.), and most
parts of the tree have a very aromatic odour. The spice we know as
cloves consists of the dried unexpanded flower buds, which are used in
the distillation of the oil. The flower stems are also used, but the oil,
although of very similar character, is not of so fine an aroma. As a
spice Penang cloves fetch the highest price, but Zanzibar cloves are
highly esteemed in commerce; it must be remembered, however, that
the majority of " Zanzibar " cloves in reality come from the adjacent
island of Pemba.
According to a writer in the Perfumery and Essential Oil Record,1
much vagueness surrounded the source of cloves, the first definite state-
ment being by the Arabian geographer, Ibn Khurdadbah (A.D. 869 to
885), when he named the spice, together with cocoanuts, sugar, and
sandalwood as a product of Java. Marco Polo, the Venetian traveller
of the thirteenth century, found cloves in Java, and assumed them to
be indigenous to that island. Later navigators showed that both these
observers had been misinformed, but it must be borne in mind that the
name Java was applied in a general sense by Arabian geographers to
the Islands of the Eastern Archipelago. It remained for Niccolo del
Conti, another Venetian pioneer trader of the fifteenth century, to clear
up the matter. He learned in Java that cloves did not actually grow
there, but were brought from the Banda Islands, fifteen days' sail,
farther east.
At the beginning of the sixteenth century Portugal was the premier
maritime power of the world, and while the Spaniards were opening
up the new and unknown West, the Portuguese were penetrating to
the old but vaguely understood East, and just a few of its world-old
mysteries were being revealed to European knowledge. One of these
mysteries solved was the origin of certain Oriental spices, notably the-
1
P. and E.OM. (1916), 20.
MYETACE^ 331
clove tree, described by Pigafetta, a shipmate of Magellan, as he saw
it growing in 1521. For nearly a century the Portuguese had the lion's
share of the clove trade. Holland then came to the fore as a naval
Power in the East, and the Molucca Islands were wrested from the
Portuguese by the Dutch, who adopted drastic measures to secure a
monopoly of the spice trade.
In spite of all their efforts their enemies and competitors managed
to run many a rich cargo of Eastern products right through to England.
In 1609 the East India Company's ship " Consent" arrived in London
with 112,000 Ib. of cloves, the duty alone on which amounted to £1400r
and the impost as much more. The price in bond at that time was from
5s. 6d. to 5s. 9d. per Ib. ex bale.
The Dutch, in desperation, endeavoured to eradicate the clove tree
from its native islands, and even made annual attacks on all young trees
that might have sprung up meanwhile, with a view to confining the
growth of this spice to a group of small islands, of which Amboyna is
the chief. This practice has only of late years been discontinued (since
1873), and though there is no restriction of cultivation in other islands,
the " clove parks " of Amboyna remained the property of the Nether-
lands Government. It is said that the original Moluccas, or Clove
Islands, now produce no cloves at all. By the eighteenth century
France had become an important factor in Eastern affairs. The
French Governor of Mauritius (or " Isle de France," as it was then
styled), De Lozier Bouvet, adopted the suggestion of the financier,
Pierre Poivre, to introduce spice cultivation into the island, in spite
of the rigorous precautions of the Dutch.
It was not until 1770 that Poivre could revert to his long-cherished
scheme regarding these valuable spice trees. The spice plantations
thrived, and became famous under the name of " King's Garden," and
to-day have developed into the " Eoyal Botanical Garden," Pample-
mousses.1 Three years later, in 1773, the French transported the clove
tree to their Western Colony of Cayenne, where, however, it does not
appear to have flourished with any marked success. At the close of
the century, an Arab, by name Harameli-bin-Saleh, accompanied a
French officer from Zanzibar to Bourbon (where the clove had been
introduced about the same time as into Mauritius), and obtained leave
to take back a small quantity of clove seeds and plants with him. This
was the beginning of the clove cultivation in Zanzibar, Harameli mak-
ing the first plantation at Mitoni, on the road to Chueni, and the enter-
prise was most successful. The local Swahili name for the tree is
" garafu," presumably a corruption of the French "giroflier". The
industry was almost destroyed in Zanzibar by the terrible hurricane
of 1872, but in spite of this reverse has in later years recovered its
position. Pemba, a small island thirty miles North-West of Zanzibar,
is also an important seat of clove cultivation, though the quality of the
product is not equal to that of the Zanzibar growth.
The clove also flourishes in the Straits Settlements. Many years*
ago it was introduced into Penang and cultivated by European planters
and wealthy Chinese settlers. Penang cloves have a high reputation
for quality, but the Eastern consumption is so great that not a great
deal of the spice finds its way on to the European market.
1
Mauritius Illustrated (Macmillan), 1916.
The spice usually known as cloves, and which is generally em-
ployed for the distillation of the oil, consists of the dried unexpanded
flower buds.
The flower stalks, separated from the cloves whilst they are drying,
are also dried and exported, chiefly from Zanzibar and Pemba, and
yield on distillation 5 to 6 per cent, of oil, as against 14 to 21 per cent,
obtained from the buds. The stalks are known in Zanzibar as Vikunia,
and in France as " Griffes de Girofle ".
The dried fruits are occasionally exported, and are known as mother-
cloves. A small amount of essential oil is obtained from them.
Clove buds yield from 14 to 21 per cent, of a heavy essential oil,
Refractive index 1-5290 ,, 1*5355
Eugenol (by absorption) 78 to 98 per cent.
The following figures represent samples examined by the Imperial
Institute Chemists, the author, and Schimmel & Co., all being of
authentic origin :—
Specific Gravity.! R
" *•"•«• (byXÛ
Amboyua 1-0490 1-5305 - 1° 1 82 per cent.
Seychelles 1-0470 1-5295 - 1° 25' | 82
M 1-0485 — - 1° 6' 86 »
t} 1-0510 ! 1-5320 1° 30' 87
tt 1-0510 1-5325 - 1° 20' 88
Ceylon 1-0456 — - 2° 30' 87
» 1-0477 —. - 2° 85
Mauritius 1-0514 - 0° 23' 89
} 1-0614 — - 0° 24' 93
t 1-0681 — - 0° 20' 96
t 1-0590 1-5345 - 0° 50' 92
, 1-0570 1-5338 - 0° 30' ! 93
Zanzibar 1-0550 1-5310 - 1° 92
) 1-0525 1-5308 - 1° 30' 91
» 1-0530 1-5316 - 1° 20' 94
An examination of the oil yielded by Zanzibar cloves from trees of

different ages, has been made by the chemists at the Imperial Institute l
.No Yield. Specific Gravity. Rotation. Bugenol.
1 8 to 9 years' old 17-8 °/0 1-056 - 0° 23' 89°/0

2 45 19-2 °/0 1-064 - 0° 30' 88°/0
3 60 18-8 °/0 1-049 - 0° 29' 8±°/o
2
4 60 „ 17-4 °/0 1-050 - 0° 37' 88°/0
5 60 „ •' 6'5 °/0 1-056 - 0° 33' 90°/ 0
6 Stems from 1 5'9 °/0 —.
—
7 2 6-3 °/0 1-050 - 0° 42' 89°/0
1 2
Bull. Imp. lust., 12 (1914), 337. Tree in full flower.
From the mother-cloves (fruit).
MYBTACEÊ 333
The value of oil of cloves depends almost entirely on the percentage of
the phenol eugenol (especially when it is required for vanillin manufacture),
and as will be seen from the following paragraphs, the method of deter-
mination used should always be stated if results are to be comparative :—
Several methods have been suggested for the determination of the
eugenol, none of which give absolutely accurate results, but from them
useful comparative results may be obtained. Umney suggested the ab-
sorption of the eugenol in a Hirschsohn flask, as used for the examina-
tion of cassia oil, with a 10 per cent, solution of caustic potash. This
strength was found to be too high, and a 5 per cent, or even 3 per cent,
solution is now preferred. The unabsorbed portion has a specific gravity
of about 0*910, so that this may be allowed for (although rarely done in
practice), since the eugenol has a much higher specific gravity. Spurge
prefers to saponify the esters first, and to make an allowance for them,
but if a 5 per "cent, solution be used, this method without any such
allowance gives a close approximation to the total amount of eugenol,
both free and combined being reckoned as eugenol. The globules of
uncombined hydrocarbons have a great tendency to stick round the
top of the flask and require some " coaxing " to rise and agglomerate
in the neck of the flask. Heat will accelerate and assist this, however.
But the source of error lies in the fact that the aqueous solution of
potash and potassium eugenate dissolves some of the sesquiterpene,
which is thus reckoned as eugenol, and a too high result is obtained.
The process proposed by Thorn, although more tedious, gives more
exact results. This depends on the conversion of the eugenol into
benzoyl eugenol. The following are the details, which should be care-
fully observed in order to secure accurate results :—
About 5 grms. of clove oil are weighed into a beaker of about 150 c.c.
capacity, 20 grms. of 15 per cent, sodium hydroxide solution added, and
then 6 grms. benzoyl chloride. On stirring, the solid mass of eugenol
sodium salt at first formed goes into solution again as it is converted
into benzoic ester, with evolution of much heat. In the course of a few
minutes the reaction ends, and on cooling a solid crystalline mass of
benzoyl eugenol is obtained. To this, 50 c.c. water is added, and the whole
warmed on a water-bath until the ester is completely melted to an oil,
well stirred, cooled, and the clear supernatant aqueous solution filtered
off. The crystalline mass is again washed with two successive quan-
tities of 50 c.c. water, and the resulting impure benzoyl eugenol is re-
crystallised from alcohol, due allowance being made for its solubility in
that medium. 25 c.c. of hot alcohol (90 per cent, by weight strength)
are poured through the filter employed in the previous washing opera-
tions, in order to dissolve any adherent crystals, into the beaker, and
the whole warmed upon the water-bath until complete solution is
effected. The solution is then cooled to 17° C., and the crystalline
precipitate thrown upon a small weighed filter paper, filtered into a
25 c.c. cylinder, and washed with 90 per cent, alcohol until the filtrate
exactly measures 25 c.c. The filter and crystals are then removed to
a weighing bottle, dried at 100° C. until constant, and then weighed.
From the total weight the weights of the filter paper and of the weigh-
ing bottle are deducted, from which the benzoyl eugenol is calculated.
To the latter weight 0*55 grm. are added, being the weight of pure
benzoyl eugenol dissolved by 25 c.c. 90 per cent, alcohol at 17° C. as
determined by experiment.
This final quantity gives the amount of benzoyl eugenol, from which
the amount of eugenol is easily calculated, eugenol having the formula
C10H12O2, and benzoyl eugenol C17H16O3, so that o^?r~ x 100 = *ne per-
centage of eugenol, if x equals the weight of benzoyl eugenol obtained,
and y the weight of oil used in the estimation. Under these circum-
stances the eugenol-content should not fall below 75 per cent., or if
estimated by absorption with potash not below 82 per cent., usually
from 85 to 90 per cent.
Thorn has recognised the inaccuracy of the foregoing, and now
recommends the following process. It consists in heating 5 grms. of
the oil in a water-bath with 20 c.c. of a 15 per cent, soda solution for
thirty minutes. After allowing the hydrocarbons to separate, the
eugenol soda solution is run off, and the hydrocarbons washed with
dilute soda solution twice, the washings being added to the original
soda solution. The reaction is now effected at water-bath temperature
with 6 grms. of benzoyl chloride. The whole is allowed to cool, and
the crystalline mass transferred to a beaker with 55 c.c. of water. It
is heated in order to melt the crystals, and well agitated with the
water to wash the benzoyl eugenol. This washing is repeated twice.
'The crystalline mass is then transferred to a beaker with 25 c.c. of 90
per cent, alcohol, and warmed till complete solution takes place. The
solution is allowed to stand till the bulk of the crystals have separated
out, and is cooled to 17° and filtered through a paper 9 cm. in diameter,
previously dried and tared. The filtrate measures about 20 c.c. and
the crystals are washed with more alcohol until it measures 25 c.c.
The paper and crystals are then dried in a weighing-glass and weighed,
.the temperature of drying being not more than 101° C. The solubility
allowance for 25 c.c. of alcohol is 0*55 grm. The total eugenol is cal-
culated from the formula
^vhere P is the percentage, a the weight of benzoyl eugenol obtained*

and b is the weight of clove oil used.
Verley and Bolsing propose the following method. It depends on the
fact that acetic and other anhydrides react with phenols in excess of
pyridine. Eugenol reacts readily, forming eugenyl acetate and acetic
acid, the latter combining with pyridine to form pyridine acetate.
This compound reacts towards indicators such as phenolphthalein in
the same way as acetic acid and therefore a titration is possible. Ver-
ley and Bolsing use from 1 to 2 grms. of the oil, which is placed in a 200
c.c. flask, and 25 c.c. of a mixture of acetic anhydride (15 parts) and
pyridine (100 parts). The mixture is heated for thirty minutes on a
water-bath, the liquid cooled, and 25 c.c. of water added. The mixture
is well shaken and titrated with normal potash, using phenolphthalein
as indicator. A blank experiment is carried out without the eugenol,
and the difference between the titration figures in c.c. of normal alkali,
multiplied by 0*582, gives the amount of eugenol in the sample taken.
As the boiling-points of eugenol and caryophyllene are both high,
no appreciable portion of the oil should distil below 245°, or even a few
degrees higher. These tests will ensure the presence of a due propor-
tion of eugenol, a point very necessary to take into account, because of
MYETACB^ 335
the frequent abstraction of part of the eugenol, which is used in the
manufacture of vanillin, or sold as pure eugenol. Absence of turpentine
of petroleum is further ensured by the ready solubility of the oil in 90
per cent, alcohol.
The principal constituent of oil of cloves is the phenol eugenol,
together with about 3 per cent, of aceteugenol (or, according to Spurge,1
from 7 to 17 per cent.—which is unlikely). The sesquiterpene caryo-
phyllene contributes the principal "neutral" constituent of the oil.
Traces of esters of eugenol, methyl alcohol, furfurol, vanillin, salicylic
acid, methyl benzoate, amyl-methyl ketone, and heptyl-methyl ketone
have also been detected. The sesquiterpene caryophyllene exists in
both the a- and the /^-modifications. Valeric aldehyde is probably
present in traces.
A series of newly-discovered constituents, present in traces only,
has also been described by H. Masson.2 These bodies are as follows :
methyl-amyl-carbinol, methyl-heptyl-carbinol, benzyl alcohol, and di-
methyl-f urf urol.
A body termed caryophyllin, C10H16O4, has been stated to be present.3
The oil from clove stems does not differ materially in characters
from that of ordinary cloves. The specific gravity, however, may fall
as low as 1-040. The eugenol-content rarely falls below 85 per cent.
The stem oil has Jbeen found to contain traces of naphthalene, a sesqui-
terpene alcohol, C15H26O,4 and a crystalline body (C21H30O)55 (?), melt-
ing at 146°.
The oil from mother-cloves has been examined by Schimmel & Co.,
who found it to have the following characters:—
Specific gravity . . . . . . . . . 1-0933
Optical rotation . . - 3° 11'
Phenols . . . . . . . . . . 8 8 p e r cent.
The phenols consisted of a mixture of eugenol and a solid phenol
melting at 44° to 45'5°, and boiling (at 754 mm.) at 309° to 310°.
Clove leaves yield about 4 to 5 per cent, of oil having the following
•characters :—
Eugenol 75 to 93 per cent.
OIL OF EUGENIA SMITHII.

6
Dawkins has obtained 0*44 per cent, of oil from the leaves of this
tree. It has the following characters :—
(1) (2)
Specific gravity 0'866 0'863
Optical rotation +35° + 34 6°
It contains 80-90 per cent, of d-a-pinene, 4 per cent, of esters, and
3'7 per cent, of alcohols.
1 2
Pharm. Jour., 70 (1903), 701, 757. Comptes rendus, 149 (1909), 630, 795.
3 4
Monatshefte (1905), 379. Berichte, 45 (1912), 1392.
5
I6id.,42(1909), 380,680.
"Proc. Roy. Soc. Victoria, Chem. Abstracts, (1917), ii. 2715.
OILS OF EUCALYPTUS.
The oils distilled from the leaves of the various species of this*
enormous genus of the Myrtacea are in many cases so dissimilar that
the generic term, eucalyptus oil, is meaningless unless the species is
quoted. Several species, however, yield oils which are very similar to
each other, and on this basis the British Pharmacopoeia describes as
eucalyptus oil the product obtained from Eucalyptus globulus and other
species, giving definite characters of the oil, the two chief of which are
the presence of a due, proportion of cineol (eucalyptol) and the absence
of appreciable quantities of the terpene phellandrene. The great varia-
bility in the oil from different trees will make it convenient to deal with
this oil, firstly with reference to the cineol value, and afterwards with
especial reference to the characters of the oils from those trees which
in many cases are in no way similar to "Eucalyptus oil, British
Pharmacopoeia". It is commonly believed that whatever medicinal
value this oil has—and it has been, and still is, used to a very large
extent as a prophylactic against influenza—is due to the presence of
cineol, or, as it was previously called, eucalyptol, so that whether this
be, in fact, the valuable constituent or not, in commerce the value of
the oil is made to depend on its cineol-content.
The quantitative determination of the cineol present is a matter of
importance. The earlier attempts in this direction gave distinctly too
low results. The chief method adopted was a series of fractionations,
retaining all those fractions distilling between 173° and 190°, cooling
them to - 15°, filtering off the still liquid portion, retaining the
crystals of cineol, refractionating the liquid portions and again freez-
ing, subsequently weighing the crystallised cineol. An average
loss of about 10 per cent., in the author's opinion, takes place in
this process, assuming the oil to contain 50 to 60 per cent, of
cineol. Scammeirs process above-mentioned has been more success-
fully applied to the quantitative determination of cineol, and yields
the most satisfactory results so far, although an error- of several per
cent, is scarcely avoidable.
There is some diversity of opinion on this matter, some chemists
maintaining that a very close result is obtained, others that very large
errors occur. In the author's opinion, in the hands of a careful worker,
results accurate to within 3 per cent, can be obtained, so long as the
cineol-content is not below 40 per cent. If the amount of cineol is
lower than this, the method is inapplicable, and the oil must previously
be fractionated.
To a known weight of oil from 1 to 1-J- times its weight of phosphoric
acid of specific gravity 1'75 should be added, drop by drop, the oil
being kept cold and continually stirred. The crystalline magma
formed is pressed between filter paper, after as much as possible has
drained off; and when the adherent terpenes and phosphoric acid
have been removed as far as possible, the crystals are decomposed
by hot water in a graduated tube. On cooling, the cineol is measured,
and from its specific gravity (-930) the weight is easiiy calculated.
The separated cineol should readily crystallise on cooling to - 3°,
otherwise it must be regarded as impure and the process repeated.
Oils rich in cineol yield a correspondingly high fraction distilling
between 170° and 190°.
MYETACBJE 337
If the oil be first diluted with petroleum ether, before treatment

with phosphoric acid, the results are rather more concordant in the
hands of different analysts.
Schimmel & Co. recommend the absorption of the cineol by a 40 to>
50 per cent, solution of resorcin in water, and reading the unabsorbed
portion in the neck of a Hirschsohn flask.
Ten c.c. of the oil containing cineol are mixed in a cassia flask of
100 c.c. capacity with so much 50 per cent, resorcinol solution that the
flask is filled for about four-fifths. The mixture is shaken thoroughly
for five minutes, and the oil portions which have not entered into reac-
tion are brought into the neck of the flask by adding resorcinol solution,,
and their volume determined. By subtracting the volume from 10 the
cineol-content of the oil is obtained, which is then expressed in per
cent, by volume by multiplication with 10.
Messrs. Schimmel & Co. have since modified the method by recom-
mending the oil to be first fractionated and the portion boiling between.
170° to 190° C. to be treated with the resorcin solution. In some cases
this gives results fairly concordant with those of the phosphoric acid1
method usually adopted, as the following results will show:—
Cineol by Direct Cineol by Absorption Cineol by
Absorption with with Resorcin Phosphoric
• Resorcin Solution. after Fractionation. Acid Process.
Cajuput Oil, normal . 62 per cent. 54 per cent. 52 per cent.

„ ,, abnormal 53 17 14 „
Eucalyptus Oil I. 82 „ 68 „ 65 „
C. T. Bennettl has, however, shown that this method is quite un-

reliable, only yielding accurate results in certain isolated cases.
In other cases, however, the results obtained are obviously too high.
An oil which yielded 95 per cent, distilling between 170* to 190° C.,
all of which was absorbed by resorcin solution, had the following char-
acters :—
Specific gravity . . . . . . 0-924
Optical rotation Nil
Cineol by phosphoric acid method 78 per cent.
,, by resorcin method 95
Other samples gave results as under :—
Cineol by Cineol by Cineol by

Direct Absorption after Phosphoric
Absorption. Fractionation. Acid Process.
Eucalyptus Oil A . 100 per cent. 89 per cent. 70 per cent.

„ ,, B . Crystallised 97 75
„ „ C. 92 73
It is evident that this modified method is not absolutely accurate

since other constituents, besides cineol, are undoubtedly included in the
portion boiling between 170° and 190° C. A further objection is the
separation of the solid crystalline double compound with oils rich in
cineol.
. and E.O.E. (1912), 269.
VOL. I. 22
The method has been criticised by H. G. Harding,1 who states that
•a pure white oil from Eucalyptus dives, which contained no cineol,
showed an absorption of 32 per cent, by the resorcinol test. Kectifying
the oil and applying the test to the portion distilling between 170° and
190° does not entirely remove the difficulty, as the results are always
slightly high, owing to retention of other constituents by the resorcinol
solution. His experiments show that the method is more reliable when
the percentage of cineol does not exceed 40 to 50 per cent., oils contain-
ing a higher percentage requiring to be diluted. Ordinary turpentine
oil must not be used for dilution, as it is likely to produce serious errors.
By employing the fraction of turpentine distilling between 156° and 160°
for dilution the error is minimised, and the following method is recom-
mended : 100 c.c. of the oil to be tested is distilled, the portion distilling
between 170° and 190° collected, and this is diluted to 100 c.c. with the
turpentine fraction. If a trial shows the percentage of cineol to be
above 70 per cent., the cineol fraction is further diluted with the tur-
pentine so that the percentage is not over 50. The temperature is
noted, and 6 to 10 c.c. is shaken with warm 55 per cent, resorcinol
solution. After five minutes' shaking more solution is added so as to
bring the oil into the graduated neck. It is then cooled and the volume
read.
A method for the determination of cineol has recently been proposed
by Dodge.2
The process is based on the fact that the terpenes of the essential
oils to be examined are readily oxidised at 0° C. by a 5 to 6 per cent,
solution of potassium permanganate, whilst the eucalyptol remains un-
attacked. Ten c.c. of essential oils are gradually added to 400 or to 100 c.c.
of permanganate solution, according to whether the essential oil is more
or less rich in terpenes. When the reaction is finished, the solution
is allowed to stand in the cold for twelve to eighteen hours, with occa-
tsional agitation; sulphurous acid or a mixture of sodium sulphite and
hydrochloric acid is added and the oily portion of the residue is brought
iup into the neck of the flask, from which it is removed by means of a
slender pipette. This oil is washed with a little alkali, then transferred
to a graduated tube where its volume is determined which indicates the
percentage of eucalyptol.
This method cannot be relied on, as the action of potassium per-
manganate is such as to react with some and not with other bodies
present in various types of eucalyptus oil.
The whole question of cineoi determination in eucalyptus oil has
recently been carefully studied by Turner and Holmes,3 who .consider
that all methods so far published are either inaccurate or at best only
approximate. They suggest the following process :—
The determination of cineol in cineol-bearing oils by means of
arsenic acid is carried out as follows:—
Deliver from a pipette 10 c.c. of the oil into a glass dish (preferably
a round-bottom one) of 50 c.c. capacity, which is imbedded in finely
cracked ice. Add 10 c.c. of concentrated arsenic acid (containing about
j85 per cent, arsenic acid), and stir until precipitation is complete.
When the mixture ceases to congeal further, allow to stand ten minutes
in the ice. At this point if the mixture forms a hard mass, indicating
1 2
Analyst (1914), 475. 3
Jour. Ind. and Eng. Chem., 4, 592.
P. and E.O.R. (1915), 21.
MYETACE^ 339
an oil rich in cineol, 5 c.c. of purified petroleum ether should be added,
and the mass mixed well. Transfer immediately to a hardened filter
paper by means of a pliable horn spatula, spread evenly over the sur-
face of the paper, and lay a second hardened filter paper over the top.
Outside of the hardened filters place several thicknesses of absorbent
or filter paper, and transfer the whole to an ordinary letter-press, bring-
ing to bear all the pressure possible for about one minute. Change the
outside absorbent papers and press again, repeating the operation, if
^necessary, until the cineol arsenate is apparently dry and separates
'readily when touched with a spatula. The pressing is not complete
when a hard mass remains which is broken up with difficulty. The
method usually requires two changes of filter paper, pressing each time
for about two minutes. If left too long in the press the compound may
decompose. Now transfer completely the compound by means of the
horn spatula to a glass funnel inserted into a 100 c.c. cassia flask with
neck measuring 10 c.c., graduated in ^ c.c. Wash the precipitate
into the flask with a stream of hot water from a wash bottle, assisting
the disintegration with a glass rod. Place the flask in boiling water
and rotate until the compound is thoroughly broken up; add enough
water to cause the cineol to rise into the neck of the flask, cool to room
temperature, and read off the volume; on multiplying the latter by 10
the percentage of cineol in the oil is obtained.
In judging whether or not petroleum ether should be added the fol-
lowing rule should be observed: Add enough petroleum ether to soften
the cineol arsenate, so as to obtain a plastic mass; the quantity neces-
sary never exceeds 5 c.c., and decreases with oils containing less than
$0 per cent, of cineol. The object of adding petroleum ether is merely
to soften the hard mass and to aid in the separation of non-cineol con-
stituents of the oil; a large excess of petroleum ether will decompose
the compound.
The above method is applicable directly to all oils containing above
50 per cent, of cineol; in oils containing lower proportions of cineol
the precipitate is not solid enough to permit convenient handling; and
if the cineol-content drops below 25 per cent, the separation of cineol
arsenate is not quantitative. It was found that the addition of an equal
volume of eucalyptol to such oils (i.e. mixing 5 c.c. of the oil with 5 c.c.
of eucalyptol) successfully overcomes this difficulty; it then only be-
comes necessary to subtract from the volume of cineol, as observed in
the neck of the flask, 5 c.c., and to multiply the difference by 10, in
order to obtain the percentage of cineol in the oil.
In order to test the reliability of the method the authors prepared,
to begin with, various mixtures of cineol with turpentine oil, and as-
certained their cineol-content in the manner above described, with the
following results :—
1. 50 volumes per cent, cineol + 50 volumes per cent, turpentine
oil; found 49*5 per cent.; 50 per cent, cineol.
2. f 0 volumes per cent, cineol 4- 40 volumes per cent, turpentine
oil; found 59 per cent.; 60 per cent, cineol.
3. 75 volumes per cent, cineol + 25 volumes per cent, turpentine
oil; found 74 per cent.; 75 per cent, cineol.
The authors found that the application of the method to mixtures
containing less than 50 per cent, cineol is not practicable.
The latest method suggested for the determination of eucalyptol is
that of Cocking.1 It is based on the formation of a compound of ortho-2
cresol and eucalyptol, which was first obtained by Bellucci and Grassi.
This compound melts, according to Cocking, at 55*2°, and he attempts
to determine eucalyptol by noting the freezing-point of a mixture of $
grams of the oil and 2*1 grams of ortho-cresol. His experiments were
carried out with a mixture of pure eucalyptol and terebene, and with a
mixture of pure eucalyptol and oil of copaiba. But as eucalyptus oil
contains various other bodies, and further, since ortho-cresol freezes at
about 30° so that a varying mixture of the compound (cresineol), melting
at 55*2°, and ortho-cresol melting at 30°, is under consideration, it is-
obvious that such an empirical method cannot be relied on. Bennett
and Salamon 3 have examined this method, and consider that it is only
useful as a rapid method in a works for grading eucalyptus oils all
derived from the same variety of Eucalyptus.
Eucalyptus oil is produced principally in Australia and Tasmania,
which practically supply the world's requirements. Small amounts
are distilled elsewhere, as in Algeria, the South of France, Italy, Por-
tugal, the Transvaal, Mexico, etc., etc., but commercially they are of
little importance.
The systematic examination of the Eucalyptus oils of Australasia i&
almost entirely due to E. T. Baker and H. G. Smith, of the Technological
Museum, Sydney, N.S.W., and the greater part of the details here re-
corded is acknowledged to their numerous valuable publications. 4
From the purely commercial point of view the following notes will
indicate the direction in which distillation of the oil for the markets is.
tending:—
Economically the industry is becoming of some importance to
Australia. Most of the old species which used to do duty for oil pro-
duction have been replaced by others economically better in every way,
and the oil of Eucalyptus globulus only remains largely as a name, its.
pride of place being taken by the products of other species. Eucalyptus
dumosa, Eucalyptus oleosa, etc., have also fallen back as oil-producing
plants. The species now mostly worked for pharmaceutical oils in New
South Wales and Victoria are Eucalyptus polybractea, the " Silver-leaf
Mallee" of Victoria and the "Blue Mallee" of New South Wales;
Eucalyptus Smithii, which is a good yielding species and perhaps the
best of all eucalyptus oils for pharmaceutical purposes; and a recent
species, Eucalyptus Australians, which produces an excellent oil, and
no doubt will be much heard of in the future. This oil gave 79*5 per
cent, eucalyptol by the resorcinol method. It does not contain objection-
able volatile aldehydes except in traces, nor does it contain aromadendral.
In Research on the Eucalypts this species is referred to under Euca-
lyptus amygdalina, and it was there shown that if fractionally separated
during the original distillation the first-hour oil was richer in eucalyptol.
This discovery remained unused for over twelve years, but is now being
employed commercially in the Nerrigundah and Yourie districts of New
South Wales, where the phellandrene has been replaced by eucalyptol.
There are a few compounds which have been described as occurring in
eucalyptus oils, which are, so far as is known, not found in other oils.
3 2
3
P.and E.O.R., 1920, 282. Gazz. Chim. ItaL, 43, II., 712.
4
P.and E.O.R., 1920, 302.
Private communication from Mr. H. G. Smith to the author.
MYKTACEJE 341
Eudesmol, which has been also named eucalyptus camphor, was
first isolated from the oil of Eucalyptus piperital by H. G. Smith, who
found it to be a crystalline body melting at 79° to 80°, and having the
formula C10H16O, and being, in all probability, an oxide. Semmler and
Mayer,2 however, consider it to be a bicyclic sesquiterpene alcohol, and
this has since been confirmed by Semmler and Tobias,8 who give the
following as its characters :—
Melting-point . 78°
Boiling-point 156° at 10 mm.
„ rotation, + 31° 21' in chloroform solution
Refractive index , 1-5160 at 20°
Formula
The same chemists have also made an examination of the sesqui-
terpene4 alcohol isolated from oil of Eucalyptus globulus by Schimmel
& Co., which they have named globulol. This body has the following
characters:—
Melting-point 88-5°
Specific rotation - 35° 29' in chloroform solution
Formula ClaHM0
Smith 5 has also isolated a new aldehyde from certain eucalyptus
oils which he has named aromadendral. It has been suggested by
Schimmel & Co. that this was identical with cuminic aldehyde, which
had previously been found in eucalyptus oil by themselves. An ex-
amination of Smith's work on the subject, however, leaves no room for
such an assumption, and it is clear that aromadendral is not identical
with cuminic aldehyde.
Baker and Smith have recorded the following details (see pages
342-44), of 118 species of eucalyptus oils, arranged in groups according
to their dominating constituent.
Aromadendral was extracted fron the higher-boiling portion of the
oil of Eucalyptus rostrata by the aid of sodium bisulphite in the usual
manner. When purified it had an odour reminiscent of cumin aldehyde,
was almost colourless, being slightly yellow in appearance, and was
highly laevo-rotatory. The specific gravity at 20° C. = 0*9534; specific
rotation [a]D - 73*94°; refractive index at 20° = 1*5066; the oxime
melted at 84° to 85°, and the phenylhydrazone at 105° to 106° C. By
arranging these results in tabulated form with those of cuminaldehyde
the differences appear distinctly marked :—
Cuminaldehyde. Aromadendral.
d 15J C 0-9818 0-9569

Optical Rotation Nil [a]D - 73-94°
Melting-point Oxime 58° to 59° 84° to 85°
,, Phenylhydrazone . 126° ,, 127° 105° „ 106°
Refractive Index at 20° 1-5066
1
Jour. ofProc. Roy. Soc., N.S.W., 33 (1899), 86. *Berichte, 45 (1912), 139Q.
4
3 Ibid., 46 (1913),
5
^026. Report, April, 1904, 51.
Jour. ofProc. Roy. Soc., N.S.W., 34 (1900), 1.
EUCALYPTOL-PINENE OlLS. 9
Specific Solubility
Refractive Specific Refractive in(-8722
Alcohol 10 Times
at Solubility
No. Species. Index Gravity Energy x Refrac-
w n<t — 1
d 16° 0. Volume tive Index.
d. Requires
1 E. Smithii . 1-4706 •9238 •5094 1-05 15-44

Do., oil of *' suckers" . 1-4707 •9151 •5144" 1-15 16-91
Do., com. crude 5-03 1-4689 •9172 •5112 1-05 15-42
2 E. Bridgesiana 1-4723 •9327 •5064 1-05 15-46
3 „ Risdoni . 1-4733 •9373 •5049 1-05 15-47
4 ,, pulverulenta 1-4688 •9280 •5049 1-1 16-15
5 ,, dealbata . 1-4705 •9268 •5077 1-1 16-17
6 ,, stricta 1-4711 •9254 •5090 1-1 16-18
7 ,, polyanthema 1-4736 •9346 •5067 1-1 16-21
8 „ oleosa1 1-4746 •9319 •5093 1-1 16-22
9 , cordata 1-4695 •9265 •5067 1-15 16-89
10 , citwrea 1-4706 •9198 •5116 1-15 16-91
11 , populifolia 1-4709 •9246 •5093 1-15 16-91
12 , Cambagei* 1-4720 •9243 •5106 1-15 16-92
13 , sideroxylon 1-4725 •9219 •5125 1-15 16-93
14 , pendula 1-4732 •9337 -5068 1-15 16-94
15 , bicolor 1-4734 •9266 •5109 1-15 16-94
16 , Maideni .1 1-4736 •9253 •5117 1-15 16-94
17 , cneorifolia 1-4747 •9194 •5163 1-15 16-96
Do., F. & Co., crude 1-4774 •9375 •5092 1-1 16-25
18 E. maculosa . 1-4741 •9278 •5109 1-17 17-24
19 ,, Morrisi 1-4693 •9191 •5106 1-2 17-63
20 ,, squamosa1 1-4692 •9202 •5099 1-2 17-63
21 ,, globulus . 1-4720 •9243 •5106 1-2 17-66
Do., Platypus bd. 4 years 1-4697 •9153 •5131 1-15 16-90
Do., do., 8 years old 1-4738 •9392 •5044 1-15 16-95
22 E. polybractea l 1-4736 •9197 •5149 1-2 17-68
Do. commer. dist. 6-04 . 1-4686 •9286 •5046 1-0 14-68
Do., do., crude dist. 7-05 1-4692 •9282 •5055 1-05 15-42
Do., same oil rectified . 1-4676 •9254 •5053 1-05 15-41
23 E. hemilampra 1-4735 •9310 •5086 1-2 17-68
24 ,, longifolia . 1-4738 •9249 •5122 1-2 17-68
25 ,, inter texta . 1-4748 •9323 •5092 1-2 17-69
26 ,, Behriana . 1-4765 •9272 •5139 1-2 17-72
27 „ Stuartiana 1-4709 •9194 •5122 1-25 18-38
28 ,, eugenioides 1-4747 •9220 •5148 1-25 18-43
29 , amygdalina 1-4760 •9104 •522 S 1-25 18-45
30 , punctata a . 1-4774 •9297 •5135 1-25 18-46
31 , Rossii 1-4741 •9202 •5152 1-35 19-90
32 , resinifera . 1-4755 •9194 •5172 1-35 19-91
33 , Seeana 1-4706 •9146 •5145 1-37 20-14
34 , camphora . 1-4733 •9072 •5217 1-4 2062
35 , rostrata var. borealis 1-4747 •9251 •5131 1-4 20-64
36 , viminalis var. (a) 1-4711 •9169 •5138 1-45 21-33
37 , goniocalyx 1-4746 •9097 •5218 1-8 26-54
38 , ovalifoliav.lanceolata 1-4711 •9119 •5166 2-0 29-42
39 , salmonophloia l 1-4738 •9069 •5225 3-5 51-58
40 , quadrangulata . 1-4692 •9075 •5170 4-0 58-76
41 , Bosistoana 1-4732 •9175 •5158 5-0 73-66
42 , melliodora 1-4706 •9041 •5205 6-0 88-23
43 , redunca 1-4720 •9092 •5191 6-0 88-32
44 , conica 1-4733 •9259 •5112 6-0 88-39
1
45 , propinqua 1-4788 •9035 •5299 8-0 118-30
46 , odorata1 (Faulding) . 1-4775 •9150 •5218
47 , occidentalis 1 1-4774 •9128 •5230 "l1 rH ^
48
'49
, dumosa .1
, microcorys
1-4760
1-4747
•9130
•9059
•5213
•5240
lie*
I ^Q ta ,T3 LsjS's
.
50 , gracilis1 . 1-4771 •9107 •5239 I 'o 2 £

r? °^
ro 1 -^
51 , paludosa . 1-4773 •9095 •5248 I hH *O p0^
J > J >
1
Denotes the presence of a small amount of aromadendral in the oil.
MYETACE^ 343
PINENE OILS ; PHELLANDRENE ABSENT.
Specific
Refractive Specific Refractive
No. Species. Index Gravity Energy
na 16° C. H° C. na-l !
d.
52 E. botryoides 1-4787 •8802 •5439 None soluble in less

53 ,, calophylla 1-4788 •8751 •5471 than 7 volumes
54 ,, dextropinea 1-4741 •8806 •5383 of 80 per cent.
55 ,, diver sicolor 1-4747 •9134 •5197 alcohol.
56 ,, lavopinea . 1-4769 •8964 •5320
57 ,, saligna 1-4760 •8940 •5324
58 ,, Wilkinsoniana . 1-4774 •9016 •5295
PlNENE-SESQUITERPENE OlLS J PHELLANDRENE ABSENT.
59 E. affinis l 1-4921 -9270 -5301 None soluble in less
60 ,. apiculata . 1-4934 -9123 -5408 than 1 volume 80
61 ,, Bacuerleni . . 1*4841 •8890 i -5445 per cent, alcohol ;
62 „ corymbosa1 . . \ 1-4895 •8867 -5520 the majority in-
63 ,, eximia . . . 1-4889 •8999 -5433 soluble in 10 vol-
64 ,, intermedia x . . 1'4878 •8838 -5519 umes 80 per cent.
65 , lactea . . . 1-4898 •8794 -5570 alcohol.
66 , maculata . . . 1-4861 •9035 -5380
67 , nova-anglica . . 1*4900 •9062 -5407
68 , paniculata . . 1*4801 •9096 -5278
69 , patentinervis . . 1-4948 •8784 -5633
70 , rubida . . . 1-5011 •9089 -5513
71 , tesselaris . . . 1-4881 •8962 -5446
72 , trachyphloia 1 . . 1-4901 •8915 -5497
OILS IN WHICH AROMADENDRAL is A PRONOUNCED CONSTITUENT ;
PHELLANDRENE is ABSENT.
73 E. albens 1-4836 -9188 -5263 With the exception
74 , liemiphloia 1-4910 •9084 •5405 of No. 74, all are
75 , marginata 1-4946 •9112 •5428 soluble in either
76 , punctata var. didyma 1-4868 •9068 •536S 1 or 2 volumes
77 , rostrata 1-4896 •9018 -5429 of 80 per cent.
78 , salubris 1-4841 •9013 -5358 alcohol.
79 , tereticornis 1-4934 •9308 i -5301
80 , viridis 1-4828 •9027 -5348
81 , Woollsiana 1-4895 •8998 -5440
PHELLANDRENE OILS CONTAINING PIPERITONE.

Specific
nd 16° C. ir c. no, - 1
d.
82 E. coriacea . 1-4902 •9120 •5375 Mostly i

83 ,, delegatensis 1-4881 •8645 •5646 10 volu
84 , dives 1-4894 •8883 •5509 cent, al ;ohol; none
85 , fraxinoides 1-4908 •8762 •5601 more sc >luble than
86 , Luehmanniana 1-4937 •8846 •5581 with 1 volume 80
87 , obliqua 1 . 1-4934 -8944 •5528 per cen
88 , oreades 1-4945 •8935 •5534
89 , piperita 1-4838 •9221 •5247
90 , radiata 1-4863 •8814 •5517
91 , Sieberiana 1-4886 •8947 •5461
92 , vitrea 1-4882 •8967 •5384
1
PHELLANDKBNB OILS IN WHICH THE SESQUITEBPENE is A PRO-
NOUNCED CONSTITUENT.
Specific
ndl6° C. H°C. nd— I
d.
93 I J. acmenoides 1-5056 •9266 •5466 No. 102 is the only

94 angophoroides . 1-4881 •9207 •5301 oil more soluble
95 capitellata 1.4828 •9176 •5261 than with 1 vol-
96 crebra 1-4844 •8989 •5388 ume 80 per cent,
97 Dawsoni . 1-5144 •9528 •5399 alcohol ; a large
98 fastigata l . 1-4873 -8948 •5446 number were in-
99 Fletcheri 1-4881 •8882 •5495 soluble in 10 vol-
100 gomphocephala. 1-4815 •8752 •5501 umes 80 per cent,
101 TicBmastoma 1-5013 -9196 •5451 alcohol.
102 m€tcrorrhyncha 1-4802 •9166 •5239
103 melanophloia . 1-4950 •8959 •5526
104 microtheca 1-4895 -8866 '•5521
105 nigra 1-4871 -8838 •5511 •
106 ovalifolia . 1-4921 •8911 •5522
107 Planchoniana . 1-4878 •9166 •5322
108 pilularis . 1-4961 •8924 -5559
109 robusta 1-4801 •8899 -5395
110 siderophloia 1-5000 •9081 •5506
111 sideroxylon v.pallens 1-4884 •9167 •5328
112 stellulata . 1-4902 •8766 •5589
113 viminalis . 1-4855 •9088 •5342
114 virgata 1-5015 •9352 •5363
OILS NOT CLASSIFIED ; CONTAINING GERANIOL AND ITS ACETIC ACID
ESTER, CITRAL, CITRONELLAL, ETC.
115 E. citriodora . 1-4651 •8887 •5233 Soluble in 1'5 vote.
Do. Mr. Ingham, Qld. 1-4678 •8829 •5298 70°/ 0 alco.atl6°C.
116 E. Macarthuri 1-4793 •9271 •5172 Soluble in 1-3 vol-
Do. cont. 64-73% ester 1-4763 •9252 •5148 umes 70% alcohol.
Do. cont. 68 -8% ester 1'4768 •9287 •5134
117 E. Staigeriana 1-4871 •8708 •5594 Insoluble in 6 vol-
umes 80°/0 alcohol.
118 „ aggregata . 1-5062 •9701 •5128 Insoluble in 10 vols.
80% alcohol.
H. G. Smith 2 has also isolated a sesquiterpene, which is present in

many eucalyptus oils in the portions boiling at above 255°, and which,
in the oil of Eucalyptus hamastoma, represents as much as 50 per cent,
of that fraction. It does not yield crystallised derivatives, but, on the
other hand, when dissolved in glacial acetic acid, it gives characteristic
colour-reactions with acids and also with bromine. When submitted
to the action of bromine vapour the oil acquires first a crimson-red
colour, then violet, and finally indigo-blue. The sesquiterpene, prepared
as pure as possible by fractional distillation, boils at atmospheric pres-
sure at 260° to 265°, and has at 19° the specific gravity O9249. Smith
proposes for the sesquiterpene the name " aromadendrene ".
This sesquiterpene, according to Schorger,3 may also be present in
the turpentine oil from Pinus Lambertiana.
1
2
3
Jour, of Proc. Roy. Soc.,N.S.W.t 35 (1901), 124.
U.S. Dept. Agric. Forest Service, Bull. 119.
MYETACBÊ 345
A ketone has also been isolated from the oil of Eucalyptus dives
ivhich Smith has termed piperitone. This body, of the formula
•C10H18O, has the following characters :—
On reduction with sodium it yields an alcohol, C10H18O, melting at
155° to 156°.
Finally, Eobinson and Smith J have separated a phenol from the oil
•of Eucalyptus linearis, which they have named tasmanol.
The phenol was removed from the crude oil in the usual manner by
shaking with aqueous sodium hydrate, washing the aqueous solution
with ether to remove adhering oil, acidifying and extracting with ether.
'The residue, which contained a small amount of acetic and butyric acids,
was washed with dilute sodium carbonate, extracted with ether, the
•ether removed and the phenol distilled. It boiled at 268° to 273° C.
(uncor.) and at 175° under 25 mm. pressure. It was optically in-
active, the specific gravity at 23° was 1*077, and the refractive index at
:22° was 1*5269. Besides being soluble in the alkalis the phenol is
soluble in ammonia, partly soluble also in sodium carbonate but not
in bicarbonate. It also dissolves slightly in boiling water. The re-
action with ferric chloride in alcoholic solution is characteristic, the deep
red colour which is first formed remaining persistent for days, after the
alcohol has evaporated. The odour reminds one somewhat of carvacrol
Tinder certain conditions. It contains one methoxy group and appears
ito have two phenolic groups in the para position to each other.
The following are the principal varieties of eucalyptus oil that have
been described:—
OIL OF EUCALYPTUS ACACI^FORMIS.
This tree is the narrow-leaved peppermint gum of New South Wales.
It contains d-pinene, aromadendrene, and geranyl acetate (?).
OIL OF EUCALYPTUS ACERVULA.

This eucalyptus is a Tasmanian tree, and is also found in South
.Australia. The oil has the following characters:—
Eucalyptol 21 per cent.
Yield 0-212
It contains d-pinene, phellandrene, eucalyptol, geraniol, geranyl
.acetate, a liquid paraffin hydrocarbon, and a solid (paraffin?) stearop-
.ten%melting at 55° to 56°.
1
Jour, of Proc. Boy. Soc., N.S.W., 48 (1914), 518.
OIL OF EUCALYPTUS ALBENS.
This tree is found principally in South Australia, Its oil has the fol-
Optical rotation . - 6-5°
Refractive index. 1-4780 at 20°
Eucalyptol. . 30 per cent.
Yield . . . 0*1
The oil contains eucalyptol, pinene, aromadendral, and esters.
OIL OF EUCALYPTUS ACMENOIDES.
This tree is the white mahogany of Queensland and New South;
Wales. The oil contains phellandrene, aromadendrene, pinene (?), and-
eucalyptol. It has the following characters :—
Yield 0-09 per cent.
OIL OF EUCALYPTUS AGGREGATA.

This tree is found in New South Wales, the oil having the following;
characters:—
Ester value . 112-2
Yield . . 0-04 per cent.
It contains d-a-pinene, and the amyl ester of eudesmic acid.
OIL OF EUCALYPTUS AMYGDALINA.
In commerce the oil known as Eucalyptiis amygdalina is understood!
to be an oil containing much phellandrene and very little eucalyptol. It
is an oil having a specific gravity about 0-855 to 0'885 and an optical
rotation of from - 25° to - 80°. This oil of commerce is probably the dis-
tillate from various species, especially from Eucalyptus dives. But as
the oil is one of great importance in commerce, where it is used to a con-
siderable extent for the purpose of " floating" mineral ores in separation,
processes, it is important that the exact nature of the true amygdalina
oil should be understood. The matter has been finally cleared up by
Baker and Smith,1 who give the following account of the tree and its
oil:—
"Historical.—This eucalyptus was described by Labillardier in his-
Plants of New Holland (1806).
"Remarks.—This name, Eucalyptus amygdalina, has almost since
the beginning of Eucalyptology been associated with the Tasmanian
flora, for it was from Van Diemen's Land that Labillardier obtained his
specimens. It is, however, with much reluctance that we announce that
we have failed to find this tree on the mainland of Australia.
" The tree passing as Eucalyptus amygdalina in the Eastern Stetes 2
3 1
Eiiealypts of Tasmania (1912), p. 62. Vide under Eucalyptus Australiana..
MYKTACE^ 347
is of medium size with a ' Peppermint' bark, opposite, sessile, cordate-
lanceolate ' sucker ' leaves, medium-sized lanceolate normal leaves, small
hemispherical fruits with a truncate or depressed rim, and the leaves
yielding a particular oil.
" As far as our researches go, trees having these characteristics do not
appear to occur in Tasmania, where the name was originally ascribed to
this species. Thus the trees going under the name of Eucalyptus amyg-
dalina in Tasmania and Eucalyptus amygdalina in Victoria and New
South Wales are not the same.
" As, however, the name has become so interwoven with the euca-
lyptus literature of Victoria and New South Wales in connection with
the economics of the tree found there, it is now almost next to impossible
to supersede the name of the tree of the Eastern States, or at least
without adding to the already long nomenclature of the genus.
" That the latter is not Labillardier's tree we are firmly convinced,,
and on the following grounds :—
" 1. The plate of Eucalyptus amygdalina of Labillardier in his Plant*
of New Holland depicts the Tasmanian Eucalypt, and certainly not the
mainland one.
" 2. The ' sucker' leaves of the former are petiolate, alternate, and
the latter opposite, sessile, cordate, obtuse.
" 3. The normal leaves of the former are smaller, and narrower.
" 4. The fruits of the Tasmanian tree are practically identical in
shape with those of Eucalyptus dives Sch., and not hemispherical like
those of the mainland Eucalyptus amygdalina.
" 5. The oil of the Tasmanian tree closely approaches in chemical
composition that of Eucalyptus dives Sch.
" Labillardier's name for the Tasmanian tree must, of course, stand,,
as that has priority, and to us it appears too late in the day to alter the
specific appellation of the other; but if a systematic distinction is neces-
sary in future, we would suggest that it might be known, to botanists at
least, as Eucalyptus amygdalina, var. Australiana. This form is faith-
fully figured by Mueller in his Eucalyptographia, and is also illustrated
by us in our work Eucalypts and Their Essential Oils (p. 168). The
varieties recorded by Bentham, we find, belong to Eucalyptus Eisdoni
rather than Eucalyptus amygdalina.
"Essential Oil.—Material of this species—known as 'Black Pepper-
mint '—was received from various localities in Tasmania, collected at
various times of the year, in order that definite conclusions might be
formed as to the specific differences between the oil of Eucalyptus amyg-
dalina of Tasmania and that of the. tree known in New South Wales
and Victoria as Eucalyptus amygdalina. Although the general character
of the oil of the Tasmanian tree places it in the ' amygdalina group ' of
these oils, yet it differs considerably from that of the New South Wales
form, and more closely approaches in constituents and physical pro-
perties the oil of Eucalyptus dives, with the exception that the Tas-
manian Eitcalyptus amygdalina contains a little more eucalyptol than.
does that of Eucalyptus dives. Commercially the oil could be utilised
for purposes similar to those to which that of Eucalyptus dives is put,
but it would not pay to submit it to fractional distillation in order to-
separate the eucalyptol portion, as is now often carried out with the oil
of the New South Wales form, any more than it would pay to do so-
with the oil of Eucalyptus dives. The yield of oil of the New South-
Wales form of Eucalyptus amygdalina is almost twice that obtained
with the Tasmanian trees, and even Eucalyptus dives appears to yield a
greater quantity of oil than does the Eucalyptus amygdalina of Tasmania.
The oil of the Tasmanian Eucalyptus amygdalina differs from that of
ihe New South Wales form in that it contains much less eucalyptol, has
a very high laevo-rotation, contains more phellandrene, and is much less
rsoluble in alcohol. The odour of the oil is also much less aromatic."
Optical rotation - 59-1° „ - 75-1°
Befractive index 1-4761 to 1-4790 at 18°
Eucalyptol . 12 „ 24 per cent.
Yield . 1-62 „ 2-04
The chief constituents of the oil are phellandrene, eucalyptol, piperi-
tone, and a sesquiterpene.
OIL OF EUCALYPTUS ANDBEWSI.
This oil is obtained from a tree growing in the north-east of New
South Wales. It has the following characters :—
Ester number . . . . . . . . . 4*3
Yield 1*27 per cent.
It contains Z-phellandrene, piperitone, and a sesquiterpene.
OIL OF EUCALYPTUS ANGOPHOROIDES.
This tree is found in New South Wales. The oil has the following
characters :—
Befractive index 1'4881 at 16°
It contains phellandrene, pinene, eucalyptol and a sesquiterpene.
OIL OF EUCALYPTUS APICULATA.
Eiicalyptus apiculata is a New South Wales tree, the leaves of which
yield O65 per cent, of essential oil containing pinene, piperitone, and a
small amount of eucalyptol, and having the following characters :—
Optical rotation - 8-6° „ - 9'3°
Saponification value 8*7 to 10-1
OIL OF EUCALYPTUS AUSTKALIANA.

The tree described up till 1915 under the name Eucalyptus amyg-
dalina, growing on the Australian mainland, was referred to under that
oil. The importance of the oil sold under that name in commerce war-
rants an exhaustive examination of the scientific nomenclature of the
trees bearing the name. This has now been undertaken by Baker
MYKTACE^B 349
and Smith,1 who have now re-named the mainland tree Eucalyptus
Australiana.
When these scientists studied theEucalypts of Tasmania, Labillardier's
. species of Eucalyptus amygdalina necessarily received much attention,
as it was from that island he obtained his material, which, of course,
stands as the authenticated species. The name, however, has long since
been also given to a tree on the mainland, and it was only when investi-
gating the species for the above research, that differences were detected
in the two trees, and these have since been followed up. In fact, the
differences were so marked that even then they raised the continental
form to varietal rank under the name of Eucalpytus amygdalina, var..
Australiana, being loath to introduce another species name to the already
long list of eucalypts. They were prepared to let it stand at that, but
the technology of this eucalyptus has since come so much to the front
in the commercial world, that they considered it best in the interest of
applied, as well as pure science, to give it specific rank, for which they
propose the name Eucalyptus Australiana for the mainland tree.
The probability of this oil becoming one of the most important pro-
ducers of eucalyptus oil induced the authors to investigate it very fully.
They were able to show that, by fractional separation at stated times
during the primary distillation, an oil richer in eucalyptol could be ob-
tained, particularly if the portion which came over during the first hour
was separated. The eucalyptol was thus more easily distilled than the
alcoholic bodies and other oil constituents in the leaf. By taking ad-
vantage of this peculiarity, and working the trees growing at Nerri-
gundah, Yourie, and neighbouring districts of New South Wales in the
same way, it has been possible to produce a product of a fairly constant
character, high in eucalyptol-content, and answering to the requirements
demanded for a first-class pharmaceutical eucalyptus oil. The results
have been so satisfactory that the species is, at the above localities, now
worked in this way, the first-hour oil being sold for pharmaceutical pur-
poses, the remainder being employed for mineral separation and for other
industrial uses.
The remarkably high yield of oil given by this species enables this
mode of working to be profitably undertaken, and the amount obtained
during the first hour is almost as great as that from many other cineol-
producing species when these are distilled right out. The second-hour
oil thus becomes practically a subsidiary product. Little advantage ap-
pears to be derived from distilling the leaves for a longer period than
two hours, as the amount of oil thus obtained is but small. The first-
hour oil, when properly prepared, is almost water-white, which fact ap-
pears to be due to the presence of the phenol, tasmanol—common to-
ting class—containing a methoxyl group, a constitution which does not
permit the formation of a quinone, as is the case with the oils of the
other large class of cineol-producing eucalypts. The amount of volatile
aldehydes in the crude oil is but small, so that altogether no rectification
of the first-hour oil is needed before placing it on the market.
The crude oil has the following characters :—
Eucalyptol . . 70 per cent.
1
Jour. Proc. Roy. Soc., N.S.W., xlix., 514.
The oil contains eucalyptol, piperitone, esters, and some free alcohols,
as well as the phenol tasmanol.
The following analyses are of the first-hour distillates, which are
being put on the market for medicinal purposes :—
Specific Gravity Rotation Solubility in Refractive

70 per cent. Index Cineol.
at 15° C. Alcohol. at 20° C.
Vols.
0-9188 + 1-7° 1-1 1-4614 Over 70 per cent.
0-9188 + 0-3° 1-1 1-4621 »» »»
0-9190 (-0*0° 1-1 1-4622 »i »>
0-9190 + 1-3° 1-1 1-4633 75 per cent, phosphoric acid method.
0-9200 + 1-5° 1-05 1-4627 Over 70 per cent.
0-9193 + 0-9° 1-1 1-4628 84 per cent, resorcinol method.
0-9186 +0-5° 1-05 1-4624 Over 70 per cent.
0-9186 -0-5° 1-1 1-4620 69-5 per cent, phosphoric acid me-
thod.
0-9195 + 0-4° 1-1 1-4622 Over 70 per cent.
0-9198 + 0-3° 1-1 1-4617
0-9191 + 1-3° 1-1 1-4633 73 per cent, phosphoric acid method.
0-9193 + 1-5° 1-15 1-4631 Over 70 per cent.
0-9199 + 0-1° 1-1 1-4622 »» »
0-9202 -1-2° 1-15 1-4636 71 per cent, phosphoric acid method.
0-9211 + 1-4° 1-1 1-4628 74 ,? „ ,,
0-9179 + 1-6° 1-15 1-4632 Over 70 per cent.
0-9195 + 1-4° 1-1 1-4631 »» »>
0-9196 + 1-2° 1-1 1-4625 81 per cent, resorcinol method. 77
per cent, by phosphoric acid me-
thod.
The second-hour's distillate and the third-hour's distillate are quite

similar to each other. They contain about 30 per cent, of eucalyptol,
together with the less desirable constituents of the oil.
OIL OF EUCALYPTUS BÛERLENI.

This tree is the brown gum of New South Wales, Its oil has the
It contains pinene, eucalyptol, eudesmol, and aromadendrene.
OIL OF EUCALYPTUS BAILEYANA.
This is one of the numerous trees known locally as " stringy bark,"
and is confined chiefly to the north of New South Wales and the ad-
jacent southern portion of Queensland. The leaves yield about 1 per
xsent. of oil, of a melissa-like odour, which, however, is partially covered
by the cineol present. Its specific gravity is variable, usually about
0*940. It appears to contain up to 25 or 30 per cent, of cineol, some
mitral, and phellandrene.
MYETACE^B 351
OIL OF EUCALYPTUS BEHEIANA.
This tree is one of the Mallees of New South Wales, South Australia,
.and Victoria. It yields an oil having the following characters :—
Specific gravity . . . . Q'9237
Optical rotation . . . . + 3-7°
Refractive index . . . . 1-4709 a t 2 0 °
Eucalyptol . . . . . 4 8 p e r cent.
Yield . 0-61
It contains eucalyptol, pinene, and phellandrene.
OIL OF EUCALYPTUS BICOLOR.
Eucalyptus bicolor is known as the Bastard Box. The oil has the
following characters):—
Specific gravity- 0-9259
It contains eucalyptol and a sesquiterpene.
OIL OF EUCALYPTUS BOSISTOANA.
This tree is also known as a Bastard Box in Victoria. The oil has
Specific gravity . . . 0-9078
Yield 0-97
It contains eucalyptol, pinene, and aromadendrene.
OIL OF EUCALYPTUS BOTBYOIDES.

This tree is the Bastard Mahogany of Victoria and Queensland.
The oil contains d-a-pinene, aromadendrene, and traces of eucalyptol.
Saponification value 15 to 21
Optical rotation + 23 -9°
Yield O'l per cent.
OIL OF EUCALYPTUS BBIDGESIANA.

This is the Gippsland woolly-butt of Victoria. Its oil has the fol-
Optical rotation ,
+ 1 O
I .00
,,
,
+ O O
O.QO
Refractive index 1-4716 to 1-4729 at 20°

Eucalyptol. 73 „ 78 per cent.
Yield . 0-57 „ 0-75 „
OIL OF EUCALYPTUS CALOPHYLLA.

This tree, the Western Australian Bloodwood, yields an essential oil
-with the following values :—
Ester value 10-5
It contains d-pinene, aromadendrene, traces of eucalyptol, and acetic
esters. Cymene is probably present.
OIL OF EUCALYPTUS CAMBAGEI.
This tree is another of the so-called Bastard Boxes of New South
Wales and Victoria. The oil has the following characters :—
Optical rotation - 0-6° „ + 5-6°
Yield 0'83 per cent.
It contains eucalyptol, pinene, aromadendral, and eudesmol.
OIL OF EUCALYPTUS CAMPANULATA.
This tree is the Bastard Stringy Bark of New South Wales. The
oil contains eucalyptol, piperitone, and eudesmol, with a large amount
of phellandrene, and has the following characters:—
«
OIL OF EUCALYPTUS CAMPHOBA.
This tree is the Swamp Gum of Victoria and New South Wales.
Its oil has the following characters :— *
Saponification value . . . . . . . 4-4
The oil contains 50 per cent, of eucalyptol, pinene, and eudesmoL
OIL OF EUCALYPTUS CAPITELLATA.
This oil has the following characters:—
Yield 0-1 „
It contains eucalyptol, pinene, phellandrene, and a sesquiterpene.
OIL OF EUCALYPTUS CAENEA.
This oil has only been partially examined. It consists chiefly of
d-a-pinene with traces of eucalyptol.
MYETACEÊ 353
OIL OF EUCALYPTUS CINEBEA.
This tree is the Argyle Apple of New South Wales. The oil has the
Optical rotation + 24° „ + 4-25°
Yield 1 to 1-3 „
It contains eucalyptol, pinene, and esters.
OIL OF EUCALYPTUS CITBIODOBA,
This tree, the "citron-scented" eucalyptus, is found along the coast
of Queensland and as far south as Port Jackson. It has been described
as a variety of the New South Wales " spotted gum," Eucalyptus macu-
lata (which itself possesses very little odour), but Baker and Smith con-
sider it to be a separate species. This variety yields a typical scented
eucalyptus oil, having the following characters :—
Optical rotation - 1° „ -f 2°
It contains a very large quantity of citronellal, one specimen, accord-
ing to Schimmel & Co., having been found to contain as much as 95 per
cent. It also contains geraniol and traces of pinene. This oil is of a
most pleasant odour, and is admirably suited for soap perfumery, pos-
sessing a far more delicate odour than ordinary citronella oil, which it
somewhat resembles in its general characteristics.
OIL OF EUCALYPTUS CNEOBIFOLIA.
This eucalypt, one of the Mallees, is chiefly found in Kangaroo
Island, South Australia. It is a comparatively small plant, seldom
reaching more than 12 to 15 ft. in height. It is known locally as the*
" narrow-leaved eucalyptus". The plant was originally looked upon
as a variety of Eucalyptus oleosa, but it is now understood to be a
separate species. The oil came into commerce some few years ago
under the name of oleosa, but is quite different from the oil which was
originally known under the same name. The oil is very rich in cineol
and has the following characters :—
Optical rotation - 3-5° ,, - 12-5°
It has a secondary odour recalling that of cumin. It contains from
50 to 70 per cent, of eucalyptol and a small quantity of aromadendral
and a sesquiterpene. This oil is much valued as a medicinal oil, and
usually conforms admirably to pharmacopoeial requirements.
OIL OF EUCALYPTUS COCCIFEBA.
This oil, a Tasmanian eucalypt, has the following characters :—
Optical rotation _ 35*8°
VOL. I. 23
It contains phellandrene piperitone, eudesmol, and traces of euoa-
lyptol.
OIL OF EUCALYPTUS CONICA.
This oil has the following characters :—
It contains pinene, traces of aromadendral, and 40 per cent, of euca-
lyptol.
OIL OF EUCALYPTUS GOBDATA.
This tree is a Tasmanian eucalypt, the oil having the following
characters :—
Bucalyptol . . . . . . . . . 6 2 p e r cent.
Yield 2-32 „
OIL OF EUCALYPTUS COBIACE^J.

This tree is the white gum of most of the Australian Colonies. Its
oil ihas the following characters :—
Yield 0-45
It contains phellandrene, piperitone, eucalyptol, and a sesquiterpene.
OIL OF EUCALYPTUS COKYMBOSA.
This tree is the New South Wales and Queensland Bloodwood. Its
It contains pinene, eucalyptol, and aromadendral.
OIL OF EUCALYPTUS COSMOPHYLLA.
This tree is a South Australian eucalypt, whose oil has the following
characters:—
Saponification value . . . . . . . 5-6
Yield 0-62 „
It contains pinene, eucalyptol, aromadendral, and sesquiterpenes.
MYBTACEÊ 356
OIL OF EUCALYPTUS CBBBEA.
This tree is the narrow-leaved iron bark of several of the Australasian
Colonies, and is found in India. The oil has the following char-
acters :—
Optical rotation - 3° to - 10*9°
It contains phellandrene, eucalyptol, and aromadendrene.
OIL OP EUCALYPTUS DAWSONII.
This tree is the New South Wales Staley gum, and its oil contains
aromadendrene as its principal constituent. It has the following char-
acters :—
Specific gravity . . . . . . . . 0*9418
Refractive index 1'5144 at 16°
It contains phellandrene and eucalyptol, as well as aromadendrene.
OIL OF EUCALYPTUS DEALBATA
This tree is found in New South Wales and Queensland. The oil
OIL OF EUCALYPTUS DELEGATENSIS.
This tree is the gum-topped stringy bark of Tasmania, New South
Wales, and Victoria. The oil has the following characters:—
Yield 1*3 to 1*9 per cent.
It contains phellandrene, piperitone, and a sesquiterpene.
OIL OF EUCALYPTUS DEXTROPINEA.
This tree is one of the stringy barks of New South Wales. The oil
The oil contains a considerable amount of d-a-pinene, a small amount

of eucalyptol, and a little geranyl acetate.
OIL OF EUCALYPTUS DIVBBSICOLOE.
This tree is a Western Australian Karri. The oil has the following
characters:—
Ester value 53*2
It contains d-pinene, eucalyptol, and acetic esters.
OIL OF EUCALYPTUS DIVES.
This tree is found in Victoria and New South Wales, and is known
as the broad-leaved peppermint. It is the tree which was originally
known as Eucalyptus amygdalina, and its oil has the following char-
acters :—
Optical rotation . . • - 55° to - 70°
Its principal constituent is phellandrene, but it also contains piperitone.
OIL OF EUCALYPTUS DUMOSA.
This plant is one of the Mallees (dwarf eucalypts forming the
" scrub " of parts of Victoria, New South Wales, and South Australia).
The oil is of a good quality from a medicinal point of view, having the
Optical rotation . .• + 2° „ + 6°
Yield . . 1 per cent.
It contains pinene, eucalyptol, and aromadendral.
OIL OF EUCALYPTUS EUGENOIDES.
This tree is a white stringy bark of Victoria, Queensland, and New
South Wales. The oil has the following characters :—
Optical rotation + 3-4° „ + 4-7°
Yield 0-7 to 0'8 per cent.
The oil contains pinene and eucalyptol.
OIL OF EUCALYPTUS EXIMIA.
This tree is the white or yellow Bloodwood of New South Wales.
It contains pinene and aromadendrene.
OIL OF EUCALYPTUS FASTIGATA.
This tree is the Cut tail of New South Wales. Its oil has the fol-
lowing values:—
MYKTACEÊ 357
Kefractive index 1-4873 at 16°
Acid value 4-9
Ester „ 7-5
It contains d-pinene, phellandrene, eudesmol, and eucalyptol.
OIL OF EUCALYPTUS FASCICULOSA.
This tree is a Tasmanian eucalypt. Its oil contains pinene, eu-
calyptol, and esters, and has the following characters :—
Optical rotation 4- 6-3°
Saponification value 22'1
OIL OF EUCALYPTUS FLETCHERI.

This tree is a New South Wales " Box " tree. It yields an essential
Specific gravity . . . . 0-880 to 0-895
Optical rotation . . . . - 12-8°
Refractive index . . . . 1-4881 at 16°
It contains about 5 per cent, of eucalyptol, pinene, and aromadendral.
OIL OF EUCALYPTUS FEAXINOIDES.
The New South Wales " white ash " yields an essential oil having
Yield 1 per cent.
It contains pinene, eudesmol, and about 5 per cent, of eucalyptol, and
probably some citral.
OIL OF EUCALYPTUS GLOBULUS.
This tree, from which a typical eucalyptus oil is obtained, is the
Tasmanian " blue gum ". (Blue gum, however, is a name applied to a
number of other eucalypts in New South Wales, Victoria, and Western
Australia.) This plant was discovered by Labillardier in Tasmania in
1792, and introduced into Europe in 1856 by Eamel. It is a native of
Tasmania and Victoria, although found to a certain extent in other
colonies. The fresh leaves yield from '8 to 1*5 per cent, of oil of a
light yellow colour. The fact that this oil was regarded in Europe as
the typical eucalypt yielding a medicinal oil, together with the occur-
rence of such numerous and closely similar species in Australia,
account for the fact that eucalyptus leaves from various trees were
indiscriminately mixed and distilled, the resulting product being
marked oil of Eucalyptus globulus. Hence the difference observed by
various chemists in the properties of this oil. The pure globulus oil,
which is now largely replaced by other eucalyptus oils, has the follow-
ing characters:—
Optical rotation + 0° 30' to + 12°
Yield 0-8 to 1-5 per cent.
The oil contains from 50 to 70 per cent, of eucalyptol, d-a-pinene,
an unidentified terpene, valeric, butyric and caproic aldehydes, iso-
amyl alcohol, a pineocarvol ester, and a sesquiterpene alcohol which
has been named globulol. This is a crystalline compound melting
at 88*5°. Eudesmol and a sesquiterpene are also present.
OIL OF EUCALYPTUS GOMPHOCBPHALA.
This tree is a Western Australian Tuart tree. Its oil has the fol-
Befractive index 1*4815
Ester value 25'7
It contains phellandrene.
OIL OF EUCALYPTUS GONIOCALYX.
This tree is known in Victoria as the " spotted gum " or " white
gum/' but in New South Wales it is usually spoken of as " blue gum "»
The oil is bright yellow, of suffocating odour, and has the following
values:—
Optical rotation + 4-3° to + 7-1°
It contains 50 to 60 per cent, of eucalyptol, a-pinene, eudesmol, and
valerianie and acetic esters.
OIL OF EUCALYPTUS GBACILIS.
This tree inhabits the same districts as Eucalyptus dumosa, and is
also found in Queensland. Its oil contains a fair proportion of cineol,
and its cultivation has attracted some attention in Victoria. It has the
Yield 0-9 per cent.
It contains eucalyptol, pinene, and aromadendral.
OIL OF EUCALYPTUS GUNNII.
This tree is the Cider gum of Tasmania. Its oil has the following
values:—
Optical rotation + 1-5*
Befractive index 1-4752 at 18°
It contains about 40 per cent, of eucalyptol, d-pinene, Z-phellandrene,

esters, and a sesquiterpene.
MYETACEÊ 359
OIL OF EUCALYPTUS HÊMASTOMA.
This tree is the Scribbly gum of most of the colonies. Its oil con-
tains much phellandrene, eucalyptol, and aromadendrene, and has the
OIL OF EUCALYPTUS HEMILAMPRA.

This tree is found in New South Wales. The oil has the following
values:—
Optical rotation . + 6'9°
It contains eucalyptol, pinene, aromadendrene, and an aldehyde.
OIL OF EUCALYPTUS HEMIPHLOIA.
This tree is found in South Australia. The oil contains eucalyptol,
pinene, and aromadendral. Its characters are as follows :—-
Eucalyptol . . . . . . . . . 2 0 p e r cent.
Yield 0-55 „
OIL OF EUCALYPTUS INTEBTEXTA.

This tree is known in New South Wales as the Candle Bark. Its
It contains eucalyptol, rf-pinene, and aromadendrene.
OIL OF EUCALYPTUS LACTEA.
This tree is known in New South Wales as " Spotted Gum ". The
oil contains pinene and eucalyptol, and has the following characters :—
Optical rotation - 0'6° „ - 1-2°
OIL OF EUCALYPTUS L^VOPINEA.

The oil from this " Silver-top Stringy Bark" has the following
characters :—
Optical rotation - 30'7° „ - 33'3°
Refractive index .• 1'4697 at 19°
The oil contains much laevo-pinene and about 5 per cent, of eu-
calyptol.
OIL OF EUCALYPTUS LARGIFLORENS.
This tree is a Tasmanian eucalypt. Its oil contains eucalyptol,
pinene, and esters, and has the following characters :—
Eucalyptol . . . . . . . . . 5 0 p e r cent.
Yield 0-67
OIL OF EUCALYPTUS LONGIFOLIA.

This oil contains eucalyptol, pinene, and a sesquiterpene, and has
OIL OF EUCALYPTUS LOXOPHLEBA.

This tree is the Western Australian York Gum. The oil contains
phellandrene and eucalyptol, and has the following values :—
Optical rotation 4-5°
OIL OF EUCALYPTUS LUEHMANNIANA.

It contains phellandrene, eucalyptol, piperitone, and probably cifcral.
OIL OF EUCALYPTUS MACAKTHUBI.
This is one of the most interesting of the eucalyptus oils as it differs
materially 1from nearly every other one. It has been investigated fully
by Smith.
The crude oil of Eiicalyptus macarthuri, obtained by steam distilla-
tion from fresh material of leaves and terminal branchlets, is reddish
in colour owing to the presence of a small amount of free acid in the
original oil. In appearance, odour, etc., it resembles more than any-
thing else the crude oil of Darwinia fascicularis, but the higher boil-
ing portion consists largely of eudesmol, the stearoptene of eucalyptus
oil, which constituent is absent in Darwinia oil. Although containing
this stearoptene no crystals were obtained when the crude oil was
placed in a freezing mixture, eudesmol being so exceedingly soluble
in the oil.
The oil had the following characters:—
Optical rotation . . . . . . . . . + 3-6°
1
Jour. Proc. Roy. Soc., N.S.W., xxxiv. 142.
MYBTACEÊ 361
It was found to contain about 10 per cent, of free geraniol and
rather over 60 per cent, of geranyl acetate. This oil should be of con-
.siderable perfume value.
OIL OF EUCALYPTUS MACRORHYNCHA.
This tree is a red Stringy Bark of New South Wales. The oil has
Yield 0-27
It contains eucalyptol, phellandrene, pinene, eudesmol, and a ses-
quiterpene.
OIL OF EUCALYPTUS MACULATA.
This t*ee is a Spotted Gum of New South Wales and Queensland.
Its oil has the following characters :—
OIL OF EUCALYPTUS MACULOSA.
This tree is also known as Spotted Gum. The oil has the following
values:—
Specific gravity (V9158
Optical rotation . . . . . . . +3*4°
Yield 1-06
The oil contains eucalyptol, d-pinene, and aromaêndrene.
OIL OF EUCALYPTUS MARGINATA.
This tree is a Western Australian Jarrah tree. The oil contains
pinene, cymene, eucalyptol, aromadendral, and a sesquiterpene. It
Yield 0*2 per cent.
L OF EUCALYPTUS MEGACARPA.
The oil of eucalyptus megacarpa l contains pinene, limonene,
dipentene, about 30 per cent, of eucalyptol, and up to 10 per cent, of
terpinene. The latter terpene was • identified in the fraction 170° to 190°,
by the formation of its nitrosite melting at 155°.
OIL OF EUCALYPTUS MICROCORYS.
This is the sallow wood of New South Wales or u turpentine tree"
of Queensland. It yields an oil having the following characters :—
1
H. G. Smith, J. Proc. Roy. Soc., N.S. Wales (1918), 52, 529.
Optical rotation . . . . . . . . +18-4°
Yield 0-56 to 2 per cent.
Cineol, pinene, and aromadendrene appear to be the only well-
ascertained constituents, but according to some the oil, when properly
prepared, forms an excellent perfume.
OIL OF EUCALYPTUS MICEOTHECA.
This is a common tree in Australia, the characters of its essential
oil being as follows :—
Eucalyptol . . . . . . . . . 5 p e r cent.
Yield 0-23
The oil contains phellandrene, pinene, cymene, eucalyptol, and a
sesquiterpene.
OIL OF EUCALYPTUS MORBISII.
Optical rotation + 3-8° „ + 6'3°
It contains about 60 per cent, of eucalyptol and some d-pinene.
OIL OF EUCALYPTUS MUBLLBBI.
The oil from this tree has the following characters :—
The oil contains 60 per cent, of eucalyptol, pinene, and geranyl'
acetate.
OIL OF EUCALYPTUS NIGEA.
This tree is a Black Stringy Bark of New South Wales. Its oil has
the following values:—
It contains phellandrene and about 5 per cent, of eucalyptol.
OIL OF EUCALYPTUS NOVA ANGELICA.
This tree is a Black Peppermint of New South Wales. Its oil con-
tains pinene, phellandrene, eucalyptol, and aromadendrene. It has the
MYETACE^ 363
Yield 0*5 per cent.
OIL OF EUCALYPTUS OBLIQUA.

This tree is a " Stringy Bark " of the western part of Australia, but
is found in the Eastern Colonies as well. Its oil contains phellan-
drene, aromadendral, and traces of eucalyptol, and has the following
characters :—
Yield 0*66 to 0'77 per cent.
OIL OF EUCALYPTUS OCCIDENTAL^.

It contains about 35 per cent, of eucalyptol, pinene, aromadendral,
and a sesquiterpene.
OIL OF EUCALYPTUS ODOBATA.
This is a South Australian Box tree, whose oil has the following
characters:—
Optical rotation - 1-1° „ + 2-3°
Eucalyptol up to 86 per cent.
Yield . 1*87 „
It contains eucalyptol, cuminic aldehyde, pinene, and phellandrene.
OIL OF EUCALYPTUS OLEOSA.
This tree forms one of the Mallee scrub group, which are all fairly
rich in cineol. It is well known in Victoria and South Australia and
is also found in the interior extra-tropical parts of Western Australia.
The leaves yield about 1*3 per cent, of an oil, having the following
characters:—
Optical rotation - 5° to + 5°
It is very rich in eucalyptol, and contains pinene, aromadendral, and
a sesquiterpene.
According to Baron Miiller, it is the best-known solvent for fossil
resins, and " is unique for many technological applications ". This oil
is not identical with much of the so-called Oleosa oil of commerce, which
is in reality obtained from Eucalyptus cneorifolia.
364: THE CHEMISTEY OF ESSENTIAL OILS
OIL OF EUCALYPTUS OBEADES.
It contains phellandrene, piperitone, and eudesmol.
OIL OF EUCALYPTUS OVAFOLIA.
It contains phellandrene, pinene, eucalyptol, and a sesquiterpene.
OIL OF EUCALYPTUS PALUDOSA.
This tree occurs in New South Wales, Victoria, and Tasmania. The
oil has the following characters:—
Specific gravity . . . . . . . . 0'902 t o 0'9056
Optical rotation + 9'9° „ + 14-2°
It contains pinene, eucalyptol, a sesquiterpene, and a valerianic
ester.
OIL OF EUCALYPTUS PANICULATA.
This tree is a "White Iron Bark" found in most of the colonies.
Its oil has the following characters:—
Yield 0-1 per cent.
It contains eucalyptol, aromadendrene, aromadendral, and an alcohol
not yet identified.
OIL OF EUCALYPTUS PATENTINERVIS.
This tree is known in New South Wales as a Bastard Mahogany.
The following are the characters of the oil:—
It contains limonene, a sesquiterpene, and citral.
OIL OF EUCALYPTUS PENDULA.
It contains about 50 per cent, of eucalyptol, pinene, and aroma-
dendrene.
MYBTACEJE 365
OIL OF EUCALYPTUS PERRINIANA.
It contains eucalyptol, pinene, and a sesquiterpene.
OIL OF EUCALYPTUS PHLBBOPHYLLA.
This tree is known as the Weeping Gum in Tasmania. It yields an
Optical rotation - 22*4° „ - 32*56
It contains Z-a-pinene, about 10 per cent, of eucalyptol, phellandrene,,
eudesmol, and a sesquiterpene.
OIL OF EUCALYPTUS PILULARIS.
Specific gravity 0'B85 to 0*903
Optical rotation - 4*3° „ + 11-1°
Yield 0*07 to 0-18 per cent.
It contains Z-phellandrene, a sesquiterpene, eucalyptol, pinene, and
an alcohol not yet identified.
OIL OF EUCALYPTUS PIPERITA.
This tree is found in New South Wales, Victoria, and Queensland,
and is known as a " Peppermint Tree". The oil contains eudesmol,
pinene, eucalyptol, phellandrene, and a sesquiterpene. Probably piperi-
tone is also present. The oil has the following characters:—
Optical rotation -2*7°
Refractive index . 1*4838 at 16°
OIL OF EUCALYPTUS PLANCHONIANA.
Yield 0*01 to 0*06 per cent..
It contains phellandrene and a sesquiterpene.
OIL OF EUCALYPTUS PLATYPUS.
This oil, according to Earl,1 has the following characters:—
Yield 1 per cent.
It contains about 60 per cent, of eucalyptol, 20 to 25 per cent, of pinene,.
and some phellandrene and aromadendrene.
1
Proc. Boy. Soc. Victoria, CJiem. Abstracts, 1917, ii. 1715.
366 THE GHEMISTEY OF ESSENTIAL OILS
OIL OF EUCALYPTUS POLYANTHBMA.
Yield 0-825
It contains pinene and eucalyptol.
OIL OF EUCALYPTUS POLYBBACTEA.
This is one of the Mallee eucalyptus trees found in New South
"Wales. Its oil has the following characters :—
Optical rotation. . . . . . . 0° ,, — 2°
It contains up to 90 per cent, or over of eucalyptol, with small
-amounts of pinene and aromadendral.
OIL OF EUCALYPTUS POPULIFOLIA.
Optical rotation + 0*41° ,, +1-2°
Eucalyptol about 60 per cent.
Yield 0'66 to 0*86 per cent.
It contains eucalyptol, pinene, and a sesquiterpene.
OIL OF EUCALYPTUS PROPINQUA.
Optical rotation . . . . . . . . -f 4*5°
It contains eucalyptol, pinene, and aromadendral.
OIL OF EUCALYPTUS PULVERULENTA.
Optical rotation . . . . . . . . + 2-1°
Yield 2-2 per cent.
It contains eucalyptol and pinene.
OIL OF EUCALYPTUS PUNCTATA.
This tree is found in Queensland and Victoria. Its essential oil
Optical rotation - 2*3° to + 4°
Eucalyptol 46 to 65 per cent.
Yield . 0-63 „ 1-19 per cent.
It contains eucalyptol, aromadendral, and cuminic aldehyde.
MYETACB^B 367
OIL OF EUCALYPTUS QUADRANQULATA.
The characters of this oil are as follows :—
It contains ^-pinene and eucalyptol.
OIL OF EUCALYPTUS EADIATA.
This tree is known as " White-top Peppermint'' in New South
Wales. The oil has the following values :—
Optical rotation - 64-8° „ - 77'8°
Yield 1-22 to 1*88 per cent.
It contains pinene, phellandrene, eucalyptol, and piperitone.
OIL OF EUCALYPTUS EBDUNCA.
This is a white gum found in Western Australia. The oil has the
Refractive index 1-4720 at 16° ,
Yield 1-2 per cent.
It contains ^-pinene, eucalyptol (about 40 per cent.), and aroma-
dendrene.
College of Dentistry U. S. C,
OIL OF EUCALYPTUS EEGNANS.
This tree is a Tasmanian " Swamp Gum ". Its oil has the following
characters:—
Refractive index 1-4882 to 1*4901 at 20°
Yield 0'8 per cent.
It contains phellandrene, eudesmol, geranyl acetate, piperitone,
traces of eucalyptol, and a sesquiterpene.
OIL OF EUCALYPTUS EBSINIFEBA.
This oil has the following values :—
It contains eucalyptol.
OIL OF EUCALYPTUS EISDONI.
Optical rotation - 0-3° to - 14-6°
Yield 1 '35 per cent.
It contains eucalyptol, phellandrene, and probably piperitone and
amyl acetate.
OIL OF EUCALYPTUS Eosn.
Specific gravity 0-9168 to 0-9215*
It contains pinene and eucalyptol.
OIL OF EUCALYPTUS EOSTRATA.
Optical rotation - 11-7° to - 15-3°
Yield . 0-1 to 0'4 per cent.
It contains cymene, aromadendral, eucalyptol, phellandrene, and'
pinene.
OIL OF EUCALYPTUS EUBIDA.
It contains pinene, a sesquiterpene, and a little eucalyptol.
OIL OF EUCALYPTUS EUDDERI.
Yield . 0-3 per cent.
It contains pinene, aromadendral, and about 5 per cent, of
eucalyptol.
OIL OF EUCALYPTUS SALIGNA.
This tree is found in New South Wales.' The oil has the following
characters:—
Optical rotation -f 32-9° „ + 35-1°
It contains d-pinene, eucalyptol, eudesmic acid, amyl ester, a free
alcohol, and a valerianic ester.
OIL OF EUCALYPTUS SALMONOPHLOIA.
MYKTACEÊ 369
OIL OF EUCALYPTUS SALUBEIS.
Refractive index 1-4841 at 16*
Yield 1*4 per cent*
It contains d-pinene, cymene, eucalyptol (10 per cent.), geranyl
acetate, and aromadendral.
OIL OF EUCALYPTUS SANTALIFOLIA.
This tree is a Tasmanian eucalypt. Its oil contains pinene, limo-
nene, eucalyptol, and sesquiterpenes ; it has the following characters :—
Eucalyptol 12 per cent.,
Yield 0-41
OIL OF EUCALYPTUS SIDEBOPHLOIA.

This tree is a " Eed Iron-bark" of Queensland. Its oil has ther
fojlowing characters :—
It contains phellandrene, pinene, and eucalyptol.
OIL OF EUCALYPTUS SIDBROXYLON.
This tree is the "Eed Flowering Iron-bark" of New South Wales
and Victoria. Its oil has the following characters :—
It contains about 60 per cent, of eucalyptol, pinene, a sesquiterpene,
and an aldehyde.
OIL OF EUCALYPTUS SMITHII.
This oil is of very great importance, since it is perhaps the best
eucalyptol-pinene oil obtainable from any species. H. G. Smith gives
the following information in regard to this tree (which has been named
after him):—
The time is rapidly approaching when it will be considered advisable,
and found to be profitable, to cultivate or re-afforest with the best species
for the required kinds of essential oils obtainable from the members of
this great genus. The time seems opportune, therefore, to direct atten-
tion to the advantages which Eucalyptus Smithii offers for cultivation.
The growth of Eucalyptus Smithii, under natural conditions of soil
and climate, is considerable, and is more rapid with the so-called
" suckers," or new growths, which spring from the stumps of the felled
VOL. i. 24
mature trees than with plants grown from seed, although with the
seedlings the increase in height usually averages, for the first year
or two, from 6 ins. to a foot per month.
Eucalyptus Smithii is a well-defined species and has a somewhat
extensive range. The oil obtained by steam distillation is one of the
richest in cineol-content of all eucalyptus species so far examined. The
yield of oil is also good, as much as from 20 to 26 Ib. of oil being ob-
tainable commercially from the leaves and terminal branchlets which
can be packed in a 400 gallon tank. The oil consists very largely
of cineol, and the terpene is dextro-rotatory pinene. In commercial
samples the amount of high boiling constituents is often very small
indeed, the original distillation not being carried to the end, and 96
per cent, or more of crude commercially distilled oil may come over
below 190° C.
In addition to pinene and eucalyptol, the oil contains a phenol,
traces of aldehydes, d-eudesmol, butyl-butyrate (?), and a sesquiterpene.
A small quantity of a solid paraffin melting at 64° is also present.
The great importance of this oil from the commercial point of view
rendered an examination of samples obtained under different conditions
desirable, and the following samples have been examined by H. G.
Smith :—
(a) Leaves from lopped trees, seven months' growth; collected
May, 1913. (b) Leaves from lopped trees, fifteen months' growth ;
collected May, 1913. (c) Leaves from seedlings, twelve months'
growth ; collected June, 1914. (d) Leaves from seedlings two and a
half years' old ; collected July, 1914. (e) Leaves from cultivated tree
at Marrickville; collected June, 1915. (/) Leaves from general
material, partly young; collected January, 1915. (g) Leaves from
general material collected three weeks later than (/). (h) Leaves
from old trees; collected March, 1913.
The constants, etc., given by the crude oils from the above material
were as follows :—
Specific Gravity Rotation. Refractive Solubility in Saponification Eucalyptol

at 15° C. a
D. Index. 70° 0 Alcohol. Number. per Cent.
Required.
(a] 0*9098 + 7-6° 1-4636 ' 1-6 vols. 4-8 67-4
at 20°
(b) 0-9157 + 6-5° 1-4635 1-2 „ 5-6 74-2
at 20°
(c] 0-9116 + 9-2° 1-4650 2-1 ,, 1-3 61-5
at 19°
(d] 0-9139 - 7-6° 1-4634 1-4 „ 4-1 69-0
at 18°
(«) 0-9198 + 47° 1-4672 1-2 ,, 2-7 75-0
at 16°
(ft 0-9156 + 5-3° 1-4571 1-1 „ 3-3 80-7
at 26°
(<7) 0-9154 + 5-1° 1-4574 1-1 „ 3-1 79-0
at 25° i
(h} 0-9210 + 4-2° 1-4604 1-1 „ 1-3 85-2
at 22°
The eucalyptol was determined by the resorcinol method.

MYETACE.E 371
FIG. 33.—Eucalyptus Smithii, B.T.B.

Photograph taken in 1911. Tree was felled in 1906 ; top branches first removed for oil distillation
in 1908. Photograph shows three years' growth. Material has been collected from this tree
for oil distillation four times in seven years. Hill Top, New South Wales. Journ. Roy.
,s'oc. jV.tf. Wales, vol. xlix., Plate XIII.
OIL OP EUCALYPTUS SQUAMOSA.
It contains about 60 per cent, of eucalyptol, pinene, and aroma-
dendral.
OIL OF EUCALYPTUS STAIGEBIANA.
This tree is the Lemon-scented Iron-bark of Queensland, the es-
sential oil being of particular interest, as it differs entirely from ordinary
eucalyptus oils. The oil has the following characters :—
Specific gravity 0-8708 to 0-880 (0-901 ?)
Refractive index . . . . . . 1'4871 at 16°
Yield . . . . . . . . 2-5 p e r cent.
The oil has been carefully investigated by Baker and Smith. In
the course of fractional distillation only a few drops came over beldw
175°, but between that temperature and 193° C. 65 per cent, distilled;
this fraction had specific gravity at 23/15° C. = 0*851, and refractive
index at the same temperature, 1-4798. Between 193° and 265° C., 23
per cent, distilled, the specific gravity of this = 0*8828 at 23° C., and
refractive index 1*4846 at the same temperature. Between 265° and 300°
C. only 2 per cent, distilled; this had a refractive index 1*5033, and was
quite acid. On again rectifying the first fraction (65 per cent.) nothing
came over below 175° C.; but 40 per cent, of the fraction distilled be-
tween 175° to 177° C. ; the rotation of this in 100 mm. tube was
- 66*2° ([a]D - 78*18°), the specific gravity = 0*8468 at 22/15° C., and
the refractive index = 1*4793. Between 177° and 179° C. 23 per cent,
distilled; the rotation was - 64*8°, the specific gravity = 0*8533° at
22/15° C., and the refractive index = 1*482. Between 179° and 184° C.
17 per cent, distilled; the rotation was — 60*9°, the specific gravity
= 0*8534, and the refractive index = 1*4828.
The crystallised tetrabromide was formed in the usual way with the
portion distilling 175° to 177° C., and these crystals, when purified to
constant melting-point with acetic ether, melted at 104° to 105° C.
From the physical properties of the several fractions it may be assumed
that nearly the whole of the terpene present was laevo-limonene, and
that the oil contained about 60 per cent, of that terpene.
An aldehyde determination in the usual way, with 30 per cent,
sodium bisulphite solution, gave 16 per cent, of aldehydes. The pre-
paration of the non-aldehydic oil was carried out quantitatively to act
as a check on the other determinations. Thirty grms. of oil gave 25*4
grms. of non-aldehydic constituents equal to 15*33 per cent, of alde-
hydes.
The rotation of the non-aldehydic oil was .— 46*8°, the specific gravity
= 0*8658 at 22/15° C., and the refractive index *= 1*4831. It was very
aromatic.
The ester determination was carried out on the non-aldehydic oil.
The saponification number was 28*3, equal to 9*9 per cent, of ester cal-
MYRTACEJE 373
culated as geranyl acetate, or 8*32 per cent, on the original oil. An
ester determination on the original oil gave 8'6 per cent.
A portion of the non-aldehydic oil was acetylated in the usual way,
and this gave a saponification number 78*47, which represents 15'14
per cent, of free alcohol, or 12*72 per cent, of geraniol in the original oil.
The oil of Eucalyptus Staigeriatia may be stated to have approxi-
mately the following constitution :—
Limonene 60-00 per cent.
Geraniol 12-72
Geranyl acetate 8-32
Citral 16*00
Undetermined 2-96
100-00
OIL OF EUCALYPTUS STELLULATA.

Optical rotation . . . . . . . . - 26*1°
Refractive index . 1 '4902 at 16°
Yield 0-3 per cent.
It contains phellandrene, a sesquiterpene, and traces of eucalyptol.
OIL OF EUCALYPTUS STEICTA.
Optical rotation . . . . . . . . — 3*4°
Yield 0*5 per cent.
It contains pinene, eucalyptol, and eudesmol.
OIL OF EUCALYPTUS STUAKTIANA.
Optical rotation . . . . . . . . + 4*7°
Yield 0-4 per cent.
It contains about 50 per cent..of eucalyptol, pinene, and some esters.
OIL OF EUCALYPTUS TÊNIOLA.
It contains 7 per cent, of eucalyptol, phellandrene, eudesmol,
piper itone, and a sesquiterpene.
OIL OF EUCALYPTUS TERETICOKNIS.
Refractive index . . 1*4934 at 16°
It contains pinene, eucalyptol (about 5 per cent.), aromadendral,
and a sesquiterpene.
An Indian oil, examined by Ghose,1 had the following characters :—
OIL OF EUCALYPTUS TESSELLARIS.

Optical rotation . . . . . . . . +8-8°
It contains pinene, cymene, eucalyptol, and aromadendrene.
OIL OF EUCALYPTUS TRACHYPHLOIA.
Specific gravity , 0'893
Yield 0-2 per cent.
It contains pinene, aromadendrene, aromadendral, and eucalyptol.
OIL OF EUCALYPTUS UMBRA.
It contains d-pinene, eucalyptol, and some esters.
OIL OF EUCALYPTUS UNIALATA.
This tree is a Tasmanian eucalypt. Its oil contains about 60 per
cent, of eucalyptol, d-pinene, and a sesquiterpene; and has the follow-
ing characters :—
Yield 0-9 per cent.
OIL OF EUCALYPTUS URNIGERA.

Optical rotation . + 10-6°
It contains about 60 per cent, of eucalyptol, d-pinene, and geranyl
acetate.
1
P. and E.O.R. (1919), 145.
MYRTACEÊ 375
OIL OF EUCALYPTUS VEBNICOSA.
Refractive index 1-4651 at 18a
Yield 0-8 per cent.
It contains about 60 per cent, of eucalyptol, and pinene.
OIL OF EUCALYPTUS VIMINAHS.
This tree is found in most of the Australasian Colonies. The oil
Eucalyptol . 35 per cent.
Yield . 0-35 to 0-74 per cent.
It contains eucalyptol, phellandrene, aromadendrene, and d-pinene.
OIL OF EUCALYPTUS VIRGATA.
It contains about 20 per cent, of eucalyptol, and Z-phellandrene.
OIL OF EUCALYPTUS VIRIDIS.
Refractive index 1*4828 at 16*
It contains eucalyptol, Z-pinene, and aromadendral.
OIL OF EUCALYPTUS VITBEA.
It contains phellandrene, eucalyptol, a sesquiterpene, piperitone,
and citral (?).
OIL OF EUCALYPTUS WILKINSONIANA.
It contains Z-pinene and eucalyptol.
OIL OF EUCALYPTUS WOOLLSIANA.
Optical rotation . - 9-5° „ - 16°
Yield 0-5 per cent.
It contains pinene, aromadendral, and eucalyptol.
OILS OF THE ANGOPHORAS.
So far only six species of the genus Angophora have been described.
They are all Australian plants, and are closely allied to the Eucalypts,
and believed by Baker and Smith to be the prototypesl of the latter;
these scientists have investigated the plants, and Smith has examined
the essential oils.
The following table gives the yields of oil distilled from material
cut as would be done for commercial oil distillation :—
Angophora Bakeri .
. . 0*31 per cent.
0-31
melanoxylon1 0-19
sp. undescribed
bed . 0-13
lanceolata (S>ydney) 0-013
.. ^
intermedia .
Varialda) 0-005
traces
subvelutina . none
cordifolia
The oil from Angophora Bakeri has the following characters:—
Specific gravity . . . . . . . . 0*8719
Refractive index . . . . . . . . 1-4660 a t 2 2 °
The crude oil was light lemon-coloured, had an indistinct odour at
first, but distinctly a secondary aromatic one. The chief constituents
were dextro-rotatory pinene, geraniol, geranyl-acetate, geranyl-valerian-
ate, a small amount of a sesquiterpene, together with a little volatile
aldehyde, and most probably a minute quantity of amyl-acetate. No
other terpene than pinene was detected and cineol was quite absent.
* The oil from Angophora melanoxylon has the following characters :—
Refractive index 1-4678 at 21-5°
The constituents of this oil are identical with those of Angophora
Bakeri, the geranyl valerianate, and the sesquiterpene being present in
rather larger amount.
Angophora lanceolata yields an oil having, the following characters :—
Refractive index . . . . . . 1-4946 at 20°
The constituents are similar to those of the other species just
described.
The approximate composition of the oils from Angophora Bakeri
and Angophora melanoxylon are as follows :—
Angophora Angophora
Bakeri. Melanoxylon.
Per Cent. Per Cent.
Dextro-rotatory pinene . . . . . 78-0 72-0
Free geraniol 4-5 5-1
Geranyl acetate 6-7 6-9
Geranyl valerianate . . . . . 6-1 9-6
Water, volatile aldehydes, and low-boiling esters 1-0 1-0
Sesquiterpene and undetermined . 3-7 5-4
100-0 100-0
1
Jour, and Proc. Roy. Soc., N.S.W., xlvii. (1913), 106.
MYBTACEÊ 377
OILS OF LEPTOSPERMUM.
The lemon-scented Leptospermum Liversedgei is a New South Wales
•shrub, from 6 to 12 ft. in height, which yields about 0*23 per cent, of
essential oil, which has been examined by Baker and Smith.1 The oil
has the following characters :•—
Optical rotation + 9;2°
The principal constituents in the oil are : (1) the aldehyde citral;
(2) an alcohol, which is probably geraniol; (3) an acetic acid ester, which
is probably geranyl acetate; (4) the terpene pinene which was dextro-
rotatory ; and (5) a sesquiterpene, which is probably the constituent
which gives the laevo-rotation to the higher boiling portion. Limonene
could not be detected by any method, and was, therefore, absent; nor
was phellandrene present. The whole of the aldehyde appears to be
citral, as proof of the presence of any other aldehyde could not be ob-
tained, and two determinations by Flatau and Labbe's method failed to
give any indication for citronellal. The secondary odour of the oil, from
which the aldehydes had been removed, strongly resembled that of
geraniol. The oils of the Leptospermums, with this exception, do not
appear to have been investigated chemically, so that the occurrence of
.-citral in the oil of Leptospermum Liversedgei is of some scientific interest.
The approximate composition of the oil is as follows :—
Citral 35'0 per cent.
Geranyl acetate . 5-35
Oeraniol 9-74 „
•d-pinene . 25-0
Sesquiterpene and undetermined 24-91
100-00 per cent.
According to Challinor, Cheel, and Penfold, the leaves of Leptosper-
flavescens, var. citratum, yield about 1/8 per cent, of oil having the
[following characters:—
Optical rotation " . . . . + 3-6°
It contains about 90 per cent, of aldehydes, which consist of citral
and citronellal in approximately equal amount. A small quantity of an
alcohol (possibly geraniol or citronellol) was found, and a trace of a
phenol. Probably aromadendrene is present.
OIL OF DAKWINIA FASCICULARIS.
This oil has been investigated by Baker and Smith.2
Darwinia fascicularis is a virgate shrub, varying in size in different
localities, about 5 ft. being the maximum height in the coast form. The
mountain variety rarely exceeds 2 ft. The leaves are slender, numerous,
=and crowded, and vary in length from four to eight lines. The flowers
.although small are attractive, being sometimes all white, or pink and
white.
1
Jour, and Proc. Roy. Soc., N.S.W., xxxix. (1905), 124.
., xxxiii. (1899), 163.
It is entirely an Australian plant, being principally found in the
neighbourhood of Port Jackson. It occurs on sandy soil mostly, and
covers many hundred acres of ground between Botany, La Perouse, and
the coast. It has been found north of Manly and also on the Blue
Mountains at King's Tableland, Wentwprth, and Lawson.
The yield of oil obtained was from 0-318 to 0'456 per cent., having a
specific gravity 0'9154, and being slightly dextro-rotatory.
It contains geraniol, to the extent of 57 to 65 per cent, in the form of
acetate, and about 13 per cent, in the free state.
OIL OF DABWINIA TAXIFOLIA.
Optical rotation . - 6-5°
This oil contains only about 5 to 6 per cent, of esters and 8 per cent,
of free alcohol. It is probable that the alcohol present is linalol and not
geraniol.
OIL OF DAKWINIA GRANDIFLORA.
Baker and Smith l have described the essential oil distilled from the
leaves of Darwinia Grandiflora, which was obtained to the extent of 0*12
per cent. This oil had the following characters :—
Ester value 100-4
The oil contains d-pinene, geranyl acetate, and probably geranyl
butyrate.
CAJUPUT OIL.
This oil is distilled from the leaves of several species of Melaleuca,.
myrtaceous shrubs growing abundantly in the Indian Archipelago, the
Malay Peninsula, and other places. Most of the oil of commerce is
yielded by Melaleuca minor. A great portion of the oil is distilled on
the islands of Bouru and Banda, whence it is brought to Macassar and
the neighbourhood for shipment. The bulk of the oil is exported in
wine bottles, although shipment in drums, to save the excessive freight,
has been resorted to. The oil has a powerful camphoraceous odour,
due largely to its high cinebl-content. It is usually of a green colour,
generally due to contamination with copper, but can be obtained white
by re-distillation. The oil has the following characters :—
Refractive index 1-4650,, 1*471
Normal oil contains up to 65 per cent, of cineol. In addition to
this body, to which the oil owes its value, 2terpineol and terpinyl acetate
have been found, and, according to Voiry, butyric, valeric, and benzoic
aldehydes and probably laevo-pinene. The low specific gravity of many
l
2
Jour. and Proc. Roy. Soc., N.S.W., 1. (1916), 181.
Jour. Pharm. Chim. (1888), 149.
MYETACE^ 379
commercial samples is accounted for by adulteration with turpentine
or petroleum. The oil is not used to any extent internally, but is em-
ployed externally as a stimulant and anti-spasmodic. Eucalyptus oil
with a high cineol-content is well able to replace it for most purposes.
Genuine Cajuput oil should contain at least 50 per cent, of eucalyptol,
as determined by the phosphoric acid process.
Much of the obscurity surrounding the origin of Cajuput oil has
been cleared up by the systematic investigation of the species by Baker
and Smith,1 who state that there had been imported into Europe from
the East, about the beginning of the seventeenth century, an oil under
the name of " Cajoepoeli" (according to Linnaeus' spelling), but under a
later spelling "Cajuput". At that time, and long after its introduction,
the botanical origin was ascribed to Linnaeus' species (Melaleuca leuca-
dendron), as the specimens forwarded to Linnaeus were reputed to be
taken from trees from which the oil was obtained, and he evidently
described it under that impression, as shown by his original specimen
now in the possession of the London Linnean Society and labelled by
him " Cajoepoeli " and afterwards by Smith as Melaleuca leucadendron,
vera.
This reputed origin of the oil, however, was shown later by
Eoxburgh to be an error, being the true source of " Cajuput" a
Melaleuca which he named Melaleuca cajuputi, but this was found later
to be identical with Melaleuca minor, described earlier in 1813 by Smith
in Bees Cyclopcedia, Vol. XXIII, and so quite a distinct tree from that
to which Linnaeus had given the above name. However, many Euro-
pean systematists in the last century regarded the two as one, but the
early Indian botanists being very emphatic over the matter, always kept
them distinct, and Baker and Smith's investigations support the latter
botanists.
Schimmel & Co.2 have examined the oils obtained from the narrow-
leaved and the broad-leaved varieties of Melaleuca leucadendrori grown
in Amani. They find that eucalyptol is entirely absenTTroin the broad-
leaved variety, and only present to a small extent, as compared with true
cajuput oil, in the narrow-leaved variety. The oil from the broad-leaved
variety contains about 78 per cent, of methyl-eugenol. The two oils had
Broad Leaved. Narrow Leaved.

Acid value. 0-4 0-7
Ester value 7-6 11-8
,, ,, (after acetylation) 15-2 84-8
Since the original description by Linnasus was published, several

species have been described which had the general facies of his tree but
differed in some important characters.
The following Melaleuca oils have been described in addition to that
from Melaleuca minor :—
1
Jour, and Proc. Roy. Soc., N.S.W., xl. (1906), 60; xli. (1907), 196 ; xliv. (1910),
592; xlv. (1911), 365; xivii. (1913), 193.
2
OIL OF MELALEUCA MAIDENI.
This tree is found in New South Wales and Queensland. The oil
Eucalyptol . 26 to 39 per cent.
The oil contains, in addition to eucalyptol, Z-pinene, Z-limonene, an
alcohol, a sesquiterpene alcohol, a sesquiterpene (?), and benzaldehyde (?).
OIL OF MELALEUCA SMITHII.
This is the common broad-leaved Melaleuca of certain districts of
New South Wales. Three samples examined by Baker and Smith had
Yield Specific Eucalyptol Rotation Refractive Saponifica-
Locality. per Gravity per Cent. a
Index tion
Cent. at 15°. D. at 22 . Number.
Hose Bay, Sydney 0-607 0-8815 About + 11-8° 1-4812 3-1

18/12/1911 1
Terrigal, N.S.W. 0-923 0-9003 less + 6-7° 1-4824 3-3
21/12/1911 than 2
Gosford, N.S.W. 0-495 0*8976 about + 5-8° 1-4806 6-5
20/9/1899 5
In addition to eucalyptol, the oil contains benzaldehyde (?) Z-pinene

7-limonene, dipentene, and a sesquiterpene alcohol, which has been
termed melaleucol. It is suggested that this alcohol may be related to
the alcohol nerolidol, in the same way as geraniol is to linalol. The
identity of this body, however, is hardly established by experimental
evidence.
OIL OF MELALEUCA THYMIFOLIA.
It contains about 53 per cent, of eucalyptol.
OIL OF MELALEUCA LINARIFOLIA.
It contains much terpenes and but little eucalyptol.
OIL OF MELALEUCA UNCINATA.
This tree yields 1-246 per cent, of essential oil which has the fol-
MYETACEÊ 381
The oil is rich in eucalyptol, and also contains d-a-pinene, a sesqui-
terpene, and a crystalline body, which may be an alcohol, melting at
72*5°. In this the name uncineol and the formula C10H18O is suggested
OIL OF MELALEUCA NODOSA.
This oil from the Melaleuca has the following characters :—
Yield . 0-664 per cent.
The oil contains much d-pinene, eucalyptol, and a sesquiterpene.
OIL OF MELALEUCA TBICHOSTACHYA.
Optical rotation + 2-3° „ -f 3-1°
Yield 1-25 to 2'58 per cent.
The oil contains a very large amount of eucalyptol, terpenes, traces
of a phenol, and terpinyl acetate.
OIL OF MELALEUCA BBACTEATA.
The oil from the Melaleuâ differs from those from all other members
of the genus. The yield of oil is about 1 per cent., having the follow-
ing characters:—
The principal constituent of the oil is methyl-eugenol, with some
eugenol, free cinnamic acid, cinnamic aldehyde, cinnamic alcohpl (?)„
phellandrene, and cinnamyl-(?)-cinnamate.
OIL OF MELALEUCA GENISTIFOLIA.
Yield . ' 0-526 per cent.
About 2 per cent, of eucalyptol is present, with 80 to 90 per cent, of
pinene, a small amount of a sesquiterpene, and 5 to 6 per cent, of ter-
pinyl acetate.
OIL OF MELALEUCA GIBBOSA.
Eucalyptol 61-5 per cent.
Yield 0-16
The oil contains eucalyptol, pinene, and a sesquiterpene.
OIL OF MBLALEUCA PAUCIFLORA.
This oil is quite different from ordinary Melaleuca oils. It contains
no pinene, the terpenes present consisting of limonene and (probably)
dipentene, with a little eucalyptol, a sesquiterpene, terpineol, and ter-
pinyl.acetate. The characters of the oil are as follows :—
Refractive index 1-4921 at 24
Yield 0-3 per cent.
OIL OF MELALEUCA—(NIAOULI).
Oil of " Niaouli " is generally stated to be obtained from Melaleuca
viridiflora, from New Caledonia. The name was given to the plant
yielding the oil by Brongniart and Gris, but as it is quite different from
the true Melaleuca viridiflora of Solander, the plant requires a new
specific name, and should not be described as viridiflora. The oil has
the following characters :-—
It contains d-a-pinene, Himonene, terpineol, eucalyptol, valeric and
benzoic aldehydes, and terpinyl valerianate (?).
OIL OF BAY.
This oil is the product of distillation of the leaves of Pimenta acris
(Myrcia acris) and probably other closely allied species, plants flourish-
ing in the -West Indies. The yield of oil obtained is from 2 to 3 per
cent., the oil coming over in two portions, firstly, alight oil which distils
over rapidly, then a heavy oil distilling over more slowly. This, of
course, means nothing more than that there are constituents of bay oil
which have widely different boiling-points. The fact that the United
States Pharmacopoeia of 1880 gave the specific gravity of bay oil as about
1*040, caused the heavier fractions to appear in commerce under that
name. Pure normal distillates, however, have a specific gravity of '965
to 1*010, and oils with a higher specific gravity must be regarded as
suspicious, being possibly adulterated with oil of cloves or oil of pimento.
Occasionally distillates with a specific gravity of 1*020 or thereabouts are
found with phenol values of 65 to 75 per cent., but these are rare.
The erratic manner in which this oil is distilled in the West Indies
results in a large majority of the oils reaching this country being merely
fractions of Bay oil. Umney l quotes the following (see opposite page)
as representing commercial samples which he has observed. Those
of very low specific gravity, however, may be actually adulterated.
Eeference to the figures recorded shows that the percentage of
phenols in oils having a specific gravity between 0*936 and 0*938 may
vary as much as from 32 to 48 per cent. The strong probability is
that the reason of the variation lies in the changes which the principal
terpene, myrcene, undergoes on keeping, and especially on exposure.
Efforts are being made to improve the Bay Leaf industry in the
West Indies, with a view to a more constant quality of oil being im-
ported.
1
P. and E.O.R. (1916), 295.
MYKTACE^ 383
Some interesting details of the experimental work being undertaken

is given by Sir Francis Watts, D.Sc., F.I.C., Commissioner of Agriculture
Phenol Specific Gravity. Phenol Specific Gravity.
Percentage. Percentage.
20 •864 48 •948
24 • -858 50 •985
26 •875 50 •951
26 •879 50 •967
28 •895 51 •953
28 •896 52 •924 Dominica
30 •896 52 •977
30 •898 Montserrat 52 •944
32 •936 52 •952
33 •945 Dominica 52 •954
34 •908 53 •969
34 •941 54 •945
36 •936 54 •949
36 •937 54 •950 Montserrat
36 •943 55 •946 Dominica
37 •932 55 •966
40 •941 55 •966
40 •948 56 •978
41 •929 56 •955
42 •948 56 •956
43 •931 58 •971
44 •935 60 1-004
45 •925 Dominica 60 •965 U.S.A.
45 •926 60 •966
45 •958 60 •974
45 •933 60 •984 Martinique
47 •937 62 •960
48 •937 64 •977
48 •938 76 1-011
tor the West Indies. He states that, in connection with the island of
Montserrat, " the results obtained from the experimental plot, 1 acre in
area, established in 1908, have given further proof that at the current
price obtained for bay oil the cultivation of this tree is a matter worth
the attention of persons having lands that are at present unused, particu-
larly on the higher lands of the island. Details of the planting and
cultivation up to the end of 1912 in connection with this plot are given
in the last annual report on the Botanic Station, and, generally, the re-
•sults obtained in 1913 are a decided improvement on those of'the two
previous years.
" Briefly, the plot was planted in 1908, and reaping of the leaves
from which the oil is distilled was commenced in January, 1911. Since
that time monthly reapings have been made. The yield of fresh leaves,
and the actual amount of oil obtained from them for the three years
ending December, 1913, is as follows :—
Yield of Leaves, Actual Yield of Oil.
Ib.
1911 . . . . 1368 6,189 c.c. = 221 oz. = 14 Ib. approx.

1912 . . . . 1940 8,615 „ = 307 „ = 19 „ „
1913 . . . . 2510 12,764 ,, = 456 „ = 28J „ „
" Not only has there been an increase in the total amount of leaves-
reaped from the plot, but also an increase in the proportion of oil
obtained from the leaves, which in 1912, on the average, was 16*7 oz.,
and in 1913 18*3 oz. per 100 Ib. of leaves as reaped.
Date of Distillation. Amount of Yield of Oil, Ounces per

100 Ib. Specific Phenol-
content,
Fresh Leaves. c.c. Fresh Leaves. Gravity. per Cent.
January 3rd 165 764 16-5 •9410 50

January 31st 162 773 16 •9496 54
March 3rd 162 732 16 •9806 70
April 1st 185 931 18 •9443 58
May 1st . 153 783 18 •9620 63
May 6th 180 909 18 •9515 60
June 12bh 160 905 20 •9288 47
June 26th 176 1115 22-7 •9714 66
July 16th 188 1149 21-8 •9520 60
August 22nd 160 814 18 •9421 53
September 26th 174 846 17-4 •9219 45
October 31st . 195 801 14-7 •9274 51
November 28th 163 830 18-1 •9242 48
December 15th 104 639 21-7 •9491 62
" The particular object of making reapings monthly was to decide

if at any season of the year the leaves yielded a higher percentage of
oil or an oil of better quality; the data collected from the reapings made
• in 1913 are shown in the preceding table.
" In considering these results it is noticed that there are abrupt
differences in certain months, e.g. the high specific gravity and phenol-
content in March, the low phenol-content on 12 June, and the striking
fall in the proportion of oil obtained in October, that need explanation ;
but, on the whole, the results are in accord with those obtained in the
previous year, when June and July gave better returns than any two
contiguous months of the year.
"Experiments both here and in Antigua have shown that specific
gravity and phenol-content are considerably influenced by the kind of
leaves collected for distillation, and the larger the amount of immature
growth included in the reapings the less satisfactory these two factors
prove to be. This is again clearly demonstrated in two tests made for
the purpose, the first on 15th December, 1913, when only mature leaves
were distilled. The specific gravity and phenol-content in this case
were as shown in the table, and in the test for comparison made on
16th January, 1914, young growth preponderated, and the specific gravity
of the oil was O8856 and the phenol-content only 33 per cent. In view
of this it is premature to say whether the rise in yield and the better
quality of the oil obtained in the middle of the year during the last two
years are due solely to the absence of young growth at the time. For
the first six months of 1914 the average \yield per 100 Ib. of leaves has
risen to 20 oz. It has been a rule-of-thumb practice to dry the leaves
for three days before distillation, but no scientific examination of thia
point has been carried out, and it is not known whether the drying in-
creases or diminishes the oil yield."
MYETACEÊ 385
The distillations were repeated in 1917 with the following re-
sults :—
Weight of Oz. of Oil Specific Phenol-

Date Distilled, 1917. Green Leaves per 100 Ib. Gravity. content
distilled, Ih. Leaves. per Cent.
January 12th . 159 16-7 •9382 50

January 19th . 159 17'6 •9414 56
January 26th . 161 17-9 •9480 55
February 2nd . 157 17-7 •9440 56
February 9th . 162 19-9 •9513 56
February 16th . • 177£ 16-7 •9504 57
February 23rd . 171 17-8 •9450 50
March 14th 177 16-1 •9462 55
March 22nd 162 16-6 •9542 57
March 27th 162 18-7 •9480 59
April llth 155 19-8 •9486 60
April 18th 145J 18-8 •9470 53
May 9th . 150 20-0 •9530 57
May 14th 150 18-2 •9453 56
May 17th 144 18-4 •9354 55
June 13th 150 16-1 •9467 56
June 21st 141 16-1 •9413 54
July llth 154 17-8 •9332 53
July 18th 158 17-6 •9433 55
July 26th 158 15-1 •9285 52
August 3rd 170 18-4 •9493 59
August 9th 162 17-1 •9480 54
August 16tli 148 18-7 •9470 55
August 23rd . 158 15.6 •9390 52
August 30th 141 18-1 •9520 55
September 6th 164 18-1 •9312 50
September 14th 147 18-2 •9420 55
September 20th 138 17-9 •9437 56
September 27th 153 18-0 •9340 50
October 4th 159 18-6 •9330 50
October 12th . 156 16-8 •9390 48
October 18th . 135 20-1 •9513 60
October 25th . 145 20-0 •9563 63
November 2nd 148 19-0 •9550 63
November 8th 168 17-8 •9490 58
November 15th 148 18-5 •9483 60
November 23rd 144 1 19-0 •9392 52
November 29th 148 19-4 •9512 60
December 6th . 145 17-6 •9446 54
December 13th 154 15-5 •9345 55
December 20th 153 15-5 •9347 54
- A sample of the oil from each distillation was forwarded to and

examined at the Government Laboratory at Antigua. It is seen that the
average yield of oil per 100 Ib. of the leaves reaped is 17*8 oz., compared
with an average of 17*3 oz. on 40 distillations in the previous year. The
interesting fact is also brought out by the data, that there has been con-
siderable improvement in the quality of the oil obtained, as indicated by
the specific .gravity and phenol-content, and a comparison with the
averages obtained in three previous years shows the following
results :—
VOL. I. 25
Season. Specific Phenol-conteiit

Gravity. per Cent.
Average 1914-1916 •9351 50-9
1917 •9441 55*0
This improvement in the quality of the oil cannot be accounted for,,
as the methods of distillation were strictly comparable with those followed
in the previous year.
As indicating the characters of the various fractions, and showing
how different the quality of the oil may be according to the time accu-
pied in the distillation, 150 Ib. of fresh leaves were distilled and the
fractions coming over during each of nine hours examined. The results*
Oil Obtained in c.c. Phenol-content. Specific Gravity.
1st ho ur 519 1st ho ur 23 1st ho ur 0-8669

2nd 126 2nd 78 2nd , 0-9241
3rd 98 3rd 89 3rd , 1-0259
4th 96 4th 93 4th 1-0381
5th 69 5th 95 5th 1-0409
6th 58 6th 96 6th 1-0432
7*th 53 7£th 99 7Jth 1-0434
9th 38 9th 96 9th 1-0436
According to Fishlockl there exists, in addition to the recognised

type of Pimenta acris, which produces the bay oil of commerce, in
various parts of the West Indies a variety closely similar in appearance,,
but yielding an oil of strong lemon scent and of little commercial value*
In Porto Eico this is known as " lemoncillo". This lemon-scented
variety is common in Dominica and St. Lucia. In Tortola it is the
kind commonly met with, the true type being rare, whereas this con-
dition is reversed in St. Jan. In Montserrat it is reported to be absent.
Fishlock examined the experimental tree plot at the Government
Station at Tortola and reported thereon as follows :—
" The trees in the plot were planted in November, 1914, by Mr. C. A.
Gomes; they had been raised from seed carefully hand-picked from-
a single tree having excellent characters growing in the station. This,
tree came from St. Jan in 1902 with some others, and was planted by
me at the station. Only two of the trees then planted have survived;
one is a tree having good characters and undoubtedly of the true variety ;
the other is unmistakably of the false or lemoncillo type. The latter
tree flowers earlier than the true variety, and, consequently, I do not
think there has been cross fertilisation.
" Upon careful examination of the plants in the plot referred to we
found that, of sixty-two living plants, twenty-two, or 35*5 per cent.r
were of the false or lemoncillo type. This appears to indicate that the
original plant, the one planted in 1902, is a hybrid, and that its progeny
are splitting up into two distinct types—roughly, 65 per cent, coming
rue and 35 per cent, reverting to the lemoncillo type.
" These observations may help to throw some light upon a subject
which has already received some amount of attention. It is, of courser
'P. andE.O.R. (1916), 803.

MYETACEÊ 387
of the highest importance that in the production of a high-class bay oil
there should be no admixture of leaves of the lemoncillo type."
It is suggested that the distillation of the oil should be carried out
at a central distillery under competent control, so that a uniform pro-
duct can be assured.
A sample of bay oil from Fiji, examined at the Imperial Institute in
1909, differed considerably from ordinary commercial bay oil. The oil
was pale brown, and had the characteristic odour of bay oil, with, in
addition, a distinct anise-like odour. On examination it furnished the
following constants : Specific gravity at 15° C., 0*961; optical rotation in
100 mm. tube at 20° C., - 1° 58'. The oil was soluble in its own
volume or more of 90 per cent, alcohol, and contained only 23 per cent,
of phenols instead of the 60 per cent, found in good bay oil, and was
unusually rich in methyl ethers. In view of recent investigations
recorded in the Kew Bulletin,1 it seems probable that the Fiji sample
consisted of oil derived from the leaves of the form of Pimento, acris
known as " Bois d'Inde Anise ".
Bay oil has the following characters (subject to the above remarks
on the irregularity of the distillation) :—
Phenols . . . . . . . . . 55 to 68 per cent.
Our knowledge of the chemistry of this oil is chiefly due to Mitt-
mann, 2 who first thoroughly investigated the oil, and to Power and
Kleber,3 who cleared up several points left in an obscure state by the
first-named chemist. According to Mittmann, pinene and probably
dipentene are present, together with the principal constituent eugenol,
and its methyl ether. He also believed a diterpene to be present, but
this was probably formed by polymerisation during the distillations he
effected. Power and Kleber do not agree thatteither pinene or dipen-
tene are present, but state that the only terpene( is laevo-phellandrene.
The oxygenated compounds which these chemists state they have
identified are eugenol, methyl-eugenol, chavicol, methyl-chavicol, and
citral. In addition to this they found a hydrocarbon of the formula.
îcHio with the abnormally low specific gravity '802. This, and other
considerations exclude the probability of this hydrocarbon being an
ordinary terpene, and the chemists above named term it myrcene, and
it is now recognised as an olefenic terpene.
The oil is sometimes adulterated with oils of cloves and pimento,
which cause an increase in the specific gravity. Turpentine is also
added at times. This alters the optical rotation and specific gravity,
and if the oil be distilled in a small fractionating flask the bulk of the
turpentine is obtained in the early fractions. Assuming that pinene is
not present at all in oil of bay, turpentine may be detected by adding
to, say, the first 10 per cent, distilled, an equal volume of amyl nitrite
and two volumes of glacial acetic acid. The mixture is kept cold in ice
and salt, and a mixture of equal parts of glacial acetic acid and hydro-
caloric acid is added drop by drop so long as a blue colour is developed.
If pinene is present a white crystalline precipitate of pinene nitroso-
chloride C10H16NOC1 is formed. Ten per cent, of turpentine can be
1
P. and E.O.R., :!October, 1918, p. 278. * Arch. Pharm., xxvii., 529.
Pharm. rendus, New York, 13 (1895), 60.
detected with certainty in this way. The oil should, when freshly
prepared, also be easily soluble in 90 per cent, alcohol, and when kept
for some time should be soluble with a slight turbidity. This oil is
largely employed in perfumery, especially in the preparation of the
favourite toilet article, bay rum.
OIL OF PIMENTO.
Pimento Oil or Allspice Oil is distilled from the fruit of Pimenta
officinalis Linn. (Eugenia pimenta De Candolle). The plant, a hand-
some evergreen, is indigenous to the West Indies, being found especially
on calcareous soil near the coast on the islands of Cuba, Hayti, Trinidad,
Domingo, Antigua, the Leeward and Windward Islands, and in abund-
ance in Jamaica. It also occurs in Mexico, Costa Eica, and Venezuela.
The bsrries are gathered in an unripe condition, as when ripe they are
filled with a sweet pulp lacking the characteristic aroma of the green
berry. These unripe berries, dried in the sun, form the pimento of
commerce, and Jamaica alone exports, chiefly from the port of Kings-
ton, about £50.000 worth per annum. The fruit, which is about the
size of a small pea or large peppercorn, has an aromatic odour some-
what recalling cinnamon, nutmeg, and pepper, with a predominating
odour of cloves. This explains the origin of the name allspice. It
yields from 3 to 4^ per cent, of oil on distillation, of a dark reddish
colour and of the same aromatic odour as the fruit.
The oil contains the phenol-eugenol with small quantities of cineol,
laevo-phellandrene, caryophyllene, eugenol-methyl ether, and palmitic
acid. The eugenol is, of course, responsible for the clove-like odour of
the oil, and the other bodies, together with one or more as yet unknown
constituents, modify the characteristic odour of the oil. A certain
amount of resin, due no doubt to the unstable nature of some of the
constituents, is usually present. The actual amount of eugenol in the
oil is approximately estimated by absorption with 5 per cent, caustic
soda solution, as in the case of oil of cloves.
It is soluble in 2 volumes of 70 per cent, alcohol, with at most slight
turbidity.
Pimento leaves yield an oil of similar composition, having the fol-
Optical rotation - 4° to - 5° 30'
OIL OF AMOMIS JAMAICENSIS.

The wild pimento of Jam lica, as it is called, is Amomis jamaicensis,
a tree growing to a height of 40 feet, found on ths limestone in the
woods of Upper Clarendon and in the Dry Harbour mountains. The tree
is a new species only named in 1919 by the Government botanists, and
experiments are being undertaken with a view to developing the dis-
tillation of its essential oil. In an experimental distillation by the
MYBTACE.E 389
Government Department, 100 Ibs. of the leaves yielded 202 c.c. of a pale
yellow mobile oil. This has been examined in the laboratory of the
Imperial Institute and found to have the following characters:—
Ester value 4-2
It is soluble in 2-5 volumes of 70 per cent, alcohol, becoming cloudy
with 6 volumes.
The principal constituent appears to be linalol, so that the oil has no
resemblance to ordinary pimento oil.
CHEKEN-LEAF OIL.
Cheken-leaf Oil is the product of distillation of the leaves of Myrtus
cheken, a plant indigenous to Chili. The yield is about 1 per cent, of a
pale yellowish-green oil, much resembling ordinary myrtle oil. Its odour
recalls that of myrtle, eucalyptus, and sage oils. According to Weiss,1
its specific gravity is about -880, and its optical rotation about + 20°; it
consists of pinene (75 per cent.), cineol (15 per cent.), and substances not
further examined.
OIL OP BACKHOUSIA.
Backhousia citriodora is a small tree indigenous to Queensland. The
leaves yield about 0*7 per cent, of essential oil which resembles lemon-
grass oil closely in odour. The oil has the following characters:—
Optical rotation 0° to - 0° 30'
Citral value 93 to 96 per cent.
The oil probably contains small quantities of a sesquiterpene.
OIL OF MESPILODAPHNE.
Mespilodaphne pretiosa is a South American tree, known as " Pris-
prioca ". It is a native of Eio Janeiro and Minas Geraes. The branches
yield 0'5 per cent, of an essential oil having an odour of cinnamon. It
Esters . . . . 4-65 per cent.
Total alcohols (as linalol) 51-8
The wood oil separates on distillation into a light and a heavy oil.
The light oil has a specific gravity 0*953, optical rotation + 8° 48', and
refractive index 1*501. It contains 35 per cent, of esters calculated as
linalyl acetate, and 66*6 per cent, of total alcohols calculated as linalol.
The heavy oil has a specific gravity 1*055, optical rotation + 3° 8', and
refractive index 1*5450. It consists chiefly of linalyl or geranyl benzoate.
1
Arch, der Pharm., 226 (1888), 666.
OIL OF EAVENSARA AROMATIC A.
The leaves of Eavensara aromatica, a large laurel tree growing on
the high plateaus of Madagascar, yield a large amount of essential oil,
which has been examined by Ferrand and Bonnafores.1 The oil con-
sists principally of a terpene, with a small amount of an oxygenated body
not identified. The terpene (?) boils at 171° to 172° and has a specific
gravity 0'881 and refractive index 1*4616.
OIL OF AGONIS FLEXUOSA.
Crozier 2 has obtained about 1 per cent, of essential oil from this
shrub, which closely resembles eucalyptus oil, containing 62 to 72 per
cent, of eucalyptol, cymene, pinene, traces of" alcohols, esters and
phenols, but no aldehydes.
ROSACES.
OIL OF KOSES.
Although at the present day oil or otto of rose is distilled almost
entirely in Bulgaria and France, only a very limited amount being pro-
duced elsewhere, there can be no doubt that the art of distilling roses
originated in Persia, and was practised on a large scale at a very
early date. The earliest record of this fact was discovered by Prof.
Fliickiger in an old work in the National Library in Paris. This docu-
ment states that between the years 810 and 817 of the Christian era,
during the reign of Kaliph Mamoun, the province of Faristan was re-
quired to pay an annual tribute of 30,000 bottles of rose water to the
Treasury of Bagdad. It is also stated by Istakhri that a considerable
quantity of rose water was produced throughout Faristan, and was from
thence sent to China, India, Yemen, Egypt, Andalusia, and Magreb (in
the Barbary States, especially to Morocco). The most important fac-
tories were at Dschur (now called Firuzabad), situate ^between Shiraz
and the coast.
The art of distilling roses was probably introduced into Western
countries by the Arabs.
The essential oil of the rose was described by Rossi in the latter half
of the sixteenth century, but was not discovered until 1612 in Persia,
and then only by accident. Sawyer gives the following historical details
of the discovery of otto of rose :—
The date of the discovery by the Persians of this valuable essence has
been ascertained by Langles to be 1612. He was thoroughly acquainted
with the languages and literature of the East, and in his excellent little
book 3 he shows that previous to this date (1612) no mention of otto of
rose is made in any work written in Oriental language, and that the
circumstances attending the discovery are for the first time described in
a work written in Persian by Mohammed Achem, entitled Tarykh mon-
tekheb lubdb, which is a history of the Great Moguls from the year
1525 to 1667. In this work mention of the essence is twice made.
1
Bull. Sci. pharmacol., 20 (1913), 403.
2
P. and E.O. Record, 9 (1918), 58.
3
Reclierches stir la decouverte de VEssence de Roses, Paris, 1804.
BOSACE^! 391
The first time, it occurs in the chapter entitled: " Marriage of the
Princess Nour-Djihan with the habitant of the paradise Djihan-guyr;
inventions and discoveries of the Queen of the World ". The second
mention is made in the chapter entitled : " History of the seventh year of
the reign of Djihan-guyr, and Feast of the New Year". According to
the translation, it appears that at the commencement of this fete, the
mother of Nour-Djihan having presented to the prince the " essence of
rose water " which she had prepared, the prince thereon attached to this
discovery his illustrious name, and called the perfume A'ther Djihan-
.guyry (Perfume of Djihanguyr); at the same time presenting to the
princess a necklace of the value of 30,000 rupees.
Another version of the circumstances connected with this discovery
is recounted by Manucci, a Venetian physician who resided about forty
years in India. He bases it on the Annals of the Mongolian Empire, an
important work translated by Catron. According to this description the
f&te was of a very costly and magnificent character, luxurious amuse-
ments of every sort being provided, the princess even carrying her ex-
travagance and prodigality to the extent of causing 'rose water to flow
through a canal constructed in the flower gardens. It then happened
that whilst the emperor and the princess were walking along the bank
of this canal they noticed that an oily stratum had concentrated on the
rose water and was floating on its surface ; this was carefully collected
and recognised by the entire Court as the most delicate of perfumes.
The distillation of otto of rose to-day, however, is essentially a Euro-
pean industry.
The Bulgarian rose plantations are situated in the Balkans, and from
the slopes of these mountains the greater portion of the otto of rose of
•commerce is obtained. The most important centre of the industry is
Kezanlik. The area under cultivation is included between the 24th
and 26th degrees of longitude east, and the 42nd and 43rd degrees of
latitude north. The geological formation is chiefly syenite, the decom-
position of which has produced a very fertile soil. The roses flourish
best in sandy sun-exposed slopes, with a south or south-eastern aspect.
The most important districts are (1) the department of Stara-Zagora,
including the cantons of Kezanlik, Nova-Zagora, and Stara-Zagora;
(2) the department of Pazardjik, chiefly the canton of Pechtera ; (3)
the department of Philippopolis, including the cantons of Karlovo,
Tchirpan, Novo-Selo, andBrezovo.
The rose country occupies especially the two valleys of the Toundja
•(canton of Kezanlik) and of the Strema (canton of Karlova) both
bounded on the lower side by a spur of the Balkans called Sredna-
Gora. The south side of this mountain supports numerous rose farms,
but their produce is inferior to that obtained from the south side of the
Balkans proper, not only in consequence of less favourable climatic and
geological conditions, but because the two indi spensable factors of the
work of distillation, namely, the water, and the wood for fuel, are much
less easy to obtain there by the distillers.
The rose cultivated in this district is Rosa damascena, a red rose,
but the hedges of the plantations are often made up of Rosa alba. The
latter are often distilled with the red roses, but as the resulting oil con-
tains more stearoptene than that of the Rosa damascena, it is rarely dis-
tilled alone.
The flowers are gathered before they commence to open, in the early
morning just before sunrise, and the picking continues till ten or eleven
o'clock, or on cloudy days during the whole day, as it is important that
the roses should not be picked when the sun's heat is on them. A
garden of an acre when well planted will yield about 100 Ib. of flowers
every day for three weeks. The roses are carried to the distilleries,
which are very numerous, and distilled as quickly as possible. How-
ever, if the flowers come in too quickly, they are sometimes left for
twenty-four hours before being distilled, the resulting oil being thereby
impaired in value. The distilleries are primitive buildings, sometimes
little better than wooden sheds. On one side the stills are kept in rows.
These are copper alembics about 3 to 5 ft. in height, resting on a fur-
nace built of bricks. The average content of each still is about 20 gal-
lons, the charge usually being 10 kilos of flowers and 75 litres of water.
The condenser is a straight or worm tube passing through a vat of
water, into which cold water continually runs. A brisk fire is kept up
for an hour to an hour and a half, and when 10 litres of liquid are ob-
tained the fire is drawn. At times 15 litres are distilled over, but the
result is an otto containing a larger amount of stearoptene. The still
is then opened and the spent petals, or rather flowers, for the green
FIG. 34.—A, copper alembic; B, condenser; C, receiver.
plants are seldom separated, are thrown away, and the residual hot
water is returned to the still with cold water to make up the 75 litres,
with a fresh charge of flowers. This operation is repeated until, as a
rule, 40 litres of rose water have been collected. These 40 litres are
now distilled, and the first 5 litres are collected in a long-necked flask.
The residual 35 litres are used ,for distilling fresh flowers. The 5 litres
distilling over are cloudy, and the oil drops gradually rise and collect
in the neck of the flask. When it has all risen, it is removed by a
small tin funnel with a tiny orifice for the water to be drawn off. The
yield is variable, a warm humid spring with intervals of strong sun-
shine being more favourable than an uninterrupted hot dry season. The
average yield in Bulgaria is about 1 kilo of otto from 3000 kilos of rose
leaves.
Adulteration of Bulgarian otto of rose is so common as to render it
a matter of the highest importance to purchase this expensive product
from dealers of repute, as the adulteration practised has been raised to>
ROSACE Ê 393
a fine art. With every advance in our knowledge of the chemistry of
otto of rose, the unscrupulous advisers of the Bulgarian sophisticators
have prepared cheap artificial products similar in characters to the
natural constituents, so that it is necessary to judge the quality of an
otto of rose with great care, since the physical characters are closely
simulated by the artificial adulterants.
Formerly palmarosa oil was almost the only adulterant used. To-day
geraniol, citronellol, and similar bodies are used to the exclusion of the
crude palmarosa oil. It is surprising that an industry of so much im-
portance should have been allowed to go on for so many years fettered
by two such great evils ; firstly, the enormous adulteration practised,
secondly, the defective methods of preparation, resulting in the spoiling
of the fine odour of much of the otto. Although climate and soil have
so great an influence on the yield and quality of the oil, there can be no
doubt that there are localities where rose cultivation and distillation could
be carried on in a scientific as well as an honest way.
Formerly the dealers were responsible for the greater part of the
adulteration, but now the small growers come in for their share of the
illicit profits, and not only do they add the adulterant to the distillate,
but frequently sprinkle the leaves with geraniol before distillation, believ-
ing that they so obtain a better " blend ".
The value of a pure oil depends on the quality of the flowers used
and on the care taken in distillation. It also depends on the amount of
solid stearoptene present, for this portion of the oil is quite inodorous.
The value of otto in the locality of its distillation is gauged almost
entirely by its melting-point. Consequently spermaceti or even paraffin
wax has been added to counteract the reducing influence of the liquid
geranium oil. Recently, too, guaiacum wood oil (so-called), an oil of
fine odour which solidifies with a fine crystalline structure at ordinary
temperatures, and consists of bodies much resembling those in oil of
roses, has been used as an adulterant.
In this connection it may be mentioned that no standard for the
quantity of stearoptene present in natural rose oil can be fixed, as climatic
conditions appear to influence the ratio of the solid to the liquid portion
very greatly. From 10 to 20 per cent, occurs in Bulgarian oil, whereas
that obtained in the south of France, in England, and in Germany, has
been stated to contain from 25 to 65 per cent, of stearoptene. In the
case of so high a content as the latter figure it is certain that the oil was
not prepared in the normal way, probably being the result of the distilla-
tion of rose water. Further, steam distilleries are being erected, and so
far as one can judge at the present moment, an otto of different properties
is obtained when distilled by steam instead of in the usual manner.
In Germany, Schimmel & Co. have laid out plantations near Klein-
Miltitz, and although the natural resources of climate and soil are not so
favourable here as in Bulgaria or Southern France, the scientific and
careful way in which the oil is obtained to a certain extent counter-
balances this, and a fairly fine otto is obtained. The amount, however,
is only very small. In Algeria a small amount of otto is produced, but
the yield is less than in Bulgaria. In Persia and Cashmere, however, it
is said that nearly 1 Ib. of otto is obtained from 1500 to 2000 Ib. of petals.
Anatolia, Hungary, Russia, and Spain also produce a small amount
of otto of rose, but apart from Bulgaria, France is the only important
rose-growing country.
-394 THE CHEMISTEY OF ESSENTIAL OILS
The roses which are under cultivation in France for perfumery
purposes exclusively are high in price, because the May rose bushes (Centi-
folia or Damascena) are of fairly weak growth; they do not grow more
ft
than 60 cm. in height, and only bear a few small roses of little
weight.
This is also a reason why these roses are specially used for " enfleur-
age,' hot or cold, for the manufacture of pomades, oils, and rose extracts.
KOSACE.E 395
But there are on the Azur coast, and in many other districts in France,
important rose gardens, which have been planted with a view to the sale
• of cut flowers for florists.
In the Lyon district (in Touraine) the florists usually sell the plant;
in the South, they export during all the winter the prematurely opened
blossoms. Thanks to rational irrigation, to a system ot removable glass
houses covering hundreds of acres, and to the application of special skill
in pruning and manuring, these roses realise up to T50 fr. each in the
winter, and it is clear that the entire profit from these rose gardens is
• cleared before the spring flowering commences. At that time all the
rose bushes flower at the same time. The flowers are no longer of any
value, and are left at the disposal of pickers for a small consideration.
Up to 1910 all these roses were sold at 0*10 fr. or 0*20 fr. per kilo ;
from that time onwards, the red variety, " Brunner," admitted to be the
best, increased in value, and fetched 30, 40, and even 60 c. per kilo. The
pink varieties, especially Van Houtte and Paul Nabonnand, the yellow
varieties, Safranos, and the white varieties, Druski, remained at lower
figures. These flowers are obtainable in millions of kilos, and it is esti-
mated that 5000 to 10,000 kilos of roses are required to produce one kilo
of essence. French otto has a clear and penetrating perfume, similar to
that of the freshly-cut flower.
In France only steam stills are used, to the exclusion of apparatus
used with open fires, which in burning the flower somewhat imparts to
the essential oil a slightly burnt odour; the French ottos obtained with
^steam do not offer this drawback.
The " Eose de 1'Hay," a comparatively new rose, is a very strong
grower. In less than two years a plant becomes a thick bush, full of
.leaves, and more than 2 metres high. It is very prolific in flowers, pro-
ducing in the month of May more than 2 kilos of roses, and continuing
to flower for at least five months.
The otto distilled from the " Eose de 1'Hay " is of a greenish-yellow
tint, but becomes yellow on keeping, and has a relatively low melting-
point, but an excellent perfume.
It will be very easy to propagate this variety all over France, and to
•obtain, in addition to the crop of the South, an important quantity of
•otto.
The characters of otto of rose vary considerably according to the
locality in which the trees are grown, and also in one locality from
season to season according to climatic and other conditions. All these
factors must be taken into consideration in forming an opinion on otto
>of rose, and it must be remembered that no published figures can be
accepted as final or exhaustive. The following may be taken as being
typical, however, of the best ottos produced in various localities :-—
BULGARIAN OTTO OF EOSE.
qno
lo*o
Optical rotation . - 1° 30' to - 4°
Refractive index at 25° 1-4580 to 1-4650
Melting-point 19° „ 22°
Citronellol . 28 „ 34
Acid value . 0-1 to 0-3
Ester ,, 0-7 „ 1-2
Stearoptene content . 15 to 20 per cent.
FRENCH OTTO OF EOSE.
In France numerous different roses are distilled, each yielding its
own characteristic otto, so that the resulting products will vary according
to the percentage of each given rose in the distilling material.
In 1904 Jeancard and Satie 1 published a paper dealing with the
analysis of otto of rose. They distilled a sample from the sepals only of
Eosa centifolia, and found it to have the following characters :—
Congealing-point
Stearoptene 51*13 percent.
Rotation. - 41°
Melting-jôint of si earoptene 14°
Acid value 6-12
Ester „ 16-28
Total alcohols 13*99 per cent.
Citronellol 13-56
This sample, as will be observed, contained practically no geraniol,
the alcoholic constituents consisting entirely of citronellol.
An oil distilled from the whole flowers, on the other hand, had^the
Rotation . - 3°
Alcohols . 88-5 per cent.
Citronellol 22-4
Congeal ing-point 25-5°
Stearoptene 32*2 per cent.
A similar oil, distilled without cohobation of the distillation waters,
and so distilled that 1 kilogram of roses gave 1 litre of rose water, had
the following quite different characters :—
Congealing-point 25-9°
Stearoptene . 58-88 per cent.
Acid value 2-24
Ester „ 14-70
Total alcohols 32 per cent.
Citronellol 15-10 per cent.
Dupont and Guerlain,2 have found samples of French otto of rose to
have specific gravities varying between O8225 and 0*8407 at 30°, optical
rotations from - 6° 45' to - 8° 3', and stearoptene-content from 26 to 35
per cent.
An authentic otto distilled from tea-roses only was found to contain
72 to 74 per cent, of Stearoptene.
Two analysis of ofcto from the rose d'hai have been published by
Schimmel & Co. The figures are as follows :—
1. 2.
Specific gravity at 30° 0*8706 0-8653
Rotation . - 1°26' - 3° 20'
Melting-point . 13° 18-6°
Acid value 1-8 1-8
Ester „ 6-3 5-6
Total alcohols 91 per cent. 91-8 per cent.
As a matter of fact, the total alcohols in this particular type of otto
consist almost entirely of geraniol, and are nearly free from citronellol.
1 1J
Bull. Soc. Chem. de Paris (1904), 934. Comptes rendus, 123 (1896), 700.
ROSACES 397
The Nabonnand roses are to-day members of the " Roses des jardins",
or mixed garden roses, used for distillation purposes. These roses, dis-
tilled by themselves, yield an otto having a specific gravity 0*8537 at 30°,
rotation - 2-2°, melting-point 19°, and ester number 42. As judged by
the usual standards set up by limited experience, this otto would be con-
demned by non-experts on account of its extraordinarily high ester-
content.
The Van Houtte roses, too, have a quite different character from any
other, in so far as they yield an otto with the very high optical rotation
- 11°, and the Brunner rose yields an otto which melts at 28°, rarely
below this.
The writer has examined authentic otto distilled from the Rose d'Hai
during 1916, and found it to melt at 8° and to have a specific gravity of
about 0-880. Its alcohol value was 90 per cent., consisting almost entirely
•of; geraniol.
398 THE CHEMISTRY OF ESSENTIAL*OILS
Mixed roses, in the fair average proportion in which they are distilled
in practice in the South of France, will give analytical values approximat-
ing to the following, but of course their limits are exceeded if certain
roses are used in greater proportion :—

Rotation - 2° „ - 4°
Saponification value . . . . . . . 15 ,, 35
Geraniol 35 „ 42
Citronellol 35 ,, 45
ROSACES 399
GERMAN OTTO OF ROSE.
1. 2.
Germaii Oil, German Oil,
Miltitz, 1900. Miltitz, 1900.
at 40° at 40°
at 30° at 33°
0-8438 0-8360
at 30° at 33°
Rotatory power . . . . - 0° 44' - 0° 52'
Congealing-point . . . . + 29*0° + 30-0°
Stearoptene-conteDt 28-50 per cent. 39-97 per cent,
Acid number . . . . . 2-3 0
Saponification number . 4-5 10-4
,, ,, after acetylisation 188-7 171-14
,, » »» formylatioa 59-21 47-9
Calculated from these figures—
Total alcohols C10H18O . 60*44 per cent. 54*00 per cent^
Citronellol in the formylation product 16-49 13-34
HUNGARIAN OTTO OF ROSE.

SPANISH OTTO OF ROSE.

Samples distilled in Chinchilla have been examined and show the-
Optical rotation . . . . . . - 1° „ - 3°
Refractive index a t 2 5 ° . . . . . 1-4520 „ 1-4568
Acid value . . . . . . . . 3 „ 5
Ester , 9 „ 12
Total alcohols . . . . . . . about 45 per cent.
RUSSIAN OTTO OF ROSE.

A sample distilled from flowers grown in the Imperial Appanages of
Kachetie (Caucasus) which had been cultivated from Bulgarian cuttings,
and has been examined by Roure-Bertrand Fils,1 had the following
characters: —
Optical rotation -4° 16'
Solidifying-point 23°
Liquefying point 25°
Stearoptene 33-5 per cent.
Acid value 5-7
Ester ,, . 4-7
,, as geranyl acetate 1-66 per cent.
,, value of acetylated oil 157-2
Total alcohols . 49-6 per cent.
Gitronellol 34
Geraniol . . . . 15-6
That is, the total alcohols contained 68'5 per cent, of citronellol and 31-5
per cent, of geraniol.
An otto of rose distilled in the Caucisus has also been examined
very fully by the same firm, who found it to have the following char-
acters :—
1
I. Physical Characters of the Complete Otto.
Colour o f t h e otto . . . . . Pale yellow
Specific gravity at 15° G 0-8618
Optical rotation, a D at 27° C. - 2° 28'
Solidifying-point . . . . . + 19° C.
Temperature at which the otto becomes com-
pletely liquid + 23-5° C.
II. Solid Portion, Insoluble in 75 per Cent. Alcohol.

Stearoptene ....... 23-1 per cent.
Elaeoptene ( b y difference) . . . . 76-9
Melting-point of the stearopfcene + 31-5° C.
Coefficient of saponification of the stearoptene 6-5
III. El(Eoptene.
Specific gravity at 15° C. 0-8809
Optical rotation, <XD at 15° C. - 2° 26'
„ ,, of the acetylated oil - 1° 16'
Decrease in rotation 1°10'
Solubility in 70 per cent, alcohol . 1 vol., then cloudy
Becomes cloudy
Solidifying-point . . . . but does not solidify
at - 15° C.
Acid value ....... 1-4
Ester ,, ....... 10-3
Saponification value . . . . . 11-7
,, ,, of the acetylated oil 259-5
„ ,, „ formylated oil . 121-3
Percentage of esters, as citronellyl acetate . 3-63 per cent.
Combined alcohols \ 2-9
Free „ V as citronellol, C10H«,()0 86-8
Total „ ) 89-7
Percentage of citronellol (by formylatiou) 35-8
,, ,, geraniol (by difference) 53-9
Composition of the alcoholic 39-9
60'1
IV. Results Calculated to the Complete Otto.
Stearoptene . . . . 23-1 per cent.
Free acids (as acetic acid) 0-37
Esters (as citronellyl acetate) 2-79
Gitronellol . . . . 27-53
Geraniol and phenylethyl alcohol 41-44
Terpenes, etc. (by difference) 4-77
SPARTAN OTTO OF EOSE.

For some few years past there has been a commercial utilisation of
the rose flowers growing naturally in the valley of Lake Burdur in the
interior of Asia Minor.
Lake Burdur is situated between the town of that name and Isbarta.
This latter is the ancient Sparta of Pisidia, which was a flourishing town
in the days of Alexander the Great. The whole of this district is in-
habited by an essentially agricultural population, who own land of mag-
nificient fertility. The climate is mild, and the valley, protected by the
mountains against cold and frost, is most favourably situated for the
culture of roses.
Most of the peasants own stills for the distillation of their flowers,
while there are other cultivators in a rather better position who buy up
EOSACEÊ 401
the roses of those whose production is very small and who possess no
distillation apparatus of their own.
The quantity of essence produced during 1912 was 300 kilos, and in
1913 to 400 kilos. Up to 1912 all this was purchased by the agents of
Bulgarian or Constantinople houses, who bought up all that was offered,,
selling it again to their fellow-countrymen who exported it again under
their own seals, principally as Bulgarian otto of rose. So it happened!
that quite an important production was entirely unknown to Western
consumers.
During the last few years, however, upon the initiative of certain of
the greater distillers, a combine was formed to bulk the entire production
of Sparta and Burdur, and sell it direct to Europe instead of passing it
through Bulgaria. This was, of course, an advantage, not only to the
growers, but also to the European consumers, in that it did away with
intermediate expenses and profits.
The product is then sent down to Smyrna, the principal port of Asia
Minor, by the railway that connects Burdur with the coast, to the
exporting agents.
The otto is of extreme delicacy of perfume and of high melting-point,
as the following analysis shows :—l
Specific gravity — 0-850
ID
Optical rotation - 3° 30''
Melting-point 24° to 25° CL
PERSIAN OTTO OF ROSE.

Specific gravity at 30° . . . . . . . . 0-830
Melting-point 21 to 22°
It is obvious from the above figures that the locality of production
must be considered in forming an opinion as to the purity of otto of rose.
Adulteration with palmarosa oil is revealed by the odour apart from
the obvious alteration in the physical characters of the sample. Alcohol
is frequently added in small quantities as it causes the stearoptene to
become less soluble, and so raises the apparent melting-point.
Alcohol can be detected by distilling a few c.c. of the sample with
water, and testing the distillate by the usual iodoform reaction. If the
sample be washed with warm water in a separator, and the refractive-
index of the washed otto be examined, it will be found to be higher thani
that of the original otto. If this excess be more than O'OOl it is almost
certainly due to alcohol.
The author, a few years ago, observed a new adulterant in Bulgarian?
otto of rose, which caused the optical rotation to be abnormally high.
This has since been identified by Schimmel & Co.2 as gurjun balsam oiL
This is detected by mixing 5 drops of nitric acid with 5 c.c. of glacial
acetic acid, and then shaking with 5 drops of the otto in question. In
the presence of gurjun oil a reddish-violet colour develops within a
minute or two.
The total alcohols are determined by acetylation in the usual manner,
and the citronellol by formylation. The formylation process is carriedi
out as follows :—
1 2
P. and E.O.R. (1913), 338. Report, April, 1912, 108.
VOL. i. 26
Ten c.c. of the oil are heated for one hour on a sand-bath in an
sacetylation flask with twice its volume of formic acid (specific gravity,
1*226). It is advisable to add a few pieces of pumice to assist the boil-
ing. The contents of the flask are cooled and 100 c.c. of water added,
and the whole transferred to a separator. The acid layer is run off, and
the oil is washed with water until the washings are neutral. It is then
dried by means of anhydrous sodium sulphate and filtered. The formy-
lated oil is then saponified with alcoholic potash in the usual manner,
free acids being first neutralised, and the percentage of citronellol in the
original oil calculated from the following formula :—
Total citronellol =0'156 x * x 10°.
w - (0-028*)
where x is the number of c.c.'s of normal alcoholic potash absorbed and
w the weight of formylated oil.
It was found by experiment that practically the same results were
obtained in the case of geranium oils, whether the oil was first saponified
or not. It is, therefore, sufficiently accurate to formylate the oil without
first decomposing the esters, since the formic acid apparently acts on the
alcohols whether combined or not.
Jeancard and Satie j determine the stearoptene as follows :—
Ten grams of the otto are weighed into a beaker and 50 c.c. of
acetone are added. The liquid is cooled to - 10° or thereabouts, without
shaking, and then filtered through a funnel kept in a refrigerating mix-
ture. The stearoptene is washed several times with cold acetone, and
dried on the weighed filter paper in vacua over sulphuric acid.
Burgess finds that for the estimation of the stearoptene 85 per cent,
.•alcohol gives the most accurate results. He finds that 5 grams of
the otto (in these experiments he also used 5 grams of a standard
solution of stearoptene in geranium oil, and in citronellol—see table), in
"25 c.c. of the solvent—or, if a weaker alcohol be used, 50 c.c.—is the
most suitable quantity for the determination. Solution is effected by
means of heat, and the liquid is then cooled in ice for five or six hours.
'The stearoptene is then filtered off on paper over a filter pump and
washed, once if 85 per cent, alcohol be used, twice if a weaker spirit be
êmployed ; the paper with the separared stearoptene is then dried in
-vacuo over sulphuric acid for twelve hours. It is not necessary to tare
the filter paper, since the stearoptene can be removed in one cake from
the paper, and weighed on a watch glass.
The appended table (p. 403) shows the results obtained with the
various solvents on otto of rose, and on standard solutions of stearop-
ftene in geraniol, and in citronellol. With acetone, he tound in some
cases that a further separation of stearoptene took place, so that he
has recorded the results in the form of the two weighings of the stearop-
tene where necessary.
By addition of alcohol and freezing the stearoptene can be almost
êntirely separated on a filter pump and 3washed with alcohol and finally
•dried. " It should then melt between 32 and 37°, usually at 33° to 34°,)
.Spermaceti, and most samples of paraffin wax, will cause this to be
rather higher, as will also " guaiacum wood " oil if present in more than
very small quantities. Salol and antipyrin have been found as solid
adulterants.
1
Bull. Soc. Chirn., Paris (1904), 934.
STEAROPTENE DETERMINATIONS. BURGESS'S ¥ABLE.
Geranium Oil. Citronellol.

Solvent. Otto of Rose.
5 per Cent. 10 per Cent. 15 per Cent. 5 per Cent. 10 per Cent. 15 per Cent.
I. II. I. II. I. II. I. II. I. II. I. II. I. II.

Per Cent. j
Per Cent. Per Cent. Per Cent. Per Cent. Per Cent. Per Cent.
75 per Cent. Alcohol 1
16-4 1 14-2 5-26 J 5-28 1
10-64 1 10-54 1
16-22 1 15-64 1
4*50 1 4-46 1
9-84 1 9-78 1
13-94 iUv.G
_ __ w
85 „ ,, 4-52 4-42 9-56 9-76 15-26 15-14 4-34 4-30 9-10 9-10 13-18 13-78 GO
90 „ „ 15-04 14-74 4-26 4-16 18 72 13-76 3-68 3-74 8-92 8-96 13-00 13-72 O
—
94 „ „ 14-4 14-1 3-84 3-88 8-58 8-56 13-40 13-44 3-20 3-16 8-24 8-50 13-00 12-66 fe
4-82 4-66 4-62 4-62
1-88 2-62 2-14 2-00
Acetone 13-8 14-0 3-68 3*84 13-38 13-44 3-12 3-08 12-16 12-16
6-70 7-28 6-76 6-62
8-46
4-63
Acetic Ether . . . . .
13-09
J
In all these cases the precipitate and filter paper were distinctly oily, showing imperfect solution of the eleoptene.
Spermaceti or stearin will be easily detected, whilst paraffin wax or
the solid constituent of guaiacum wood oil (which is of an alcoholic
nature) are not so easy of detection. As the stearoptene of pure rose oil
consists of hydrocarbons, no fatty acids will be obtained by saponification,
whereas spermaceti and stearin will yield on saponification and decom-
position of the resulting salts with hydrochloric acid, palmitic and
stearic acids respectively, which may be identified by their melting-
points (palmitic acid from 55° to 62°, and stearic acid from 62° to 68°).
Paraffin will be indicated by the more granular structure of its crystals
than that of the normal stearoptene, whilst the solid portion of guaiacum
wood oil consists chiefly of a solid alcohol and will give an acetylation
value which the pure stearoptene will not.
The following tables are given by Schimmel:—
1. 2. 3. 4. 5. 6.
German German Oil from F'hilippople

Oil, Oil, Bulgarian Bulgarian from ou r Expert.
Miltitz, Miltitz, Oil Oil
1900. 1900. (Kazanlik). (Kazanlik). Distilled Purchased.
by Himself.
at 40° at 40° at 30°

; Specific gravity 0-8372 0-8304 0-8566
at 30° at 33° at 25° at 25° at 25° at 25°
0-8438 0-8360 0-8598 0-8594 0-8634 0-8614
at 30° at 33° at 30° at 25° at 25° at 25°
Rotatory Power - 0° 44' - 0° 52' - 2° 20' - 2° 43' - 2° 58' - 2° 36'
CoDgealing-point + 29-0 ' + 30-0° + 20-0° + 20-4° + 19-6° + 20-4°
Stearoptene - con-
tent . 28-50 °/0 39-97 °/0 18-62 °/0 18-83 °/0 18-49 «/0 20-55 °/0
Acid Number 2-3 0 0 2-3 0
Sap. Number 4-5 10-4 11-03 7-0 11-1 10-1
Sap. Number after
Acetylisation 188-7 171-14 216-0 204-1 214-7 211-0
Sap. Number after
Formylation 59-21 47-9 92-9 96-8 104-0 100-6
Calculated from
these figures:—
Total Alcohols
C10H180 . 60-44 °/0 54-00 °/0 70-88 ° 0 66-27 °/0 70-37 °/0 68-93 °/0
Citronellol in the
Formylation Pro-
duct . 16-49 °/0 13-34 ° / 0 25-88 °/0 26-96 °/0 28-97 °/0 28-03 %
Values obtained direct in analysing oils free from stearoptene :—

Spec. Gravity at 15° 0-8857 0-8886 _ 0-8862 0-8774 _
Rotatory Power 20° - 0° 56' - 1° 2' 1 — - 2° 49' - 2° 38' —
Sap. Number after
Acetylisation 271-55 261-64 255-8 254-8 —
Sap. Number after * —
Formylation 74-70 81-22 125-28 127-4 —
Total Alcohol 93-78 % 90-80 °/0 — 87-04 °/0 86-63 °/0
—
Citronellol 20-81 °/0 22-63 °/0 — 34-90 °/0 85-50 °/0 —
Of the chemistry of oil of roses, although fairly well understood now,

much controversial matter has been written. Eckart 1 states'that a small
1
Inaugural Dissertation, Breslau, 1891.
BOSACEÊ 405
quantity of ethyl alcohol exists in the oil. If this is so, which Poleck
denies, it is in all probability the result of fermentation taking place in
the leaves, by keeping them too long before distillation. Markovnikoff
and Eeformatsky1 originally stated that the liquid portion of rose oil
consisted chiefly of an alcohol of the formula C10H20O, which they termed
roseol. Poleck and Eckart claimed that this alcohol had the formula
C10H18O, and was identical with geraniol. They, however, proposed the
name rhodinol (which was applied to an alcohol C10H20O from geranium
oil by Barbier and Bouveault) for it. Bertram and Gildemeister2 then
showed that the alcohols from rose oil were in reality a mixture of two
bodies, of which they agreed that geraniol C10H18O was the chief con-
stituent. Tiemann and Schmidt explained these differences, proving
that the alcohols consisted of about 75 per cent, of geraniol C10H18O and
25 per cent, of an alcohol C10H20O, which was identical with that obtained
by reducing citronellic aldehyde. Hence they naturally insisted on the
name citronellol, whilst Eckart claimed to have isolated an alcohol of the
formula C10H20O which he named rhodinol. For many years rhodinol
was regarded as an impure citronellol, but the two bodies are now known
to be separate individuals. Much confusion has unnecessarily been
caused by various chemists giving names to alcohols they had isolated from
different oils in an impure state, and refusing to alter these names after
it had been conclusively proved that they were, when pure, identical with
already known bodies. Lemonol, reuniol, and roseol are all either
geraniol or citronellol, or mixtures of them. The relationships of
rhodinol and citronellol are discussed in Volume II. Traces of esters of
these two alcohols, and of free acids resulting from their decomposition
also occur. The stearoptene was regarded by Markovnikoff as consist-
ing of a single paraffin hydrocarbon of the formula C16H34, melting at 37°,
but Schimmel & Co. have separated two hydrocarbons melting at 22° and
41° respectively from the stearoptene. This has been confirmed by
Dupont and Guerlain. These chemists suggest that the ester, which
appears to be found in larger quantity in French oils than in any other,
is an important odoriferous constituent, and is destroyed by repeated
distillation with water. They separated the liquid portion of the oil and
found it had an optical rotation of - 10° 30', which decreased to - 7° 55'
after hydrolysis. Charabot and Chiris invariably find rose water acid,
which tends to confirm this hypothesis.
Phenyl ethyl alcohol has recently been shown to be a normal con-
stituent of otto of rose, but it appears to be mostly, if not entirely lost or
destroyed by the Bulgarian method of distillation. Nerol is also present
in small amount as well as, probably, farnesol, a sesquiterpene alcohol
C16H26O, present in oil of cassie flowers. Eugenol, linalol, and nonylic
aldehyde are also present in traces.
OIL OF ALMONDS.
Oil of bitter almonds is obtained from the kernels (seeds) of the
ordinary bitter almond, Primus Amygdalus (Amygdalus communis), a
tree which is cultivated in Europe, Asia, Northern Africa, and Cali-
fornia. The kernels of the peach and apricot yield essential oils which
are practically identical with that from the almond, and many samples
of " almond oil " of commerce are no doubt derived from peach and
1
Jour. Praki. Chem., II, 48 (1893), 293. *Ibid., II, 49 (1894), 185.
apricot kernels. No distinction will be made between these three oils,,
as they differ in no sensible degree, except for the fact of their actual
origin.
Bitter almond oil does not exist as such in the almond kernel, but
results from the hydrolysis of a glucoside, amygdalin, under the influence
of the naturally existing ferment emulsin. The fatty oil is obtained
from the kernels by expression, and the press-cake crushed and digested
with water, when the following reaction ensues :—
C,0H27NOn + 2H20 = C7H60 + 2C6H12O6 + HCN.
Amygdalin. Benzaldehyde. Dextrose.
Amygdalin, taking up two molecules of water, yields benzaldehyde
dextrose, and hydrocyanic acid. Amygdalin is a crystalline body, with-
out any smell of the bitter almond, and does not yield the oil except
under the influence of a hydrolytic agent, such as the natural ferment
emulsin, or by boiling with dilute acids. The action of the ferment is-
destroyed by heat or by warm alcohol. Hence if dried and powdered
b.tter almonds are shaken with boiling water and distilled, no oil is
obtained. After the fixed oil has been expressed the press cakes are
ground up and soaked for about twenty-four hours in twice their weight
of water, to which a quantity of salt is usually added. The whole is then
subjected to distillation. Some trouble, however, is experienced during,
the process, as the large quantity of albuminoids present causes excessive
frothing. To remedy this, the press-cakes are coarsely powdered and at
once immersed in boiling water to coagulate the albuminoids and dissolve
the amygdalin. The emulsin is, of course, rendered inactive, so that on
cooling, a quantity of emulsin of the fresh cake in cold water is added
to the previously treated mass. This is allowed to stand, until the
emulsin will have converted the whole of the amygdalin into essential
oil. The mixture is now distilled. As hydrocyanic acid is a very deadly-
substance, it is necessary to use great care that none of the vapour is
allowed to escape into the air. The distillation is effected by direct steam
in most cases. The oil of almonds so obtained contains a considerable
amount of hydrocyanic acid, the remainder being principally benzalde-
hyde, C6H5 . COH. The absolutely natural oil is a regular commercial
article, but much is deprived of its hydrocyanic acid before being sold,
and is then listed at a correspondingly high price as " Oil of Almonds
(S.A.P.)" (i.e. Sine Acid. Prussic.). The following methods are used
to deprive the oil of this poisonous constituent:—
The oil is mixed with its own volume of water, and the mixture left
on a water-bath with red oxide of mercury, slaked lime, and ferrous
chloride, out of contact with the air. After all the prussic acid has been
decomposed, the oil is rectified and contains no trace of prussic acid.
This process was suggested by Redwood. Liebig used oxide of mercury
only. Mackay prefers agitating at intervals for forty-eight hours with a
mixture of lime and liquor potassae. To detect any traces of prussic acid
left in the oil, a little of it is dissolved in alcohol, and a few drops of
solutions of ferrous sulphate and ferric chloride are added. Slight excess
of caustic soda solution is then added, and the precipitate is dissolved by
the addition of dilute hydrochloric acid, when a blue colour or precipitate
(due to the formation of Prussian blue) appears if any hydrocyanic acid
is present. Benzaldehyde is very readily oxidised by the oxygen of the
atmosphere to ben zoic acid, so that the oil almost invariably contains
KOSACEÊ 407
traces of this body, and if kept in bottles that are not .quite full the
oxidation becomes more rapid, and crystals of benzoic acid are deposited.
This is more especially the case when the oil has been freed from prussic
acid. According to Schimmel & Co., 10 per cent, of alcohol added to
the oil retards this oxidation.
There appears to be little doubt that the action above indicated for
the decomposition of amygdalin does not take place as simply as in-
dicated. Recent researches by Kosenthaler l and others indicate that
the enzyme is not a single body but a mixture of ferments, and that the
system amygdalin-emulsin gives rise to the following series of reactions,
which end up with the oil containing benzaldehyde, hydrocyanic acid,,
and benzaldehyde-cyanhydrin:—
1. Amygdalin, under the influence of amygdalase (one-of the fer-
ments), yields mandelonitrile glucoside and glucose.
2. Mandelonitrile glucoside, under the action of prunase (another
ferment), yields d0££ro-benzaldehyde-cyanhydrin and glucose.
3. Z>0#£ro-benzaldehyde-cyanhydrin is resolved by d-oxynitrilase into
benzaldehyde and hydrocyanic acid.
4. Benzaldehyde and hydrocyanic acid unite again, under the in-
fluence of rZ-nitrolese, to form rfe#£ro-benzaldehyde-cyanhydrin,.
and also unite, naturally, to form the inactive cyanhydrin.
5. rZ-oxynitrilase effects the resolution of the inactive cyanhydrin,
giving rise to laevo-benzaldehyde-cyanhydrin.
Bitter almond oil is a highly refractive liquid of powerful odour
Optical rotation 0° to + 0° 10'
A higher specific gravity indicates a very high amount of hydrocyanic
acid, or an abnormal amount of benzaldehyde-cyanhydrin.
The oil is more soluble in water than almost any other essential oil,.
1 part dissolving in 300 parts of water at ordinary temperature.
Bitter almond oil, deprived of its prussic acid, has the following,
characters :—
Boiling-point 179°
Optical rotation 0° to + 10'
The oil should not contain more than 1 per cent, of benzoic acid as
determined by titration with decinormal alkali: higher percentages in-
dicate that the oil is old or has been badly stored, and its odour and
perfume value are proportionally lower as the benzoic acid increases.
The constituents of the oil are, as above indicated, benzaldehyde, tc*
which the almond odour is due, hydrocyanic acid, and benzaldehyde-
cyanhydrin, C6H5CH(OH)CN, which, however, is easily decomposed into
its components by distillation with water, so that an oil which has been
deprived of its hydrocyanic acid directly after distillation may be practic-
ally free from benzaldehyde-cyanhydrin.
The principal adulterant of this oil is synthetic benzaldehyde which
is almost impossible to detect, unless it contains, as it very frequently
does, traces of chlorine, due to impurities formed in the course of manu-
facture.
l
Arch. der Pharm., 251 (1913), 85.
Another adulterant, of a much grosser character, is oil of mirbane.
This is the cheap almond oil substitute so largely used for perfuming
common toilet soaps. Chemically it is nitrobenzene C6H5NO2, more or
less mixed with impurities, of which the most common is nitrotoluene,
-which sometimes itself forms the greater part of cheap nitrobenzene.
Indeed, nitrotoluene in any great quantity may be regarded as an adulter-
ant of nitrobenzene. The latter, when pure, is a yellowish liquid of
specific gravity at 0° of 1*200, boiling at about 206°, and solidifying at
-t- 2° to -t- 3°. It has a coarse almond-like odour, and is poisonous when
taken internally, and irritating to the skin when used externally. The
cheapness of artificial benzaldehyde should discourage its use in even the
very cheap toilet soaps. Nitrotoluene C6H4(CH3)NO2 exists in three
isomeric modifications, and nitroxylene (BgHgXCH^NOg in more still.
These bodies are found to a considerable extent in the cheaper qualities
of nitrobenzene. Consequently it is important that commercial samples
should have physical characters in approximate agreement with those
Above quoted.
To detect the presence of this objectionable substitute in oil of almonds
a little of the oil is warmed with iron filings and acetic acid. The nitro-
benzene is reduced to aniline C6H5NH2, which is distilled off and col-
lected. To the distillate a few drops of solution of ordinary chloride of
lime is added. If aniline be present the liquid yields the characteristic
^violet colour. Pure benzaldehyde combines with sodium bisulphite to
iorm a crystalline compound without the characteristic almond odour.
Samples adulterated with nitrobenzene, when shaken with excess of
bisulphite of sodium solution, so that the benzaldehyde is entirely com-
bined, then have the characteristic coarse nitrobenzene odour.
The determinations of importance in the examination of this oil are
*(1) the determination of chlorine, or at all events its detection qualitatively,
if present; (2) the determination of benzaldehyde, and (3) the determina-
tion of hydrocyanic acid.
The Determination of Chlorine.—Many methods have been suggested
for the detection and determination of chlorine, but most of them are
merely qualitative. Of these the following are useful :—
(a) By simple combustion. This method depends on the fact that on
combustion a portion of the chlorine present in the organic compounds
existing as impurities, forms hydrochloric acid, which can be detected by
means of silver nitrate.
A piece of filtering paper about 2 inches by 1 inch and rolled in the
shape of a spill, is saturated with the oil, the excess of oil is thrown off
and the paper is placed in a small porcelain dish which in its turn re-
poses in a larger dish, measuring about 8 inches in diameter. The paper
is ignited, and a beaker of a capacity of about 2 litres, moistened inside
with distilled water, is quickly placed over the paper. The sizes of the
dishes used must be such that the rim of the larger dish must stand out
well all round from the beaker. After the flame is extinguished the
beaker should be left in position for about one minute, after which the
products of combustion which have been deposited against the moist
sides of the beaker are rinsed out with a little distilled water, and
filtered. The filterate, acidulated with a drop of nitric acid, must remain
dear when silver nitrate solution is added.
Care must be taken that the filter paper is free from chlorine. This
should be determined by a blank experiment. This process has been
EOSACE^ 409
-strongly recommended by Schimmel & Co., but there is considerable
doubt whether it will detect minute quantities of chlorine.
(b) The sodium test is distinctly more delicate, and is carried out as
follows :—
A piece of pure metallic sodium about half the size of a pea is dropped
into 0*5 c.c. of the oil in a dry test tube, and heated until all chemical
action has ceased. The test tube and contents are immersed whilst still
hot in 10 c.c. of distilled water in a porcelain dish. The solution is
filtered, acidulated with nitric acid, and silver nitrate solution added.
Any turbidity or opalescence indicates the presence of chlorine com-
pounds.
A blank test should be performed to ensure the absence of chlorine
in the materials employed.
(c) The lime combustion method gives good results as a qualitative
test, although it will often fail to detect very minute traces, say below 0*08
per cent. It is carried out as follows :—
A mixture of 1 c.c. of benzaldehyde and 5 grams of lime are placed in
the bottom of a platinum crucible about 3 ins. in depth, a layer of lime
placed on the top and the crucible covered and gently heated; a con-
siderable escape of benzaldehyde takes place, so that it is obvious that
the results can have no quantitative value.
The temperature is then gradually increased until no further vapours
ure driven off. The mixture is then dissolved in dilute nitric acid, filtered
and tested in the usual manner with silver nitrate.
(d) The method of Carius for the determination of chlorine in organic
compounds is, of course, absolutely quantitative, but is very tedious.
Salomonl has recommended the following method, and appended are the
results obtained compared with those yielded by the Carius' method and
the obviously inadequate lime method.
About 1 gram of benzaldehyde is heated in a retort with 40 c.c. of
•concentrated sulphuric acid, the fumes collected in a solution of silver
nitrate, and the heating continued until no further precipitate insoluble
in hot dilute nitric acid is obtained in the silver nitrate solution. This
takes about three hours.
The solution of silver nitrate is acidified with dilute nitric acid, boiled
so as to decompose any silver sulphite that might have been formed, and
the precipitate filtered, washed, etc.
A slight modification consists in using a mixture of 40 c.c. concen-
trated sulphuric acid and 5 c.c. concentrated nitric acid, the nitric acid
•being added last to the mixture of sulphuric acid and benzaldehyde.
The hydrochloric acid was evolved more rapidly, and slightly higher
results were obtained in certain cases, due probably to better oxidation.
In using this method the heating must be very gradual, and the
mixture should not be allowed to froth until the end of the operation.
The Determination of Benzaldehyde.—It is doubtful whether there is
any accurate method for the determination of benzaldehyde in essential
-oil of almonds, in the presence of hydrocyanic acid, except in so far as
the actual free aldehyde is concerned. The most modern investigation of
.this question is that of F. D. Dodge.2
The results obtained by the use of the methods for chlorine determina-
1
2
P. and E.O.R. (1917), ±1.
Eighth International Congress of Applied Chemistry, Washington (1912), xvii. 15.
tion described on p. 389 are as follows, and certain of the samples were
checked by means of a Carius determination :—
Lime Method Sulphuric Acid Nitro-sulphuric Carius Method,

No. Chlorine, per Cent. Method, per Cent. Acid Method, per Cent.
per Cent.
1 •19 1-83 2-14 2'2

2 Not weighable 0'13 0-13 0-15
3 •20 1-8 1*9 2-0
4 •19 1-7 1-7 1-9
5 nil trace trace trace
6 •17 — 1-63
7 •28 2-66
8 •17 — 1-42
—
The United States Pharmacopoeia have adopted the method devised

by Sadtler, but this is not very satisfactory. It is based upon the forma-
tion of the phenylhydrazone. The benzaldehyde is added to an excess
of phenylhydrazine in alcoholic solution, and the phenylhydrazone is
filtered off. The uncombined phenylhydrazine is then neutralised with
semi-normal hydrochloric acid, and the amount of acid required is de-
ducted from the quantity required to neutralise the same quantity of
phenylhydrazine in a blank experiment. Unfortunately, the end point
with methyl orange is not sharp, and the method cannot be considered a
satisfactory one. The low minimum of benzaldehyde required for ben-
zaldehyde and bitter almond oil (85 per cent.) is practically an admission
that low results are obtained by this process. The method devised by
Ripper gave better values, although these, too, are only approximately
accurate. Eipper shakes up the aldehyde with a bisulphite solution of
known strength and titrates back the excess of bisulphite with iodine
solution at a low temperature. According to Dodge, the most suitable
manner of carrying out this method is as follows: 0*15 gram aldehyde
or bitter almond oil is weighed in a flask containing exactly 25 c.c. of a,
say, i n. bisulphite solution, and brought to solution by gentle shaking.
The flask is then closed, left standing in ice water for one and a half to-
two hours, after which the ice-cold solution is titrated with deci-normal
iodine solution, starch being used as an indicator. A blank test is carried
out in the same way, the benzaldehyde-content being calculated from
the difference (1 c.c. deci-normal iodine solution = 0*0053 gram benzal-
dehyde). The reaction is completed as soon as the blue colour persists
for a few seconds. By this method Dodge, in the case of pure benzalde-
hydes, found from 94*8 to 99'0 per cent.
Determination with hydroxylamine (Walther's method as modified by
A. H. Bennett) offered no advantages as compared with the iodometric
process, inasmuch as in the case of pure benzaldehydes only 93-5 and
95'1 per cent, were found. On the other hand, the estimation with
phenylhydrazine recommended by Denis and Dunbar gives useful,
although at times rather too high, values (95-1 to 100'9 per cent.), but
in this method the unstable character of the reagent is a disadvantage.
In this process 10 c.c. of a solution of the oil of 5 per cent, strength are
mixed with 10 to 15 c.c. of a fresh 10 per cent, solution of phenylhy-
drazine, the liquid shaken, the flask tightly closed, and allowed to stand
KOSACEJE 411
in the dark for twelve hours. 200 c.c. of water are now added, and
the liquid filtered through a Gooch crucible, and the precipitate washed
with cold water, ,then with 10 c.c. of 10 per cent, alcohol, dried for three
hours in vacuo over sulphuric acid at 70° to 80°, and weighed. The
weight multiplied by 5'408 gives the number of grams of benzaldehyde
in 100 c.c. of the solution.
Kleber's method, based on the use of phenylhydrazine is also ac-
curate for the determination of the free benzaldehyde. Slightly modified
by Schimmel & Co. this method is as follows :—
To 2 c.c. of a solution of the oil (about 5 per cent, strength), 10 c.c~
of a fresh alcoholic solution of phenylhydrazine are added and allowed to
stand for an hour in a stoppered flask holding about 50 c.c. Twenty c.c..
of deci-normal hydrochloric acid are then added and the flask gently
shaken. Ten c.c. of benzene are then added and the mixture is shaken
well and poured into a separator. The acid layer separates clear,
and is measured and filtered, and 20 c.c. of the filtrate is titrated with,
deci-normal potash, using di-ethyl-orange as indicator. From this the
titration figure for the full volume of the acid liquid is calculated. A
blank experiment is carried out without the almond oil, and each c.c. of
deci-normal potash in excess of that used in the estimation = 0'0106 gram
of benzaldehyde.
Dodge has proposed another method for the quantitative estimation,
of benzaldehyde. This is based upon Cannizzaro's reaction :—
2C6H5CHO + KOH = C6H5COOK + C6H5CH2OH.
He made tests with alcoholic potash solution, which showed that the
reaction does not proceed quantitatively when the solution is of less than
twice normal strength. Good results were obtained with a 2*5 normal
solution. Ten c.c. is allowed to stand for twenty-four hours at ordinary
temperature with from 1 to 2 grams of benzaldehyde, after which the
unattacked alkali is titrated back with semi-normal hydrochloric acid. A
blank experiment is carried out without the almond oil. The difference
shows how much of the alkali has entered into reaction, expressed in
c.c. of semi-normal potash. By multiplying the number of c.c. by the
molecular weight of benzaldehyde (106) and dividing by the quantity of
oil employed in the test, the aldehyde-content is obtained.
In the case of pure artificial products, Dodge found this figure to be
from 99*03 to 100*3 per cent. He lays stress upon the fact that in
measuring the 2'5 normal potash solution it is necessary to proceed with
great care, because so small a difference as 0'05 c.c. represents an error
of not less than 1 to 2*5 per cent, benzaldehyde.
In the case of natural bitter almond oil the method gave no useful
results, presumably because the saponification of the benzaldehyde-
cyanohydrin into mandelic acid was incomplete.
It is apparent that in natural bitter almond oil all these methods only
estimate the free benzaldehyde, and not that which is present in com-
bination with hydrocyanic acid. This is shown by the following results
(see table on p. 412).
The Determination of Hydrocyanic Acid.—Hydrocyanic acid may be
approximately estimated by dissolving 1 gram of oil in 5 c.c. of alcohol,
and adding 50 c.c. of water. Then add ammonio-silver nitrate solution
and shake well. Acidify slightly with nitric acid, and collect, wash, and
dry the silver cyanide precipitated. Ignite and weigh the silver, four
parts of which correspond to practically one of hydrocyanic acid.
Sample No. 1. Sample No. 2. Sample No. 3.
HCN . . . . 3*6 per cent. 2*8 per cent. 2*4 per cent.
Equivalent quantity of
cyanohydrin 17*6 „ —
Gale, quantity of free benzal- —
dehyde . . . . 82-4 „ 86-2 per cent. 88*2 per cent
Estim. by Ripper's method . 81-3 to 82-1 per 80 percent.; 81*4
cent. per cent.
Estim. with hydroxylamine . 78*9 per cent.
Estim. with phenylhydra- — —
zine (Denis and Dunbar's
method) . . . . 83-2 „ 83-6 per cent. ; 85-2 per cent.
87*2 per cent.
For an exhaustive examination of the various processes proposed for

the determination of hydrocyanic acid, the reader is referred to a series of
papers by Runne in the Apatheker Zeitung.1
OIL OF CHERRY LAUREL.
Cherry Laurel Oil is distilled from the leaves of Primus laurocerasus,
an evergreen shrub, a native of South-eastern Europe and Asia Minor.
Most of the oil is distilled in the south of Switzerland and in Italy. It
is obtained also in England and Germany, together with the official
cherry laurel water, by distilling the leaves in the ordinary way. It has
It contains benzaldehyde, prussic acid, benzaldehyde-cyanhydrin, and
possibly traces of benzyl alcohol, and, indeed, differs very little from oil
of bitter almonds.
OIL OF WILD CHERRY BARK.
The bark of Prunus virginiana yields about *2 per cent, of essential
oil of specific gravity about T050, and optically inactive. It closely re-
sembles oil of bitter almonds.
OIL OF MEADOW SWEET.
This oil is obtained by the distillation of the flowers of Spiraea Ul-
maria, which yield about 0*25 per cent, of oil.
It contains salicylic aldehyde, C6H4(OH)(COH), a terpene, methyl
saliglate, vanillin, and hetrotropin.
CALYCANTHACEjC.
OIL OF CALYCANTHUS.
2
Scalione has examined the essential oil of Butneria occidentalis, or
Calycanthus occidentalis, which he obtained to the extent of 0-27 per cent,
of the leaves and twigs. The oil had the following characters :—
l
Apotheker Zeitung, 24 (1900), 288, 297, 306, 314, 325, 333, 344, 356.
2
Jour. Ind. Eng. Chem., 1916, 729.
RUTACEÊ 413
On fractionation the oil gave the following results. The oil was.
fractionated with a 3-bulb Le Bel fractionating column :—
Frac- Fractionation Per cent. Specific Specific Index of
tion Temperatures Distilled Gravity Rotation Refraction
No. °C. over. 15° C. at 15° C. 15° C.
1 154-170 8-51 0-8810 + 16-42 1*4590
2 170-180 54-83 0'9119 + 5-85 1-4585
3 180-190 9-47 0'9215 + 6*56 1-4650
4 190-200 2-48 0'9290 + 9-52 1-4665
5 200-220 8-75 Q'9635 + 36-42 1-4817
6 220 over 10-22 0-9365 + 18-85 1*4793
7 5-01 0-9171 1-4884
Fractions 5, 6, and 7 were obtained under reduced pressure at 150°-180°. The
boiling-points of these fractions were redetermined at atmospheric pressure.
The oil was found to contain about 8 per cent, of pinene, 60 per cent,
of eucalyptol, 9 per cent, of borneol, 19 per cent, of linalyl acetate, with
a little camphor, methyl salicylate, and sesquiterpene alcohol.
From the dry twigs of Calycanthus floridus Miller, Taylor, and Eskew 1
obtained from 0'25 to 0*53 per cent, of a pale yellow essential oil having
a camphoraceous odour. Its characters are as follows :—
25°
Specific gravity at — 0-9136 to 0*9209
Optical rotation + 2*84° + 6-6°
Saponification value 12*5 16-6
(after acetylation) . . . 65*7 75-1
Eucalyptol is present in the oil, as well as a-pinene, salicylic acid (?),
borneol and, possibly, linalol. Bornyl esters of formic and acetic acids
are also" present.
RUTACEit.
LEMON OIL.
This oil, one of the most important of all the essential oils from the
commercial point of view, is obtained by various processes from the fresh
peel of the ordinary lemon, Citrus limonum (Citrus medico, subsp. Lim-
onum). The tree is a native of India, and was introduced into Southern
Europe, probably first into Spain, and thence to the South of France and
Italy. There are numerous varieties and hybrids, but the ordinary lemon
forming the fruit of commerce is the Genoese lemon. This is cultivated
on the Mediterranean littoral, especially between Nice and Genoa, in
Calabria, Sicily, Spain, and Portugal, and on nearly the whole coast of
Liguria. Many of the British Colonies are now cultivating this fruit,
Australia for many years past having filled its own requirements for
lemons; the trees are also extensively grown in New South Wales,
Florida, California, and Jamaica, and will, probably, shortly produce the
oil in considerable quantities. The oil is obtained in the South of Europe
between the months of November and March, or April, and the processes
used are the following: (1) The spugna or sponge process, by which
1
the oil is removed from the burst oil cells of the peel by a sponge. (2)
The ecuelle method, by which the lemons are rolled about in vessels
covered with spikes and the oil collected in a receptacle in the handle of
the vessel. (3) Machine processes. (4) Distillation. This method gives
a very inferior oil, and is often applied to the peels from which all the oil
obtainable by other processes has been obtained. (5) Expression in bags
in ordinary presses, now rarely, if ever employed.
The sponge method is the typical process in use in the chief lemon
oil districts—Sicily and Calabria ; the ecuelle method being employed
•chiefly in the South of France and North of Italy, and to a certain ex-
tent, of course, in the south.
The sponge method of obtaining lemon oil has been described by
many manufacturers. Probably the description by Mr. Arthur Barrett 1
is as accurate as any. It is as follows: " The principle on which
ihe extraction of the essence is carried out may be illustrated in this
way. If you hold a piece of lemon peel up to the light, and turn
it inside out, a fine shower of mist will be seen to be forcibly ejected.
This is not all oil, but a mixture of oil and water. Most people are
unpleasantly acquainted with this phenomenon, though many may
not have actually seen it, for in peeling a lemon or orange with the
fingers a little of the oil is often ejected into the eye, causing a con-
siderable amount of pain. By turning the lemon peel inside out
almost the whole of the essence is removed from the peel, for each
little globule of oil appears to be surrounded by water, and the liquid
which remains adherent to the peel consists principally of water. As
it is impossible to turn every piece of peel actually inside out, the
following method is adopted : One man takes a lemon in his hand, and
with three rapid strokes with a large knife cuts off nearly all the peel in
three slices. The central portion which is left consists of most of the
pulp with a little of the peel—top and bottom. This is simply, pressed
for making lemon juice. The slices pass to a second workman, who sits
on a low chair with a common quality bath sponge, worth about sixpence,
in one hand. With the other he presses the slice of peel against the
sponge, pressing the edges of the peel only with his fingers, the object
being to press the convex piece of lemon peel as nearly flat as possible.
The amount of pressure used is very slight, and at first sight it seems in-
credible that the oil globules can have been broken; but, if you try the
experiment of turning this exhausted peel inside out, nothing more can
be extracted. The sponge is periodically squeezed. One man working
in this way can extract 1-J Ib. (English) essence of lemon per day. To
ensure the cells being fully charged with moisture it is usual to allow the
lemons to stand in water for a short time ; and I myself propose washing
the lemons in a stream of running water."
The Scorzetta process is a variation of the ordinary sponge method.
The fruits are cut into two halves, the pulp is removed with a kind
of spoon, and all the parts of the peel are then pressed against a sponge
by constantly turning it in the palm of the hand. This method has the
.advantage that the peels remain unbroken, and retain their original
appearance. After they have been deprived of the oil, they are salted,
and then exported under the name "Salato". The pulp also remains
unimpaired, so that it yields its full supply of lemon juice. After having
passed twice through the pressers it is used for feeding cattle.
1
EUTACEÊ 415
The ecuelle process, which is employed in the North of Italy and the
13outh of France, depends on the preliminary breaking of the oil globules
by means of spikes or knives, and varies in detail, according to the quan-
iity to be operated upon. A simple ecuelle is a saucer-shaped vessel,
about 8 to 10 ins. in diameter, usually made of copper, tinned inside,
and covered inside with short spikes, about J to J in. long. In the
bottom of the saucer is a hole about •£ to ^ in. in diameter, leading to a
hollow tube about 4 or 5 ins. long. A fruit is placed in the vessel,
and, by means of a rapid rotary motion, the oil cells are broken by the
spikes. The escaping oil flows into the hollow tube, which is periodically
emptied.
Various purely mechanical appliances have been devised for obviating
the necessity of hand labour, but most of these have proved of little
value.
An apparatus, known as the thermopneumatic extractor, has been
FIG.
invented by Montfalcone for the extraction of all varieties of citrus oils.
The inventor claims that a far higher yield of oil of equal quality is
•obtained by the use of his apparatus, which is described as follows:—
1 is a hollow cylinder of sheet iron, the interior surface of which is
studded with a large number of metallic knife-points. This cylinder
revolves on two axles, attached to it at diagonally opposite points. Its
^capacity is such that, when charged, it is capable of holding 1200 or 1500
lemons. The cylinder having been properly charged, say with the above-
mentioned number of lemons, together with a small quantity of water, it
is set in motion by aid of the shafting and pulleys, driven by the small
steam engine. The fruits are thereby made to come in contact with the
metallic lancets, and their whole surface gradually becomes punctured
-•sufficiently to cut or rupture the cells containing the essential oil, which
escapes. The cylinder, 1, has double walls, the space between them
being intended for the circulation of a current of steam, which is admitted
:to heat the water and to facilitate the extraction of the oil, while, at the
same time, the vapours are rarefied or aspirated by the vacuum-pump, 2,
The axles of the cylinder on both sides are hollow : that on the side look-
ing towards the engine is embedded in such a manner that steam fronp
the boiler may be admitted at will, either into the double walls of the
cylinder or into the interior of the cylinder itself ; while the hollow pas-
sage in the other axle communicates with a condensing worm, the outlet
of which descends into a cylindrical vessel, 3, intended to receive the
condensed products, consisting of water and essential oil. When the
apparatus is first set in motion, the pump begins to produce a vacuum
during the first revolutions of the cylinder. Steam being now cautiously
admitted into the double walls of the cylinder, the water is raised to boil-
ing at a comparatively low temperature, and the vapours charged with
the essential oil rapidly pass over into the receptacle. With a two-horse-
power engine and a boiler designed for a five-horse-power engine, five
such machines may be driven at once, and the operation, including the
time required for charging and emptying, is completed in three-quarters
of an hour.
The United States Department of Agriculture have recently devised a
machine for the peeling of citrus fruits and the expression therefrom of
the essential oil. Although only in the experimental stage, it promises
to be very successful.
Lemon oil vari- s to a considerable extent, according to the period of
the harvest, to the season, and to the climatic conditions, so that it can
only be properly judged by the analyst when all these features are taken
into account.
The greater part of the oil of commerce is produced in the district of
Messina, on the north-east of the island of Sicily, and the adjacent dis-
tricts along the coast to the west; a considerable amount is produced in
the Palermo province, and all along the east coast of the island ; and a
large amount also in Calabria, which is chiefly exported from Eeggio.
An approximate idea of the relative production of these districts is seen
from the export returns during 1905, which were as follows :—
From Messina 742,567 kilos.
„ Reggio . . . . . . 95,319 „
„ Palermo 26,041 „
„ Catania 4,317 „
| Apart from the alteration in rotatory power suggested above as coin-
ciding with the time of the crop, although possibly having no direct rela-
tion to the quality of the oil, it is found that the oil obtained from round
about Barcelona (near the northern coast) and from the plains of Syracuse
(on the south-eastern coast) possess the highest average rotations of all
the oils, this figure varying from + 64° to + 65°. The following figures
are found for the various districts :—
From + 57° to + 71° . . Messina and neighbourhood, Nizza di Sicilia.
,, + 61° „ 4- 63° . . Acireale, S. Teresa di Riva, Scaletta, S. Lucia.
Patti, S. Agata, S. Stefano.
,, + 63° „ + 64° . . Catania, Giarre, Giardini, Acireale, Lentini.
i 99 + 64° „ + 65° . . Barcelona, Syracuse.
---'.Palermo oils are usually about + 57° to + 61°, and the Calabrian
oils + 59° to + 62° 30'. In the author's experience these limits are of
very small value and cannot be taken as in the least degree conclusive.
Cool rainy weather appears to have some effect on the optical rotation,
but all one can say conclusively is that the average rotation observed
during one season's crop is sometimes 2° or 3° higher or lower than that
of the preceding year. The Palermo oil and the Messina oil differ some-
BUTACE.E 417
what in their odour, etc., so that a trained nose can discriminate between
them.
The table on opposite page, covering analysis by Schimmel & Co.,
gives an outline of the differences between the oils of different districts-
during a given season (1908).
Lemon oil contains a considerable number of constituents, of whieh-
the principal is the aldehyde citral, which is present to the extent of1 from,1
4 to 5*5 per cent., rarely up to 6 per cent. Burgess and Page have
isolated a hydrocarbon, which is interesting as being quite different from)
the terpenes so generally found in the citrus oils. It has the following
characters :—
aD Of j Residue
Origin. Pressed in a
D,,, on Citral
20°c. I the First
^150-
10 per Cent. Evaporation .
|
Palermo : January 0-8578 + 60° 2' + 57° 42' 2-6 per Cent. 5-2 per Cent. 1
February 0-8590 + 57° 15' + 55° 10' 3-0 5-4
!
l March 0-8577 + 59° 44' + 56° 40' 2-6 6-4 „
! S. Agata : January 0-8580 + 59° 10' + 56° 8' 2-8 „ 6-3
February 0-8583 + 58° 40' + 55° 50' 3-6 „ 5-5
March 0-8575 + 61° 36' + 58° 12' 2-6 5-5
Barcelona : January 0-8570 + 62° 4' + 58° 30' 2*2 5-9 „
February 0-8580 + 60° 40' + 57° 50' 2-4 5-7 „ !
March 0-8575 + 59° 0' + 54° 24' 2-8 „ 5-2 „ j
Messina : January 0-8583 + 57° 53' + 52° 24' 3-0 6-5
February 0-8586 + 58° 26' + 53° 88' 3-0 6-0
March 0-8591 + 56° 50' + 53° 30' 3-2 5-7
S. Teresa : January 0-8600 + 59° 18' + 58° 0' 3-2 „ 7-1 , r
February 0-8607 + 57° 20' + 54° 50' 3-0 7-2
March 0*8610 -r 57° 24' + 54° 36' 2-8 6-6
Taormina : J anuary 0-8569 + 62° 20' + 60° 40' 2-4 5-8 , r
February 0-8572 + 62° 16' + 59° 26' 2-7 „ 6-0
March 0-8580 + 60° 52' + 59° 10' 2-4 5-3
Giardini : January 0-8575 + 61° 0' + -: 8° 4' 2-8 5-7
February 0*8589 + 59° 20' + 56° 40' 2-8 „ 6-0 , ;
March 0-8585 + 59° 56' + 56° 48' 3-0 „ 5-3
Mascali : January 0-8569 + 61° 44' + 58° 40' 2*4 4-7 , 1
February 0-8574 + 62° 40' + 59° 18' 2-8 4-4
March 0-8578 + 60° 14' + 56° 4' 2-7 4-3
Acireale : January 0-8588 + 60° 12' + 57° 24' 2-6 6-5
February 0-8583 '+ 59° 38' + 56° 20' 2-2 „ 5-6 , ;
March 0-8590 + 58° 22' + 55° 0' 2-8 5-9 . •
Acicatena : January 0-8580 + 60° 6' + 56° 28' 3-2 4-9 , |
February 0-8586 + 60° 14' + 58° 0' 3-5 5-1 1-
March 0-8580 + 59° 12' + 56° 24' 3-0 4-9
Catania : January 0-8576 + 61° 52' + 59° 20' 2-8 5-0
February 0-8580 + 58° 16' + 5,o° 26' 2-6 5-4
March 0-8589 -f 59° 50' + 56° 50' 2-8 5-1
Syracuse : January 0-8580 + 59° 28' + 57° 24' 2-9 6-7
February 0-8583 + 60° 35' + 59° 22' 2-8 „ 7-0
March 0-8575 + 62° 6' + 60° 32' 2-6 5-3
Specific gravity . 0'7257

1
Jour. Chem. Soc., 85 (1904), 1328.
VOL. I. 27
Analysis agreed with the formula C8H]6 or C8H18. It is probably octy-
lene. Pinene appears to be present in traces, as well as camphene,
phellandrene, and y-terpinene. The bulk of the oil, however, consists of
d-limonene which is present to the extent of about 90 per cent. Methyl-
heptenone, octyl aldehyde, nonyl aldehyde, citronellal, terpineol, linalyl
acetate, geranyl acetate, bisabolene, cadinene and methyl anthranilate
have all been found present in traces.
Citraptene, or " lemon camphor," a solid substance, which appears to
be dimethoxy-coumarin, is present to the extent of about 2 per cent, in
the oil. This is a non-volatile substance dissolved out from the peel by
the expressed essential oil.
Citraptene, which appears to be identical with limettin, has been care-
fully examined byE. Schmidt.1
The early work of Brissenot, Blanchet, and Sell and Mulder is referred
to, as is also the analysis by Berthelot. This brings us up to the first of
the recent workers, Crismer, who gave 143° to 144° as the melting-point,
and C10H10O4 as the formula of the stearoptene of lemon oil. Schmidt
isolated a crystalline body melting at 146° to 147° and having a blue
fluorescence in alcohol solution, and he states that this body is the
citraptene of Crismer, and the limettin of Tilden and Beck. Theulier
had already stated that a crystalline body melting at 145° and an
amorphous one melting at 76° were the chief constituents of the solid
mass obtained on the distillation of lemon oil; of these citraptene is the
principal.
Schmidt gives 146° to 147° as the melting-point of this body, for
which the name citraptene is retained. Three analyses gave the fol-
lowing results :—
Carbon. Hydrogen.
C
Calculated for CnH10O4.
63-92 5'04 C 63-98
63-83 5-01 H 4-85
63-82 4-75 O 31*17
This formula is in agreement with that assigned to limettin by Tilden
.•and Beck.
Citraptene contains two methoxyl groups ; when treated by Zeisel's
anethod to remove the methyl groups, the demethylated citraptene,
<C9H6O4, yields phloroglucin and acetic acid on fusion with alkali.
Citraptene has the general character of an acid anhydride, according
to Schmidt, its corresponding acid being unstable and rapidly converted
into a lactone.
Citraptene appears to be a di-methoxy-coumarin of the formula—
C . OCH,
HCX\C.CH:CH
CH 3 OC\/CO . CO
Lemon oil has the following characters :—

Specific gravity . 0'854 to 0'862 (usually 0'857 to 0'860).
Optical rotation + 54° „ + 66° ( „ + 57° „ + 62°).
Refractive index 1-4745 „ 1*4760 (rarely below 1-4750).
Fixed residue (at 100°) 2 to 6 per cent. ( ,, over 4 per cent.).
Citral 4 ,, 6 ,, (usually 4'2 to 5*5 per cent.).
1
Archiv. der Pharm. (1904), 288.
EUTACEÊ 419
During the latter part of June and the month of July in some seasons,
a number of samples of undoubted authenticity have been examined and
found to have an abnormally low optical rotation sometimes as low as
+ 51°. In some cases the odour of the lemon oil is quite abnormal, and
gives one the impression that it had been contaminated with neroli oil.
'The reason of this appears to be that the spring lemons (" bianchetti"),
which are rarely used for pressing for oil, as the oil is inferior and the
yield small, are in such seasons being pressed in large quantities; and
where this neroli odour is found, it is probable that some quite immature
fruits have been used for pressing.
If pure lemon oil be carefully distilled from a three-bulbed fractionat-
ing flask, and the first 10 per cent, collected, its optical rotation will
rarely differ from that of the original oil by more than 5°, or at most 6°,
the rotation of the fraction being lower than that of the oil. The size of
the flask and the rate of distillation cause considerable variation in this
figure, so that unless a marked difference is found, such as would result
from adulteration with an appreciable quantity of turpentine, too much
stress must not be laid upon the result of a test which, after all, is em-
pirical in its nature.
Adulteration, which was until recently very frequent, is still common.
'Turpentine was the regular adulterant, with, at times, the poorer quality
distilled oil of lemons. But adulteration with turpentine is now so easily
detected that the sophistication is frequently carried out in a more scien-
tific manner. Mixtures with the proper specific gravity and optical rota-
tion can easily be made up from turpentine and orange oil—the poorer
qualities of the latter of course being used—and such mixtures are often
used to adulterate the oil. But the most formidable adulterant from the
analyst's point of view is one that has only come into vogue during the
last few years, viz. the terpenes obtained in manufacturing the " terpene-
less" or concentrated oils of lemon and oil of orange, the latter being
sometimes added to turpentine to raise the optical rotation.
The terpenes are sometimes used alone, sometimes together with a
little citral obtained from lemon-grass oil. It is a common custom to
export oil of lemons with a guaranteed citral-content, and to sell it upon
that basis. In judging of the value of such a basis for the market value
of the oil, the following points should be noted :—
1. The value of the oil depends on its percentage of all the oxygenated
constituents, which are soluble in weak alcohol.
2. The terpenes are practically odourless and insoluble, therefore
valueless for the general purposes for which lemon oil is employed.
3. The percentage of terpeneless oil obtained by careful fractionation
is an indication of the value of the oil.
Some samples of lemon oil produced in Spain have recently been
examined, and, as instancing the differences between oils manufactured
in different districts, have the following characters which would be con-
sidered impossible in the case of pure Sicilian oils :—
Citral 3-1 to 3-2 per cent.
The optical rotation of the first 10 per cent, distilled was found to be
-about 3° higher than that of the original oil.
The most important method of analysis applicable to lemon oil is the
determination of the citral-content. A great many methods have been
suggested for this, most of which yield only approximate results.
From a lengthy experience in these processes, the author has no
hesitation in saying that the most accurate method fo*r the estimation of
citral in lemon oil is that devised2 by J. Walther,1 with a slight modifica-
tion suggested by A. H. Bennett.
This process depends on the formation of an oxime with hydroxy-
lamine in alcoholic solution, and determination of the amount of hydroxy-
lamine used in the process, according to the equation :—
C9H15CHO + H2NOH = C9H15: NOH + H,O.
The process is carried out as follows : A mixture of 20 c.c. of lemon
oil, 20 c.c. of 90 per cent, alcohol, 20 c.c. of a 5 per cent, solution of
hydroxylamine hydrochloride in 80 per cent, alcohol, and 8 c.c. of normal
alcoholic potash solution is gently boiled for thirty minutes under a
reflux condenser. A similar mixture, without the lemon oil, is treated
in exactly the same manner. After cooling, the condensers are washed
down with water to restore any traces of hydroxylamine to their respec-
tive flasks, and the contents of the flasks diluted with about 200 c.c. of
water. A few drops of phenolphthalein are added to the flasks, and the
contents first neutralised with semi-normal alkali. The hydroxylamine
is now titrated with semi-normal sulphuric acid solution, using methyl
orange as indicator. A few drops of the indicator should be added to the
flask, so that a general indication of the approach of the end reaction is
given, but the end reaction itself should be observed by the familiar pro-
cess of " spotting " on a white tile, on drops of the indicator. Each cubic
centimetre of half-normal acid used in the blank experiment, over that
used in the assay experiment, is equivalent to 0*076 grm. of citral.
A process depending on the use of cyanacetic acid was proposed by
the author 3 some years ago, which depends on the condensation of
cyanacetic acid with citral in alkaline solution, according to the following
equation:—
ON
C9H1SCHO + CH2CN . COOH = C9H15CH . C<f , TT n
N ' "^^2^'^"
COOH
The procedure is as follows : 200 c.c. of the oil are concentrated to
25 c.c. in a Wurtz flask under a pressure which should not exceed 15
mm. The 175 c.c. of terpenes contain a little citral, but the quantity is
so small that it may be neglected. Ten c.c. of the residue, of which the
specific gravity is known, are shaken with a solution of 5 grms. cyan-
acetic acid and 5 grms. ordinary KOH in 30 c.c. water in a small
absorption flask with a long graduated neck, and the non-absorbed
residue read off as usual. (The specific gravity of citral is so near that
of the concentrated oil used that it may be taken as identical.)
This process does not give satisfactory results, and is only quoted
here so that the author may definitely withdraw it as a process as-
sociated with his4 name.
E. M. Chace has elaborated a method for the determination of citral
depending on the fact that fuchsine-sulphurous acid develops a red
coloration with aldehydes, the depth of which depends on the amount
2
*Pharm.
3
Zentral., 40 (1899), 621 ; 41 (1900), 585.
4
Aiwlyst, 34 (1909), 14.
Chemist and Druggist, 56 (1900), 376. Jour. Amer. Chem. Soc., 28, 1472
BUTACEJE 421
of aldehyde present. The determination is carried out by comparison
with solutions of citral of known strength.
The solution of magenta-sulphurous acid is prepared as follows :
0*5 grm. of magenta is dissolved in 100 c.c. of water and a solution con-
taining 16 grms. of sulphur dioxide is then added. The liquid is allowed
to stand until it is decolorised and its volume is made up to a litre with
water. Such a solution cannot be kept longer than two or three days.
Secondly, alcohol of 95 per cent, strength must be prepared absolutely
free from aldehyde. For this purpose the alcohol is kept for several
•days in contact with a caustic alkali, it is then distilled and the distillate
is boiled under a reflux condenser for a few hours with meta-phenylene-
diamine hydrochloride (25 grms. of the hydrochloride per litre). The
alcohol is then separated by distillation and made up to the desired con-
centration.
Lastly, a O'l per cent, solution of citral in 50 per cent, alcohol is
prepared.
These solutions are made up at a temperature of 15° C., and all the
operations are carried out at this temperature. It is particularly recom-
mended that a higher temperature be avoided.
Two grms. of each of the essential oils to be examined are diluted to
100 c.c. with the alcohol free from aldehyde. Four c.c. of each of the
solutions are introduced into cylinders of identical dimensions, 20 c.c of
alcohol free from aldehyde are added, then 20 c.c. of magenta-sulphurous
acid, and the volume is made up to 50 c.c. with alcohol. After thoroughly
mixing, the solutions are placed in a water-bath at 15° C., and compared
in regard to their colours with the necessary standards. An error of 1
per cent., however, may be made in this determination.
K. S. Hiltner l has devised a process depending on the yellow colour
developed when citral reacts with meta-phenylene-diamine. The process
is best carried out as follows:—
A standard solution of citral is made containing O'OOl grm. per c.c.
A 1 per cent, solution of meta-phenylene-diamine hydrochloride in
dilute alcohol is prepared, well shaken with bone black and filtered.
About 1-5 grms. of oil of lemon are weighed into a 50 c.c. flask, and
made up to the mark with 95 per cent, alcohol. From 2 to 4 c.c. of this
solution are transferred to a Nessler tube, 10 c.c. of the reagent added,
and the liquid made up to 25 c.c. with alcohol. A similar amount of the
standard solution is treated in the same way, and the colours developed
accurately matched.
The amount of citral is easily calculated from the amount of the
standard solution used.
L. D. Little2 has devised the following method :—
Reagent.—Dissolve '200 grm. of diaminophenol hydrochloride (com-
mercially known as Amidol) in 100 c.c. of 65 per cent, alcohol, preferably
distilled over KOH. The use of aldehyde-free alcohol does not seem to
make any difference in the results, as acetaldehyde has no apparent effect
upon the reagent. Eecently distilled absolute alcohol is sufficiently
exact, as the reagent remains clear and colourless for several hours.
Standard Citral Solution.—A solution of pure citral in 50 per cent,
alcohol, containing '001 grm. per c.c.
1
Jour. Ind. Enq. Chem., I (1909), 798.
2
Jour. Amer. Pharm. Assoc. (1914), 3, 553.
Solution of Oil of Lemon.—Weigh from 1 to 2 grms. of the oil and
dilute to 50 c.c. with 50 per cent, alcohol.
Place 2 c.c. of the standard citral solution in a 250 mm. colorimeter
tube (using preferably a Schreiner colorimeter), add 20 c.c. of 65 per
cent, alcohol and 15 c.c. of diaminophenol reagent, and make up to 50
c.c. with 65 per cent, alcohol. Place 2 c.c. of the oil solution in the
other tube with 15 c.c. of the reagent and make up to 50 c.c. with 65
per cent, alcohol, mixing the contents of both tubes thoroughly and
allowing them to remain for five to ten minutes at rcom temperature,
when the maximum colour is reached. The reading and calculation
are made at once, or a reading can be made at the expiration of fifteen
or twenty minutes in duplicate. The calculation of percentage of citral-
content in the extract is made by placing the standard citral tube at the
30 mm. mark and adjusting the tube containing the extract under ex-
amination so that the two small disks of colour as observed through the
two immersion1tubes are similar in tint.
C. Kleber's method, which gives very fair results, depends on the
use of phenyl-hydrazine.
Two c.c. of oil, accurately weighed, are mixed with 10 c.c. of 2 per
cent, alcoholic phenyl-hydrazine solution, and allowed to stand one
hour in a glass-stoppered bottle of 50 c.c.; then 20 c.c. of deci-normal
hydrochloric acid and 10 c.c. of benzene are added, and the whole
shaken thoroughly. The mixture is transferred to a separator, and the
lower layer of 30 c.c. run through a small filter. Twenty c.c. of filtrate
are titrated, after the addition of ten drops of ethyl orange 1 : 2000, with
deci-normal caustic potash to distinct yellow coloration. By a similar
blank experiment without oil the acid equivalent of the hydrazine solu-
tion is determined. From the difference between the two experiments
the citral-content is calculated, each c.c. of deci-normal caustic potash
corresponding to 0'0152 grm. citral. A number of analyses made in
this way with mixtures of definite quantities of citral with tsrpenes
were found to be well in accordance with the calculated results.
An absorption method depending upon the formation of a soluble
sulphonic acid with sodium sulphite using phenolpbthalein as an indi-
cator, gives fairly good results :—
C9H15CHO 4- 2Na2SO3 + 2H2O
= C9H17(NaSO3)2COH + 2NaOH.
Prof. Tiemann, in his elaborate work on the aldehydes of lemon-
grass oils has, among other important reactions, shown that if citral be
agitated with a neutral solution of sodium sulphite, a sodium salt of the
sulphonic acid results, as shown by the above formula. By taking ad-
vantage of the sodium hydrate formed by this reaction, phenolphthalein
is used as an indicator to show when all the citral has been combined;
and the fact that the above sodium salt is quite soluble, has made the
estimation of citral fairly accurate and simple. The procedure is as
follows: A saturated solution of sodium sulphite is prepared. To
50 c.c. of such solution in a Hirschsohn flask, 25 c.c. of the oil are
added, and two drops of an alcoholic solution of phenolphthalein. The
whole is then heated on a water-bath to nearly boiling-point, constantly
shaking. A deep red colour appears almost at once, which shows that
the action has commenced. A few drops of sulphurous acid are then
cautiously added, and this is continued until no further colour is pro-
1
Schimmel's Bericht, April, 1912, 64.
EUTACE.E 423
duced after a further addition of SO2. The oil is then measured by add-
ing sufficient sulphite solution to drive the oil into the neck of the flask.
The obvious advantage of this method is that the end of the reaction
may be ascertained to a certainty, while the above bisulphite method
depends on the continual shaking for a period of not less than one hour.
The only objection to this process is that the reading of the meniscus
in the neck of the flask is a little difficult owing to the presence of
flocculent matter.
Numerous other methods for the determination of citral in lemon oil
have been proposed, but the foregoing may be taken to cover the most
accurate, and to lembrace all that are likely to be of any practical value.
E. M. Chace has published an elaborate study on the detection of
traces of pinene in lemon oil, deducing from the presence of even a very
FIG. 39.—Photomicrograph of crystals from lemon oil ( x 100).

a, 6, Limonene nitroso-chloride crystals from lemon oil; c, Limonene and
pinene nitroso-chloride crystals from a lemon oil mixed with 5 per cent, of turpen-
tine ; d Pinene nitroso-chloride crystals from turpentine.
minute quantity in the oil that turpentine is present. As pinene ap-
pears to be a natural constituent of the oil and adulteration with tur-
pentine would not be practised except on a scale that would render it
remunerative, there appears to be no doubt that Chace's deductions are
inaccurate, and the presence of traces of pinene cannot be held to in-
dicate adulteration of lemon oil.
Chace points out that the nitrosochlorides of pinene and of limonene
crystallise in different forms, and makes use of this property to detect
pinene. For this purpose he distils, in a Ladenburg flask, 5 c.c. from
50 c.c. oil, and from this he prepares the nitrosochloride with the use of
ethyl nitrite according to Wallach's method. The mixture is left for
fifteen minutes in a freezing mixture; the crystals which separate off
are then collected, washed with 50 c.c. 95 per cent, alcohol, the mother-
l
Jour. Amer. Chem. 8oc.t 30 (1908), 1475.
liquor again placed in the freezing mixture for fifteen to twenty minutes,
and the crystals which are thus still formed are added to those first ob-
tained. The crystals, well washed with alcohol, are, after drying, dis-
solved in as little chloroform as possible, and a little hot methyl alcohol
is then added so that on cooling crystallisation takes place. Finally, a
little more methyl alcohol is added, and the crystals are then filtered off.
FOP the examination under the microscope the crystals are best embedded
in oil. In this manner Chace claimed to be able to detect an admixture
of even 2 per cent, turpentine oil, whilst as little as 0*5 per cent, turpen-
tine oil could be detected when a three-bulb Glinsky fractionating head
was employed.
Bocker l has elaborated the following method for the determination
of the hydrocarbons present in the concentrated or so-called terpeneless
and sesquiterpeneless oils of lemon of commerce :—
Citral is first estimated in 10 c.c. of oil by the sulphite method. When
the oil which has not entered into reaction is less than 6 c.c., the estima-
tion is repeated with another 5 or 10 c.c. The oil left over from these
tests is bulked, and 5 c.c. of this citral-free oil is placed in a 600 to
700 c.c. separator, into which, immediately previously, 500 c.c. of alcohol
of precisely 51 per cent, by volume, cooled down to from 0 to - 2° C.,
has been introduced. The separator is closed with a cork and the con-
tents are repeatedly shaken, when the aromatic bodies of the oil are dis-
solved by the alcohol, while the hydrocarbons are left behind almost
quantitatively. The separator is then placed in a cooling-bath at 0° C.,
cork downwards, for six to ten hours. It is then taken out of the freez-
ing mixture, carefully turned back to its proper position and placed in a
stand. When the alcoholic solution has cleared to a point at which only
a slight film remains (which in certain conditions may take up to two
•days) it is drawn off to about 10 c.c., any oil-drops which may still adhere
to the sides of the funnel being rinsed down with ice-cold 51 per cent,
alcohol, so that all the oil which has remained undissolved is brought
together. When the mixture has become perfectly clear, the oil, being
freed as far as possible from the last traces of alcoholic solution, is trans-
ferred to a measuring tube calibrated to -*$ c.c., and the vessel rinsed out
with a little more ice-cold 51 per cent, alcohol. It is advisable to use a
separating funnel of which the lower part ends in a narrow graduated
tube. As soon as the oil is completely cleared (when the froth is very
persistent a few drops of dilute acetic acid should be added), the volume
is read off and calculated to the original oil.
The method may be completed by estimating not only the quantity
but also the character of the hydrocarbons. Thus, from 100 to 200 c.c.
of oil is fractionally distilled in vacuo. The distillation is only continued
up to the point where the separate fractions of about 10 c.c. each still
show dextro-rotation. These fractions are put together as the " terpene-
containing portion " of the oil, the rest constituting the " sesquiterpene-
containing portion ". Each of these portions is then freed from citral
by means of Na2SO3, and in both cases the residue is treated with 100
times its quantity of ice-cold 51 per cent, alcohol, as described above, a
large glass flask being, if necessary, substituted for the separator. The
alcohol solution is separated by means of a siphon from the portion which
has remained undissolved. The oils which have been separated are
estimated quantitatively, and from the values thus obtained the per-
i Jour. Prakt. Chem. (1914), 89, 199.
EUTACB^l. 425
ventage of terpenes and sesquiterpenes in the original oil is calculated.
For purposes of further identification the rotation is estimated, and, if
necessary, the characteristic derivatives are prepared. The terpenes,
of which the principal constituent is d-limon§ne, are characterised by a
pronounced dextro-rotation ; they yield a liberal proportion of limonene
tetrabromide, whereas the sesquiterpenes, which consist chiefly of
bisabolene, are laevo-rotatory and may be identified from the bisabolene
4 rihy drochloride.
OIL OF ORANGE.
There are two varieties of ordinary orange oil in commerce, almost
identical in composition and properties, but with odours and flavours
somewhat different. These are the sweet and bitter orange oils, ob-
tained in the same manner as oil of lemon, from the peel of Citrus
aurantium subsp. sinensis and Citrus aurantium subsp. amara respec-
tively. With regard to the origin of the trees, Prof. Sadebeck (Plant
Cultivation in the German Colonies, and their Products) says : " The
orange tree is probably indigenous to South-eastern Asia, and thence
has spread to the Sunda Islands, further India, Persia, Arabia, Syria,
North Africa, and Southern Europe. Towards the end of the ninth
-century of the Christian era, it appeared in Arabia, and since A.D. 1002
in Sicily." An oil is prepared by distillation, but it is much inferior in
every respect to the expressed oil. Considerable parcels of West Indian
oil have been placed on the London market, the examination of which
shows this to be equal if lnot superior to Sicilian oil.
According to Umney the chief centres of cultivation in the Medi-
terranean littoral are Hyeres, Cannes, Grasse, Nice, Mentone, Bordi-
ghera, San Eemo, Savone, and Nervi, near Genoa. In Algeria there are
many districts where orange trees flourish. Perhaps the most beautiful
plantations of Europe are the orange groves of Milis in Sardinia, those
of Soller in the island of Majorca, the gardens of Sorrente, near Naples,
the Messina plantations near the foot of Mount Etna, and those of
Eeggio in Calabria.
The sweet orange is largely cultivated in the West Indies and in the
Southern States of North America. In Florida it grows wild in great
abundance and is also exclusively cultivated for its fruit.
The bitter or Seville orange is known as Citrus bigaradia (Duhamel),
Citrus aurantium var. amara (Linnaeus), and Citrus vulgaris (Eisso), of
which some twelve varieties are known. The sweet or Portugal orange
is known as Citrus aurantium (Eisso), of which no fewer than nineteen
varieties are known.
Orange trees require plenty of air and light to enable them to resist
the attacks of parasitic insects and various diseases to which they are
subject. Pruning is carried out in May or June, after the flowering
period. The inner branches are carefully removed, also dead wood and
decayed growth.
The flowers, which expand towards the end of April, furnish on
distillation the sweet oil known as neroli oil, and orange flower water
as a by-product. Preference is given to the products of the bitter
orange, which differs from the sweet orange in its larger and more
numerous flowers, the leaves having larger winged petioles and the
1
P. and E.O. R. (1916), 246.
fruits having a rougher rind, covered with oil vessels, and containing;
an acid and very bitter juice.
A tree twenty to thirty years old yields annually from 15 to 20 kilos-
of flowers. In Grasse alone 200,000 to 300,000 kilos are produced
annually. A hundred kilos yield at least 40 kilos of orange flower
water and 100 grms. of oil.
At an age of twenty to twenty-five years the trees produce the
maximum yield of fruits, usually from 600 to 1000 oranges per annum.
In Spain and Algeria trees exist which produce 2000 to 3000 fruits-
annually. The peel is used for liqueurs and for the manufacture of
marmalade, as well as for the production of the essential oil.
There are three distinct types of essential oil obtained from the
orange, namely, the flower oil, known as neroli oil, the oil from the
leaves and young shoots known as petitgrain oil, and the peel oil,,
known simply as " orange " oil.
Sweet orange oil, prepared in a similar manner to lemon oil, has the
Optical rotation -f 94° „ + 99°
On distilling the first 10 per cent, in a Ladenburg flask, this fraction
should have an optical rotation, should be equal to or at most about 1°
lower than that of the original oil. The aldehyde-content, calculated as
decylic aliehyde, determined by the phenylhydrazine method described
under lemon oil, varies from 1*4 to 2'5 per cent.
On evaporation on a water-bath, sweet orange oil yields from 1*5 to-
4 per cent, of fixed residue, which has an acid value of 11 to 30 and an
ester value of 115 to 170. Spanish orange oil, however, which is ex-
pressed from a dark-skinned orange, yields from 7 to 9 per cent, of fixed
residue.
West Indian orange oil occasionally has .a refractive index as low as
1'4700, but this is an exceptionally low value.
According to Schimmel & Co., Jamaican sweet orange oil contains-
from 2*3 to 3*2 per cent, of aldehydes calculated as decylic aldehyde
from a phenylhydrazine determination, whilst the bitter oil contains only
0*75 to 1-5 per cent.
The oil consists principally of dextro-limonene which is present to
the extent of about 90 per cent, or over. Decylic aldehyde is one of the
principal odorous constituents of the oil; linalol, Z-terpineol, d-terpineol,
nonyl alcohol, methyl anthranilate and traces of caprylic acid esters are
also present.
Bitter orange oil only differs very slightly from sweet orange oil, and
the composition of the two oils is practically identical. The physical
characters of the oils vary to a trifling extent, those of bitter orange oil
being as follows :—
Non-volatile residue 2-5 to 4*5 per cent.
The optical rotation of the first 10 per cent, distilled should be higher
than, or not more than 1° lower than the rotation of the oil itself.
An orange oil prepared in an abnormal method from Manila oranges
has been examined by Gibbs and Agcaoili,1 according to whom the
1
Philip p. Jour. Sci., vii., A. 6.
EUTACE^S 427
orange commonly found in the Manila market is a green, loose-skinned

orange of the mandarin orange type. From the peel the essential oil
was obtained by rubbing under water to disintegrate the oil cells, strain-
ing the liquid through muslin and extracting the squeezed pulp with
petroleum ether. This was then shaken with the watery liquid and
separated. This was repeated three times. The petroleum ether was-
evaporated at a pressure of 12 to 15 mm., at a temperature below 50°,
until all the solvent was expelled. The yield and characters of the oil
in three cases are as follows :—
No. Oil from 100 Specific Gravity. Rotation. Refractive Ester

Peels. Index. Number.
1 0-8416 + 58-9° 1-4560 13

2 19-33 grs. 0-8620 + 83-4° 1-470 7
3 14-0 grs. 0-8481 + 79° 1-468 10
OIL OF TANGERINE ORANGE.

The Tangerine oil of commerce, also known as oil of Mandarin
orange, on account of the custom of presenting the orange in question
to the Mandarins in Japan, is obtained by expression from the peel of
Citrus nobilis (Citrus madurensis). The tree is cultivated in Italy,
Malta, the Azores, and several other places.
The peel of the fruit yields an essential oil with a slight blue-violet
fluorescence, due to the presence of a small quantity of methyl anthra-
nilate. The oil has the following characters :—
Non-volatile residue 2 to 4 per cent.
The optical rotation of the first 10 per cent, distilled is about 2° to 3°
higher than that of the original oil.
A Spanish sample of Tangerine oil has been found 1 to have the fol-
Non-volatile residue 8 per cent.
A number of Mandarin orange oils prepared in Japan have been
examined,2 but as they appear usually to be prepared by distillation they do-
not always agree in physical characters with Italian oils, nor are they, as.
a rule, nearly so fragrant. These samples had the following characters :—
Specific Optical Rotation

No. Gravity. Optical Rotation. of 1st 10 per Cent.
Distilled.
1 0-8489 + 92° 35' + 91° 32

2 0-8528 + 73° 36' + 66° 10'
3 0-8541 + 68° 5' + 60° 48'
4 0-8483 + 92° 20' —
5 0-8478 i + 90° 56' —
6 0-849 + 90' 35' —
7 0-848 + 94° —
1
Schimmel's Bericht, October, 1911, 39.
2
Schimmel's Report, October, 1914, 21; P. and E.O.R., 5 (1914), 72.
The principal constituent of this oil is d-limonene. Dipentene is
also present. Methyl anthranilate and methyl methyl-anthranilate are
ulso present, and traces of an unknown aldehyde.
The determination of the anthranilic acid esters is of importance in
the essential oils of this group which contain it. The only method of
any value is that of Hesse and Zeitschel,1 which is as follows :—
About 25 grams of the oil are dissolved in two to three times this
quantity of dry ether and the solution cooled to 0° in a freezing mixture,
and a mixture of 1 volume of sulphuric acid in 5 volumes of ether added
drop by drop until no further precipitation takes place. The precipitate
is collected in a filter and washed with dry ether. The compound of the
ester with sulphuric acid is then dissolved in water, and titrated with
semi-normal alkali, using methyl orange as indicator. If S grams of
oil be used, and A c.c. of semi-normal alkali be required for the titration,
then the percentage oihnethyl anthranilate is
A x 3-775
OIL OF NEKOLI.
This oil is distilled from the fresh flowers of the bitter and the
sweet orange. The former, which is the more valuable, is known as
"Oil of Neroli, Bigarade " (which is ordinary neroli oil), the latter as
"Oil of Neroli, Portugal". The greater part of the neroli oil of com-
merce is distilled in the south of France, one of the chief centres being
Vallauris. The yield of oil varies greatly according to the time of the
season when the flowers are collected. The gathering of the flowers
commences about the last week in April and continues till the last week
in May, or possibly a little later. The early gathered flowers yield about
half a gram of oil per kilo, whilst those gathered late in May yield
double this quantity. The petals are separated from the sepals and
covered with water in the still, and the contents heated by means of coils
of superheated steam. The oil coming over is separated, and the water
is sold as orange flower water.
There are numerous orange gardens in Spain, Algeria, Sicily, Greece,
and Turkey in Asia, but only a small amount of oil is distilled in these
countries. A small quantity of oil, which is equal in perfume value to
the oil distilled in France, is prepared in Tunis and Algeria, the principal
Tunisian centre being the district of Nabeul, where about 60,000 kilos
of flowers are dealt with annually. The distillation is in the hands
of Arabs, many of whom use small stills which take only 3 kilos of
flowers.
The neroli oil industry is also being well developed in Malaga.
From the port of Malaga northward along the Biver Guadalhorce
right up to Alora, a distance of 50 kilometres, the flowers are grown in
great profusion. On some days as much as 6500 kilograms of flowers
are dealt with at the distillery established at Alora. Needless to say,
however great the arrival of blossom it must be dealt with immediately.
In the photograph reproduced 2 one of the series of stills used at
Alora for this work is illustrated. It takes a charge of from 400 to 450
kilos of flowers.
1 2
Berichte, 34 (1901), 296. From P. and E.O.R. (1913), 137.
d
H
t>
o
a
fe
FIG. 40.—Gathering orange flowers at Bar-sur-Goup, near Grasse.

[Roure Bertrond Fils.
431
French neroli oil usually has the following characters : —
I Bigarade Oil. j Portugal Oil.
Specific Gravity. 0-870 to 0-881 0-865 to 0-870

Optical Rotation + 1° 30' „ + 9° 8' + 25° „ + 45°
Kefractive Index 1-4675 „ 1-4738 1-4730 ,, 1-4750
Ester No. . 30 „ 70 about 15
FIG. 42.—Neroli oil still at Alora.
FIG. 43.—Orange garden at Nabeul (Tunisia). [ViaL

These limits, however, are from time to time found to be too narrow,
some Bigarade oils being slightly laevo-rotatory, and, occasionally, the
ester value being lower than 30. But most oils fall within the above
limits.
The following tables, compiled by M. Jean Gras of Cannes, show
the characters of oils distilled during two seasons :—
1901 NEROLI OILS.
Specific Optical Saponifica- Solubility in 75 per Yield of Oil

Distilled on Gravity Rotation tion No. Cent. Alcohol per 1000 kilos.
at 15°. at 22°. at 24°.
May 23 . 0-875 + 5° 2' 39 in two volumes 0-900

24. 0-874 + 4° 28' 40 j j 0-870
25. 0-875 + 5° 25' 41 » > 0-980
26. 0-875 + 5° 10' 37 » 1-020
27 . 0875 + 5° 45' 34 1-150
28. 0-875 + 5° 46' 37 f 1-160
29. 0-874 + 6° 15' 31 t 1-200
30. i. 0-874 + 4° 55' 33 ? 1-120
31 . 0-875 + 5° 34 1-150
June 1 . 0-874 + 6J 32 f 1-020
, 2. 0-873 + 4° 40' 36 9 1-210
, 3. 0-875 + 7° 39 t 1-400
, 4 . 0-876 + 6° 46' 34 ' 1-500
1904 NEROLI OILS.

Specific Gravity
Yield per Cent.
Saponification
Optical
at 15° C.
Distilled Rotation
No.
on 1 = 100 mm. Solubility in Alcohol of 80 per Cent, at 22°.

t=20°.
May 11 0-65 0-874 |+1° 81' 43 f l vol. in 1 vol. alcohol, insoluble when
„ 12 0-80 0-874 \ more alcohol was added
„ 13 0-89 0-874 + 1°45' 45 1 vol. in 1-5 vol. alcohol, insoluble
when more alcohol was added
„ 14 0-81 0-875 + 2° 8' 46 insoluble
„ 15 0-83 0-874 + 1°32' 45 do.
,, 16 0-78 0-874 | + 1° 33' 47 do.
„ 17 0-87 0-874
„ 18 0-77 0-875 + 2° 8' 53 do.
„ 19 0-77 0-875 + 1° 45' 56 do.
„ 20 0-77 0-875 + 2° 20' 45 do.
„ 21 0-87 0-875 + 2° 21' 47 1 vol. in 1 vol. alcohol, insoluble when
more alcohol was added
„ 22 0-90 0-876 + 2° 21' 46 1 vol. in 1-2 vol. alcohol, insoluble
when more alcohol was added
„ 23 1-00 0-875 + 2° 30' 43 do.
„ 24 1-03 0-874 + 2° 44' 45 1 vol. in 1 vol. alcohol, insoluble when
more alcohol was added
„ 25 1-06 0-874 -r3°5' 46 do.
„ 26 1-07 0-874 + 3° 8' 44 do.
.* 27 1-07 0-874 + 3° 30' 45 do.
.. 28 1-02 0-874 + 3° 12' 47 do.
„ 29 1-11 0-874 + 3° 31' 48 do.
,, 30 1-15 0-874 + 3° 48' 50 1 vol. in 1 vol. and in every propor-
tion
„ 31 0-91 0-874 + 2° 51' 48 do.
June 2 0-80 0-875 + 4° 20' 49 do.
Total 0-97 0-875 + 2° 50' 47 1 vol. in 1 vol. alcohol, insoluble when
Quantity more alcohol was added
EUTACEÊ 433
l
Koure-Bertrand Fils state that certain constituents of neroli oil are
destroyed by steam distillation in the ordinary method. They state that
slight modification in the distillation process produces distinct alterations
in the physical characters of the oil, especially the optical rotation. They
have therefore carried out an exhaustive examination of neroli oil made
by an extraction process, with subsequent distillation.
For this purpose they treated in May
and at the end of October about 300 kilos
of flowers.
The flowers were extracted by three
washings with petroleum spirit. The
three solutions were united, dried, and
filtered, then the solvent was distilled off,
care being taken to expel the last traces
in vacuo. The residue from this distilla-
tion is a brown, viscous mass composed
of vegetable wax, the colouring matter
Fio. 44.—Arabian still in Tunisia
and the essential oil of the flower.
(native distillation of neroli oil). This brown residue was then sub-
jected to distillation in a current of steam.
In a suitable rectifying apparatus the es-
sential oil alone is carried over, free from any waxy matters. The water
condensed in the course of this operation is exhausted with ether, after
saturation with common salt, and the evaporation of the ether leaves a
residue which is termed the soluble essential \ oil. The portion which
floats on the surface of the condensed water and which is isolated by
simple decantation is termed the direct essential oil; the name of total
essential oil is given to that which is obtained by mixing the two former
oils in proportion to their yields.
The characters of the essential oils so obtained are set out in the.
following tables:—
(a) Direct Essential Oils.
May. Autumn.
Density at 15° C 0*8883 A.OOCfi
Index of Refraction nd15 1 1-474 1-469

Rotatory Power . . . . 0 ° 40' 4° 98'
Solubility in 80 per Cent. Alcohol . . 1 vol. and over 1 vol. and over
Acid Value . . . . . . 0*7 0-7
Coefficient o f Saponification . . . 71 '4 96-6
Total Esters (as Linalyl Acetate) . 25*0 per cent. 33-8 per cent.
Coefficient of Saponification of the Acetylated
Oil 172*2 185-9
Total Alcohol ( a s Linalol) . . . . 54 '4 p e r cent. 59-3 per cent.
Methyl Anthranilate , 2'43 „ 1-57 ,,
1
1
Bulletin, April, 1910, 43.
VOL. I 28
(b) Soluble Essential Oils.
M*y. Autumn.
Density at 15° C 0-9434 0-9124

Index of Refraction nd15 1-498 1-483
Rotatory Power (1 = 1 0 0 mm.) . . . . - 1° 46' - 3° 20'
Solubility in 80 per Cent. Alcohol 1 vol. and over 1 vol. and over
Acid Value . . . . . 0-7 1-05
Coefficient o f Saponification . . . . 61-6 58-8
Total Esters (as Linalyl Acetate) . 21-5 per cent. 20*6 per cent.
Oil . 164-7 173*7
Total Alcohols ( a s Linalol) . . . . 51*6 per cent. 54*8 per cent.
Methyl Anthranilate . . . . . . 13-2 12-4
(c) Total Essential Oils.

May. Autumn.
Density a t 1 5 ° C . ... 0-8899 0-8887

Index of Refraction wd15 . 1-478 1-476
Rotatory Power (I = 100 mm.) . - 0° 48' . - 4° 6'
Solubility in 80 per Cent. Alcohol 1 vol. and over 1 vol. and over
Acid Value . . . . 0-7 1-0
Coefficient of Saponification 70-2 95-8
Total Esters (as Linalyl Acetate) 24-6 per cent. 33-4 per cent.
Oil 163-1 179-5
Total Alcohol (as Linalol) . 51-0 per cent. 57-0 per cent.
Methyl Anthranilate . . . 3-53 „ 2-74 „
Spanish neroli oil differs in character from the French distillate.

The figures for two typical samples examined by Umney l are as follows:—
SPANISH NEROLI OIL.
(Distilled at Alora.)
Specific gravity -860
Optical rotation 4-25°
Solubility 1 in 1 vol. of 90 per cent, alcohol. Not soluble in 80 per
cent, alcohol.
SPANISH NEROLI OIL.
(Distilled at Malaga.)
Specific gravity . •861
Solubility 1 in 1 vol. of 90 per cent, alcohol. Not soluble in 80 per
cent, alcohol.
Spanish neroli oils examined by Schimmel gave the following re-
sults :—
^P.widE.O.R. (1913), 137.
EUTACE^l 435
Bigarade (Bitter). «' Portugal "
(Sweet).
Specific gravity . 0*871 0'857
Optical rotation + 10° 54' + 42° 47'
Acid value 1-37 1-6
Ester value 37-67 6-86
Methyl anthranilate 0'5 per cent. 0*3 per cent.
Spanish oils have a specific gravity up to 0*885 and an optical rota-
tion varying from + 9° to + 29°.
Various other oils distilled in different parts of the world have been
examined with the following results :—
SICILIAN OIL.
Optical rotation + 2° 54' „ 56° 30'
ALQBBIAN OIL.
SYRIAN OIL.
Specific gravity . . . . . . . 0*8758
Ester value . . . . . . . . 51*5
Umney and Bennett have examined a Chinese neroli oil derived from
Citrus triptera. It had a specific gravity 0*850 and optical rotation -f
35°. It contained 4'8 per cent, of esters calculated as linalyl acetate, and
21 per cent, of free alcohols as linalol. It contained much limonene,
camphene, linalyl acetate, methyl-anthranilate and a paraffin.
Methyl anthranilate, determined as described under tangerine orange
oil, is present to the extent of 0'2 to 1'5 per cent, in ordinary neroli oil,
or 10*5 to 16 per cent, in the oil extracted from the distillation water.
Neroli oil contains Z-a-pinene, Z-camphene, limonene, dipentene,
decyl aldehyde, phenyl-ethyl-alcohol, nerol, linalol, rf-terpineol, nerolidol,
geraniol, acetic esters of the various alcohols present, indol, traces of
benzole, palmitic, and phenyl-acetic acids in the form of esters, linalyl
acetate, and one or more paraffin hydrocarbons. None of these bodies,
however, are responsible for the characteristic fluorescence of the oil.
Ernst and Hugo Brdmann l have examined the oil, and found that the
portion which distils about 115° at a pressure of 10 mm. leaves on sap-
onification a crystalline acid of melting-point about 140°. This acid was
completely identified as anthranilic acid (o-amidobenzoic acid), and it
occurs in the oil as its methyl ester. The pure body, methyl-o-amido-
benzoate, is an oil solidifying at low temperatures in crystals, melting at
24-5° and boiling at 127° at 11 mm. Its specific gravity is 1-163 and 26°.
It is easily soluble in dilute mineral acids (on account of its basic
character), alcohol or ether, and yields a crystalline hydrochloride. It is
strongly fluorescent. Schimmel & Co. have found in the oil obtained by
*B*riehte (1899), 1213.
the extraction of the fresh flowers with petroleum, and extracting the
petroleum extract with alcohol, traces of phenyl aceto-nitrile and a
crystalline body melting at 158°, a ketone with a jasmine-like odour,
possibly identical with jasmone, and a high boiling sesquiterpene alcohol
(nerolidol ?), with traces of a base apparently belonging to the nicotine
series.
OIL OF PETIT-GRAIN.
The original oil of petit-grain was obtained by the distillation of the
small unripe orange berry, which, according to Pereira, rapidly underwent
decomposition. The petit-grain oil of to-day, however, is distilled from
the leaves and young shoots of the bitter orange.
The best petit-grain oil is distilled in the south of France, a certain
amount also in Algeria and Spain, and a large amount of less perfume
value is distilled in Paraguay, which form the bulk of the oil of
commerce.
The distillation in Paraguay is carried on in small factories in the
immediate vicinity of orange forests, as the total absence of all means of
communication renders it impossible to centralise the production. Every
group of factories is managed and superintended by one employee. The
woods have always the character of timber forests of the most diverse
varieties, among which is found a sort of undergrowth of smaller dimen-
sions, with patches almost completely covered with orange trees, which
the inhabitants call manchones. Such manchones are scattered about the
forests at certain distances.
In specially favourable situations the bigaradier predominates, in
others the latter is found mixed with the sweet orange and with another
species called assessu, which is a variety of the two first-named. This
species is used preferably for the manufacture of petit-grain oil.
Although the orange forests are very numerous in Paraguay, they
afford but rarely the preliminary conditions necessary for normal working,
as they are mostly far removed from inhabited centres. The leaves are
gathered all the year round, but chiefly between October and April, during
which period the bulk of the oil is produced. For this purpose the trees
are cut down at a height of about 2 ins. from the ground ; the leaves and
young fruit are distilled together, and the wood of the trees is used as
fuel for the boiler.
During the past few years a number of samples of Paraguay petit-
grain oil have been found which had an optical rotation up to + 8° or
+ 9°. This appears to be due to the distillation material containing
small, immature fruits, the essential oil of which contains much dextro-
limonene. Normal Paraguay petit-grain oil has the following characters:—
Specific gravity . . . . 0'885 t o 0-900
Optical rotation . . . . - 3° to -f 11° (usually under + 5°)
Refractive index . . . . 1-4590 t o 1-4655
Acid value . . . . . 1 ,,3
Ester „ 105 „ 166
The oil is soluble in 1 to 2 volumes of 80 per cent, alcohol, but in the
case of oils with a high dextro-rotation, the presence of limonene may
cause a slight turbidity in the solution. Subject to the same consideration,
the oil is soluble in 3 to 5 volumes of 70 per cent, alcohol.
French petit-grain oil has the following characters :—
EUTACE^ 437
Eaters 50 to 70 per cent.
Schimmel & Co.1 give the following as the characters of petit-grain
oils of various origins :—
Origin. Specific Gravity. Rotation. Esters.
Calabria . . . 0-8746 + 18° 26-3 per cent.
Spain . . 0-8849 + 8° 25' 28-6
Jamaica . . 0-8846 - 6° 30' 28-7
West Indies . 0-8531 + 43° 36' 2-1
South America 0-887 -t-2 0 36-5
Syria . . 0-8857 - 3° 24' 27-1'
It is obvious that the W. Indian sample is not a normal petit-grain
oil at all, but has been distilled chiefly from immature orange fruits.
The twigs and leaves of the lemon, lime, and mandarin trees also
yield similar oils, which have been termed " petit-grain oils ". The
lemon product has been termed " oil of petit-grain citronnier ".
Boure-Bertrand Fils 1 have prepared four different petit-grain oils
from the branches of the bitter orange, the sweet orange, the lemon, and
the mandarin-tree, and have found these oils to possess the constants
given below :—
Sweet Orange. Bitter Orange. Lemon. Mandarin.
«*»" . . . . 0-8980 0-8584 0-8806 1-0643

oD . - 4° 20' + 53° 52' + 30° 44' + 2° 20'
SaponifL-ation Value 161-4 12-5 43-8 265-0
Ester Value after Acety
lation . 203-0 47-4 130-6
Solubility In 3-5 vols. In 0-5 vols. In 1 vol. In 1 vol.
70 per cent. 90 per cent. 85 per cent. 90 per cent.
Alcohol. Alcohol. Alcohol. Alcohol.
The oil distilled from the corresponding parts of the lemon tree has
an odour resembling that of petit-grain oil, with a secondary odour of
lemon. It has the following characters :—
Ester value 14 ,, 46
It contains camphene (?), limonene, geraniol, linalol (?) and citral.
Jeancard and Satie give the following figures for the " petit-grain "
oil of lemon :—
Specific Gravity. Rotation. Esters.
Lemon Petit-grain . . 0-8763 + 13° 20' 12-25 per,cent.
Mandarin petit-grain oil has the following characters:—
The oil appears to vary in character to a considerable extent according
to the proportion of twigs and leaves present in the distillation material.
This oil may contain 65 per cent, of methyl-anthranilate.
1
Bulletin, October, 1910, 42.
Lime " petit-grain " oil has the following characters :—
An oil distilled from the unripe orange fruits, analogous to the old-
fashioned petit-grain oil, is manufactured and offered under the name of
"oil of orange peas". Its specific gravity is about *852 to '854 and its
optical rotation 4- 75°. It is intermediate in composition between orange
oil and neroli oil. It contains methyl-anthranilate and also traces of
a pyrrol compound.
Umney and Bennett have examined a Buenos Ayres oil resembling
ordinary South American petit-grain oil, but having more free alcohols
and less esters than those oils. Pinene, dipentene, furfural, geraniol,
linalol, and geranyl acetate were found to be present. Its specific gravity
was 0*887, optical rotation + 2°, esters 36*5 per cent., and free alcohols
as geraniol 38*4 per cent.
Terpinyl acetate has been used recently as an adulterant of petit-
grain oil, and in 1912 a serious dispute took place as to the purity of a
sample suspected of containing this adulterant, several chemists holding
antagonistic opinions on the subjectr The sample was eventually re-
ferred to the author, and terpinyl acetate was found to be present, the
following method of investigation being adopted.
|The oil had the following characters :—
Specific gravity at 15'5° 0*8965
Optical rotation + 1° 10
i Refractive index at 20° 1-4650
Ester value (as ImaLyl acetate) 1 40*5 per cent.
The peculiar odour of the oil suggested the presence of an added
ester, the indication being that of terpinyl acetate.
The oil was examined, in the first place by means of a series of
fractional saponifications, and secondly by the fractional distillation of a
large quantity of the oil. >- -
The three saponifications were carried out under identical conditions,
except that the times allowed for the reaction were 30 minutes, 75
minutes, and 120 minutes respectively. The results obtained were as
follows:—
S.V.
3 0 minutes' saponification. . . . . . . . . 115*7
75 „ 122*5
120 „ 124-8
The increase in values by prolonging the time of saponification is a
strong indication of terpinyl acetate, which is, as is well known, an ester
much more resistant to the action of alcoholic potash than linalyl acetate.
A much more marked indication is found by taking the differences in
the saponification values as suggested by Schimmel & Co. About 2 to 3
grams of the oil are saponified—(1) with 20 c.c. of semi-normal potash for
two hours; (2) the same amount of oil is used, but only 10 c.c. of semi-
normal potash, diluted with 25 c.c. of alcohol, and the saponification
allowed to proceed for one hour. Under these conditions Messrs.
Schimmel & Co. have shown that pure or nearly pure terpinyl acetate
will show a difference of practically 90 in the saponification value.
On the sample in question the following results were obtained :—
KUTACB^ 439
( 1 ) T w o hours' saponification . . . . . . . 124
(2) One hour's „ 101'5
Difference 23*5
A large quantity of the oil was then repeatedly fractionated under re-
duced pressure. The difference in boiling temperatures of this group of
alcohols and esters is considerably less under very low pressure than at
normal pressure. Attempts to fractionate at normal pressure were suffi-
ciently definite to strongly support the whole of the preceding results,
although the characters of the fractions in question only showed ap-
proximations to those of terpinyl acetate. After a series of fractionations
a fraction was finally obtained boiling at 217° to 221°, which had a clear
and definite odour of terpinyl acetate, and whose specific gravity was
0-917, and refractive index 1*4773 at 20°. A fractional saponification of
this fraction, by the method above described, gave the following results :—
T w o hours' saponification . . . . . . . .192
One hour's „ 160
Difference 32
By reducing the pressure to about 11 to 14 mm., and collecting the
fractions boiling from 100° to 118° and refractionating three times, a
fraction was obtained boiling at 110° to 115°, which had the following
characters:—
Specific gravity '. . . 0'9205
Saponification value (two hours) . . . . . . . 199
„ „ (one hour) 164
Difference 35
Similar fractionations were made with the saponified oil, and fractions
were obtained having a marked odour of terpmeol, although the body
could not be obtained in a pure condition.
Petit-grain oil contains camphene, /?-pinene, dipentene, limonene,
Z-linalol, d-a-terpineol, geraniol, esters of linalol and geraniol, a sesqui-
terpene, and methyl anthranilate.
OIL OF LIMES.
There are three distinct oils found in commerce, the one, hand-pressed
oil obtained from the Citrus limetta (Italian), the others being the dis-
tilled and hand-pressed oils respectively from Citrus medica var. acida
(West Indian). Expressed oil is prepared from the fruit in December
and January. In the south-west of Italy the tree is known as limoncello
di Spagna. The Italian oil somewhat resembles lemon oil, but with a
much richer odour, somewhat recalling the odour of bergamot. It con-
tains pinene, limonene, and probably dipentene, linalol, linalyl acetate,
and citral. It has the following constants :—
Optical rotation . . . . . . . . . . + 58°
Saponification value . . . . . . . . . 75
Adulterants such as lemon oil and terpenes are frequently used and
may be detected by distillation tests as given for lemon and orange oils.
Distilled oil of limes, the usual oil of commerce, is obtained from Jamaica,
Dominica, and Tahiti, but chiefly from the island of Montserrat, the
harvest lasting from September to January. The oil is really a by-
product obtained by distillation during the concentration of the lime-juice,
and the peculiar odour is due to the partial decomposition of the oxy-
genated constituents. Citral decomposes into cymene when boiled with
dilute acids. It contains pinene, limonene, cymene, dipentene, bisabolene,
and Z-terpineol, melting-point 35°, and another alcohol having a strong
lime-like odour forming a urethane, melting-point 131°, but not yet
identified. Distilled lime oil has the following constants :—
Hand-pressed West Indian limes oil is of considerably higher value
than the distilled oil. Its characters are as follows :—
Fixed residue . . . . . . . . 9 to 18 per cent.
Citral . . , 6„9
The fixed residue has a saponification value of 160 to 180. This oil
contains citral, bisabolene, methyl anthranilate, and citraptene.
The leaves of the West Indian lime tree yield an oil on distillation,
Acid value 3 „ 5
Ester „ . 22 „ 25
Aldehydes 43 per cent.
The author has examined an oil distilled from the flowers of the
Italian lime tree, and found it to have the following characters :—
It contains linalol and methyl anthranilate.
OIL OF BEBGAMOT.
This oil is obtained by expression from the fresh peel of the fruit of
Citrus aurantium subsp. Bergamia, the ordinary bergamot. The chief
centre of the industry is Southern Calabria, which is practically the only
province in which the tree is cultivated, extensive plantations being
situated at, and in the neighbourhoods of, Beggio, Melito, Gallico,
Arangea, Sancta Catarina, S. Lorenzo, Palizzi, Staiti, etc. Almost all
the oil is expressed by machines, but as these are usually adjusted for
globular fruits, any that have the oblong lemon shape are treated by
hand. Hand-pressed oil is, however, rarely met with in commerce. The
trees are best grown on well-irrigated, low-lying lands, and are frequently
cultivated amongst the lemon and orange trees. The fruit is gathered in
the months of November and December and the first week or two in
January, when the manufacturing season is over. The resulting oil is
of a green colour, due to the presence of chlorophyll (not to the presence
of copper, as sometimes stated).
The bergamot tree is a very delicate one, and any inclemency of the
weather will adversely affect the fruit v ry seriously. Excess of either
i-a
>
Q
a
fe
FIG. 45.—Manufacture of the oil of Bergamot in Calabria.

[Roure-Bertrand Fits,
moisture or drought, too much sun, mist, or early autumnal rains will
sometimes change the whole aspect of the crop in a few days.
Bergamot oil is one which is adulterated with considerable skill, the
use of artificial esters being fairly common for the purpose. A compre-
hensive examination is therefore necessary, as the physical characters
can be, and frequently are, standardised to those of a pure oil.
A pure bergamot oil has the following characters :—
Specific gravity 0-881 to 0-886 (rarely 0-880 to 0-887)
Optical rotation + 8° „ + 22° (in some seasons to + 25°)
Acid value 1 „4
Esters as linalyl acetate . 34 per cent, to 42 per cent, (rarely
to 45 per cent.)
On evaporation of the oil on a water-bath it leaves a non-volatile
residue of 4*5 to 6*5 per cent, (rarely a little outside these limits). This
non-volatile residue should have an acid value of 18 to 30, and an ester
value of 115 to 180.
The above characters may be somewhat altered if fallen, unripe fruits
be used in the preparation of the oil. Oil from such fruits may have a
specific gravity as low as 0-879, and an ester content of 26 to 33 per cent.
Under the name " Nero de Bergamotto " is understood a bastard berga-
mot (Bergamottella), which, if mixed with the ordinary fruits when
pressed, will raise the specific gravity and lower the ester value. The
oil from these bastard fruits has a specific gravity 0*890 to 0*898, and an
ester content of 20 to 35 per cent.
Distilled bergamot oil, obtained by distilling the residues from the
expression process, is of very low odour value, having a specific gravity
as low as 0-865 and an ester content which may fall as low as 5 per cent.
The principal adulterants used to-day consist of artificial esters, with
or without a neutral oil such as lemon terpenes. Esters of the non-
volatile acids, or which are themselves of low volatility will be found in
the evaporation residue of the oil, which if over 6 per cent, will at once
arouse suspicion. The saponification value of this residue will therefore
be increased if such esters are present. If the saponification value is
over 185, it is almost certain, and if it is over 195, quite certain, that such
an adulterant is present. Ethyl citrate is the principal ester of this type
used as an adulterant. One per cent, of triethyl citrate added to the oil
will raise the saponification value enormously—for example, from 175 to
220.
In determining the ester value of the oil, it should be carefully
watched for the first five or ten minutes. The clear liquid will very soon
become turbid, on account of the separation of potassium citrate (which
is not very soluble in alcohol), if citric acid esters are present, and
eventually become clear again. Deniges l has devised a test by which
the presence of citric acid can be positively decided.
\Deniges' test consists in vigorously shaking 10 c.c. of the solution
with 1 to 1*5 grams peroxide of lead, adding 2 c.c. solution of mercuric
sulphate, and filtering. Of the filtrate, 5 c.c. is heated to boiling-point,
after which a 2 per cent, solution of permanganate of potassium is added
by drops, with stirring, until the latter ceases to become decolorised
immediately. If citric acid is present a flocculent, white or pale yellow
precipitate shows itself after the first drop.
l
Bull. Soc. Ph., Bordeaux (1898), 33.
O
CO
FIG, 46.—Filtering apparatus for the oil of Bergamot.
\Ro\ire-Bertrand Fils.
Citric acid can also be detected by precipitating as calcium citrate.
This test is carried out by saponifying about 2 grams of the oil, or the
residue of evaporation of 5 grams of oil, with alcoholic potash, diluting
the solution with water, neutralising with hydrochloric acid, removing the
alcohol on the water-bath, and then extracting the solution with ether, and
filtering. For the calcium test the solutions are rendered faintly alkaline
with a trace of caustic soda, after which a few drops of concentrated
chloride of calcium solution are added and the whole boiled. Any citric
acid which is present is shown by a precipitate, which is often formed
only after some time.
Oxalic acid, resulting from the use of ethyl oxalate as an adulterant,
is^ similarly detected, the calcium precipitate then'having the usual char-
acters of calcium oxalate.
With the exception, however, of triethyl citrate, nearly all the non-
volatile esters are to a great extent removed mechanically during the
evaporation in the oil vapour. To detect, for example, glyceryl acetate,
ethyl oxalate, ethyl tartrate, and ethyl succinate, the evaporation should
only be proceeded with until about 10 to 15 per cent, of the oil is left in
the dish, and this residue tested for the various acids.
Terpinyl acetate is indicated by a difference to be observed in the
apparent ester value by different times of saponification. This ester is
far more resistant to the action of caustic alkali than is linalyl acetate,
and requires two hours at least for complete saponification. Hence, if
the oil shows a difference in the saponification value in thirty minutes
and in two hours, which amounts to more than from 1 tol 2, terpinyl
acetate is almost certainly present. The following table shows the
effect of this partial-saponification on the two esters and on adulterated
oils :—
Time of Saponification. 5 mius. 15 mins. 30 mins. 45 mins. 1 hr. 2hrs.
Linalyl Acetate E. No. 191*5 217-5 223*2 223-7 223*1 224-7

Terpinyl ,, 108-2 166-8 209*7 233-4 245*8 262-7
Bergamot Oil 80-3 94-5 97'3 97-5 97*8 98-5
,, ,, + 5 °/0 Terpinyl Acetate 82-5 94-8 101'2 102-1 104-7 107-2
« + 10°/0 79-9 96-4 102*8 105-2 108*3 112-5
,, + 25% „ 78-8 100-6 1081 116-4 119*0 126-8
Fractional saponification, with the use of varying amounts of caustic

alkali, will also reveal the presence of terpinyl acetate.
The following table will indicate the differences observed when about
N
2'5 grams of the oil are saponified (1) with 20 c.c. of -^ alkali for two
A
N
hours, and (2) with 10 c.c. of -^ alkali, diluted with 25 c.c. of alcohol for
A
one hour :—
1
EUTACE^ 445
20 c.c. x 10 c.c. (and

Oil. 2 hours. 25 c.c. Alcohol) Difference.
x 1 hour.
Bergamot (1) 100-5 98-6 1-9

Bergamot (2) 108 105-5 2-5
with 5 per Cent. Terpinyl
Acetate . . . . 117 102-5 H-5
" with 10 per Cent. Terpinyl i
Acetate . . . . 121 104-0 17-0
The above table represents the behaviour on fractionation at 3 mm.

pressure of two samples of bergamot adulterated with terpinyl acetate and
a sample of pure bergamot oil.
The author * has recommended the examination of the last 10 per
cent, left on evaporation of the oil on a water-bath, since the heavy arti-
ficial esters accumulate in this fraction. The refractive index of this 10
per cent, should not be below 1*5090, and the saponification value should
not exceed 190. The figures given on p. 446 represent nine samples of
adulterated oil, all sold as genuine bergamot oil.
Glyceryl acetate, which is an artificial ester commonly used in the
adulteration of bergamot oil, is detected fairly easily on account of its high
solubility in dilute alcohol. The test is carried out as follows 2 : Ten c.c.
of bergamot oil and 20 c.c. of 5 per cent, alcohol are well shaken in a
separating funnel, and after the solutions have separated and become
clear the watery solution is run off and filtered. Ten c.c. of the filtrate
are exactly neutralised with deci-normal alkali, and then 5 c.c. of semi-
normal alkali run in, and the whole saponified under a reflux condenser
for one hour. In the case of pure bergamot oil 0*1 or at most 0*2 c.c. of
semi-normal alkali will have been used up by the saponification, whilst
each 1 per cent, of glyceryl tri-acetate present in the oil will be represented
by practically 0*5 c.c. of semi-normal alkali.
Schimmel & Co. have proposed to detect esters of fixed acids by an.
estimation of the amount of volatile acids obtained by distilling the
acidified saponification residues, and comparing this figure with the
amount of acid indicated by the saponification valued
In this determination about 2 grams are saponified in the usual
manner, and the saponification residue rendered slightly alkaline, and
evaporated to dryness on a watsr-bath. The residue is dissolved in 5 c.c..
of water and acidified with 2 c.c. of dilute sulphuric acid. This liquid is
now distilled by passing a current of steam through it, and when no
further acid comes over, the distillate (about 300 c.c.) is titrated with deci-
normal alkali, using phenolphthalein as indicator. The alkali consumed in
this neutralisation is nearly identical with that used in the direct saponi-
fication, if all the esters present are those of volatile acids, as is the case
with pure bergamot oil. The distillation value should not be more than
5 to 10 below the direct saponification value (i.e. milligrams of KOH per
1 gram of oil). When esters of non-volatile acids have been used as
adulterants the difference is enormous. For example, an oil co ntaining.
2 per cent, of ethyl citrate yielded a direct saponification valueo f 109*1
1 2
P. and E.O.R. (1911), 14. SchimmQl'sBericht, April, 1911, 151.
I. II. Pure Bergaraot Oil.
Fraction. fej
Per Cent. aD> Per Cent. Per Cent. a
W
D20°. «D. W
D20°. . «D. W
D20°.
W
1. to 40° 2 + 36° 35' 1-47225 10-6 -1- 52° 34' 1-47235 18-6 + 58° 16' 1-47303
2. 40 „ 50° 38-8 + 60° 5' 1-47274 28-5 + 64° 47' 1-47264 18-9 + 68° 51' 1-47245
3. 50 „ 68° " 5-6 4- 17° 15' 1-46545
4. 68 „ 72° 9-1 - 11° 32' 1-46030

} 3-9 + 8° 35' 1-46664
21-4 - 15° 20' 1-45781
5. 72 „ 78° 8-7 - 11° 20' 146001 20-2 - 11° 16' 1-45331 GO

CO
6. 78 „ 82° 12-1 - 8° 56' 1-45871 14-8 - 6° 12' 1-45991 — — —

7. 82 „ 88° 20-1 - 3" 42' j 1-46011 19-5 - 2° 16' 1-46229 • — — —
8. 88 „ 91° 5-4 - 1° 30' 1-46387 — ~ — — — —
9. Residue 12-5 — 14-0 — — 15-3 — — r1
QQ
! 1. 2. 3. 4. 5. 6. 7. 8. 9.
Specific Gravity . . . . . . 0-885 0-884 0-884 0-8855 0-886 0-886 0-886 0-885 0-878
i Optical Rotation 4- 16° 4- 16° 30' + 16° 30' 4- 18° + 23° 4- 17° 4-20° + 26° 4- 27°
Refractive Index a t 2 0 ° . . . . 1-4660 1-4660 1-4662 1-4658 1-4660 1-4660 1-4681 1-4675 1-4691
EUTACEJE
!
Apparent Esters as Linalyl Acetate . 39°/0 39-5 °/0 - 39% 38-8 % 39-5 % 40% 41% 34 %
!
Fixed Residue . . 6-5 % 6-3 % 4-2% 6-4 % 7-2% 4-5 % 6-9 % 4%
,, ,, Saponification Value of 257 225 160 239 236 252 172 242 162
,, ,, of Saponified Oil . 5-3% ; 5% 4-1% 4-9 °/0 4'7 °/0 5'4 % 4-2 % 5-4 % 4%
Refractive Index of last 10 per cent. . 1-5040 1-5042 1-5085 1-5042 1-5040 1-5050 1-5070 1-5050 1-5091
! Increase in Ester Value in one hour . 1 38%
— — — — 4-1 % — —
i
All these were adulterated with ethyl citrate except Nos. 3 and 7, which contained terpinyl acetate, and No. 9, which was adulterated
with lemon terpenes.
and a distillation value of 92*8, and one containing 5 per cent, of ethyl
succinate gave a direct value of 127*6 and a distillation value of 91*5.
Umney i has made a critical study of this method, and recommends
the following apparatus to be used in the process (see Fig. 47):—
(a) A 3 litre Jena glass flask.
(b) A rubber connection, the removal of which, of course, immedi-
ately cuts off the steam supply.
(c) A long-necked CO2 flask of Jena glass and 150 c.c. capacity.
(d) The most suitable splash head for the operation.
(e) A Da vies' condenser.
(/) A 500 c.c. Erlenmeyer flask.
FIG. 47.
The results obtained, unless the special precautions described be
adopted when calculated as percentages of .ester in the oil, are consider-
ably too high. Whilst some of the causes may be apparent to many,
nevertheless the following is a list constructed to include the more im-
portant of these causes, and will serve to indicate in what manner the
necessary amendments should be made :—
1. The use of methylated spirit (unpurified by further distillation)
' in the preparation of the standard potash solution employed by some
experimenters in the saponification of the oil.
2. The use of hydrochloric acid in neutralising the excess of alkali
after saponification.
3. The employment of water in the steam generating flask which
has been insufficiently boiled to free it from carbon dioxide and other
impurities.
4. The sulphuric acid, used to acidulate before distillation, may be
advantageously replaced by phosphoric acid. This modification, whilst
1
P. and E.OM. (1914), 116.
EUTACE^ 449
in many cases not absolutely essential, is desirable on account of the fact

that sulphuric acid is liable to become reduced by certain constituents of
oils, particularly of old oils, which frequently contain substances of a
resinous nature. In such cases the v latile acid products of the reduc-
tion pass over along with the true acids of the oil undergoing examina-
tion.
The relations which the abnormal results obtained bear to the above
outlined conditions are clearly shown by the appended figures :—
Method.
Percentage of Ester
found.
1. Oil saponified by solution of potash in unpurified methy-

lated spirit. Excess of alkali neutralised by hydro
chloric acid and the acids liberated, previous to dis-
tillation b y sulphuric acid . . . . . . 47-28
2. As 1, but the excess of alkali after saponification neutra-
lised by sulphuric acid 43-51
3. As 2, but the methylated alcoholic potash replaced by a
solution of potash in 96 per cent. (60 o.p.) alcohol 41-38
4. As 2, methylated alcoholic potash (the spirit being
previously purified by distillation over potash) being
used instead of the solution of potash in unpurified
spirit . . . . . . . . . . 41-45
5. As 2, the methylated alcoholic potash being replaced by
a solution of potash in absolute alcohol purified by
distillation over potash . . . . . . . 41-00
(>. A ** blank " experiment, employing for distillation the 1-5 c.c. deci-normal
residue resulting from the evaporation of 25 c.c. of the sodium hydroxide
alcoholic potash used in 5, previously neutralised by was required for
means of sulphuric acid the neutralisation
of the distillate
7. Ester found in 5 less the amount of ester equivalent to
the volume of deci-normal sodium hydroxide used up in
t h e blank experiment . . . . . . . 39-69
It is evident that, in order to obtain accurate results, the method of

working must be clearly and minutely adhered to, especially in view
of the fact that the determination of ester by the method of steam distilla-
tion is a very valuable indication as to the purity of an oil, serving to
detect the fraudulent addition to oils of such esters as diethyl succinate,
triethyl citrate, and diethyl oxalate, the free acids of which are non-
volatile in steam. It will not detect glyceryl acetate or terpinyl acetate.
The method, yielding reliable results and including modifications, devised
to remove the sources,of error above-mentioned, is as follows :—
About 2 grams of the oil (bergamot or lavender) is accurately weighed
into a carbon dioxide flask, and 15 c.c. neutralised alcohol added along
with a few drops of phenolphthalein solution, and the whole is just
boiled on the steam-bath. The acid number is ascertained by titra.ion
with deci-nor ral alcoholic potassium hydroxide, 25 c.c. semi-normal alco-
holic potash (made with 90 to 96 per cent, spirit, preferably distilled over
potash) is now added, and the whole boiled under a reflux condenser for
one hour, the excess of potash, after saponification and addition of 40 c.c.
VOL. i. 29
of carbon dioxide-free water, being neutralised by means of semi-normal
sulphuric acid. This titration gives the figure from which the ester per-
centage is calculated.
A few drops of semi-normal alcoholic potash are added, and the
liquid allowed to evaporate on the steam-bath.
To the residue is added 10 c.c. of dilute phosphoric acid, prepared by
mixing about 3*5 c.c. of 88 per cent, acid with 100 c.c. of carbon dioxide-
free distilled water.
The carbon dioxide flask is now immediately attached to the appara-
tus, and the distillation is commenced.
It should here be noted that the distilled water in the steam generat-
ing flask must have been allowed to become entirely free from carbon
dioxide by at least half an hour's preliminary boiling.
The whole apparatus must be thoroughly cleansed and freed from air
by allowing steam from the generator to blow through for a few minutes
before attaching the carbon dioxide flask.
Distillation is allowed to proceed, the water in the generator being
kept boiling as quickly as possible, and the volume of liquid in the
smaller flask being kept at about 10 c.c. by means of a small flame.
The time taken for the collection of the required 250 c.c. of distillate
is usually about thirty minutes.
The distillate is collected in a 500 c.c. Erlenmeyer flask having a
mark upon it to indicate the level of 250 c.c. Phenolphthalein solution
and a sufficient excess of deci-normal sodium hydroxide solution are added
to the distillate and the excess of alkali determined by back-titration.
Bergamot oil contains as its principal constituent linalyl acetate, to
the extent of up to over 40 per cent. It contains limonene, pinene,
camphene, bornylene, bisabolene, Z-linalol in the free state, dihydrocumic
alcohol, nerol, terpineol, and about 4 to 5 per cent, of the solid body
bergaptene, C12H8O4. \
OIL OF SHADDOCK.
The shaddock is the fruit of Citrus decumana, usually known in this
country as the grape fruit. It is a large fruit, native to China and Japan,
and introduced into the West Indies by Captain Shaddock, whence its
name. The oil, which is not known to any extent in commerce, has a
specific gravity of about *860 and an optical rotation of + 90° to -f 95°.
It is a typical Citrus oil, containing much limonene, but its constituents
have not yet been carefully examined.
According to Brooks, the le ives of the tree Citrus decumana growing
in the Philippines, which is probably a variety of the European tree,
yields 1*7 per cent, of an oil having the following characters:—
Specific gravity at 30°
—6 0*870
ou
Optical rotation at 30° + 22-9°
Ester number 10
It contains dipentene, 15 per cent, of linalol, and 1 per cent, of citral.
H. F. Zoller* has examined the oil obtained by steam distillation
from the peel of Citrus decumana grown in the United States. He
found it to have the following characters :—
i
Jour. Ind. Eng. Clwm. (1918), 10, 5, 364.
EUTACBÊ 451
1. 2.
Specific gravity 0 845 0'860
Optical rotation +72-5° + 78-5°
The constituents present, with their approximate quantities, are as
follows:—
a-pinene . 0-5 to 1-5 per cent.
d-limonene 90 „ 92
Linalol 1 „2
Citral 3 „5
Geraniol . 1 „2
Geranyl acetate, linalyl acetate, and citronellal are probably present
in traces.
OIL OF CITRON.
This oil is expressed from the fresh peel of the fruit of Citrus medica
var. vulgaris, the ordinary citron, a native of the Himalayas, which was
cultivated by the Aryans from very early times. In France the fruit is
known as a " cedrat"—the French " citron " being our lemon. Conse-
quently ** essence de citrons " must not be confused with citron oil. The
tree flourishes in the south of Europe, particularly in Italy, the fruit
sometimes weighing from 10 to 14 Ib. Several other varieties of this
plant exist and appear to be used for expression, when the figures given
below will be exceeded; for example, some varieties yield an oil with a
specific gravity of about 0*870 and optical rotation about + 67°. This
oil, which is seldom met with pure, should have the following constants :
specific gravity *851 to *854, rotation + 77° to 82°, refractive index about
1*4750. It contains chiefly limonene, dipentene, citral, and a crystalline
body ; melting-point 145°. The usual adulterants are lemon and orange
oils and their terpenes. The odour of this oil is very little superior to
that of good lemon oil, whereas the price demanded does not justify its
extensive use in commerce.
OILS OF XANTHOXYLUM.
Thorns, about two years ago, reported on the essential oil of the fruit
of Japanese pepper, Xanthoxylum piperitum, which yielded 4*33 per
cent, of the oil. Schimmel & Co. have stated that the chief constituent
of the oil1is citral. The oil has now been more exhaustively examined by
Duruttis. He finds the oil to have the following characters :—
From the fraction 175° to 177° (specific gravity = 0-8469, optica
rotation = + 55*7°) a tetrabromide melting at 120° and a nitrosochloride
melting at 93° to 95° were obtained. This fraction appears to be a mix-
ture of dipentene and dextro-limoneue. The oil consists of terpenes to
the extent of about 90 per cent. The fractions boiling over 180° were
treated with sodium bisulphite, and the compound formed treated in the
usual manner, when a body was liberated which was found to be cumic
aldehyde, which was identified by its forming a semi-carbazone melting
at 210°, and by oxidation to cuminic acid melting at 115°. In the fraction
1
Arbeit, a. d. Pharm. Inst. L'niv., Berlin, 60.
melting at 180° to 184° free palmitic acid was detected. Geraniol was
found in the oil, but in small quantity only.
Asahina and Konnol have also examined the oil recently, and state
that they find 13 per cent, of citronellal present. The oil which they
examined had the following characters :—
,, rotation + 45'45°
They also identified d-/?-phellandrene and cumic aldehyde.
There has recently been imported into this country a " Japanese
pepper " which Holmes has identified as the fruit of Xanthoxylum alatum,
Its essential oil has been examined by Umney 2 and found to have a
specific gravity 0*889, and an optical rotation - 23°. It contains a crystal-
line stearoptene melting at 80°.
Shinosaki3 has examined the essential oils distilled from the leaves of
Xanthoxylum ailanthoides, and found them to have the following char-
acters :—
Full-grown Half-grown Young
Leaves. Leaves. Leaves.
Specific gravity . . 0-8437 0-8385 0-8390
Optical rotation . . - 6° 35' - 5° 75' - 6° 63'
Refractive index . 1-4474 1-4408 1-4440
Saponification value 2-81 4-21 1-83
The principal constituent of the oil is methyl-nonyl-ketone, terpenes, and
about 1-5 per cent, of phenols.
The essential oil of the Formosan plant known as Yamakosho may
be mentioned here, its botanical origin being unknown, but the oil having
been reported on also by Shinosaki.4 From the leaves he obtained 1*2
of a brownish-yellow essential oil having an odour of camphor. It had
Ester value after acetylation . . . . . . . 48 66
It contains eucalyptol and hydrocarbons.
The oil from the fruits of Xanthoxylum acanthopodium known as-
" Wartara seeds " has been examined by Schimmel & Co.5 The oil had
On distillation in vacuo (14 mm.) the oil gave the following fractions :—
Fraction. Boiling-point. Specific Gravity a D at 18-5°. Quantity of

at 22°. Distillate.
1 65° to 70C >)-841 + 0°26' 45 c.c,

2 70° „ 80° 0-846 + 4° 17' 9
3 80° „ 90° 0-856 + 11° 38' 34
4 90° 0-865 + 13° 43' 19
5 90° to 100° 0-865 + 12° 39' 27
6 100° „ 130° 0-939 - 6° 2' 7
1
3
ApotJieker
Zeit., 32 (1917), 556. . and E.O.R. (1912), 37.
4
Jour. Soc.
Chem. Ind., 34 (1915), 1270.
5
Jour. Chem. Ind. Tokyo, 18 (1915), 1081. Report, April, 1900, 49.
463
Fraction 1, at atmospheric pressure, boiled at 175° to 176° and yielded

with bromine a tetrabromide melting at 125°. It consisted of almost pure
dipentene.
Fractions 3 to 5 were united and again fractionated, yielding a liquid
having the properties of d-linalol. Its specific gravity was 0*868, optical
rotation + 14° 20', and boiling-point 78° at 14 mm. pressure. The
identity of this body with linalol was proved by its conversion into citral
and Z-terpineol.
The citral obtained in the oxidation with a chromic acid mixture
yielded the characteristic naphtocinchoninic acid with a melting-point
between 197° and 200°. Treatment with formic acid produced Z-terpineol
with a melting-point of 35°. An alcoholic solution containing 3*6 per
cent, of this terpineol had the specific rotatory power [ao] = — 10° 14' at
18°. Treatment with carbanil yielded terpinylphenylurethane melting at
112° to 113°.
It is thus proved that d-linalol, previously found only in coriander oil,
is also a constituent of wartara oil.
The oil from Xanthoxylum senegalense (Fagara Xanthoxyloides) has
been examined by Priess, and found to have the following characters : —
„ rotation ......... - 1° 20'
Acid value .......... 2-19
Ester ,, ........... 58-5
The oil contains methyl-nonyl-ketone, and, probably, decyl aldehyde-
Dipentene, linalol, a sesquiterpene, esters, and the lactone xanthotoxin
were also isolated from the oil.
Thorns, who isolated this body, considered it to be a coumarin-like
compound, related to citraptene. His latest investigations l have con-
firmed the correctness of this supposition. He obtained a solid substance
(melting-point 128°) which was separated by repeated recrystallisation
into two bodies, xanthotoxin (melting-point 145° to 146°) and bergaptene
(melting-point 190° to 191°), the latter a constituent of bergamot oil. The
two bodies are isomeric, but bergaptene is a phloro-glucinol derivative,
whereas xanthotoxin is derived from pyrogallol.
From a botanical point of view the occurrence of . xanthotoxin and
bergaptene in this oil, and of bergaptene in that of bergamot oil, is in-
teresting, for the two plants are closely related, belonging to subdivisions
of the same botanical family,
The following formulae indicate the relationships of the two bodies : —
OCH3 OCH3
co HO/XCH •. CH
OH CH [ j
-O\yO . CO
Xanthotoxin. Bergaptene.
OIL OF EVODIA SIMPLEX.
An oil distilled in E6union from Evodia simplex has been examined
by Schimmel & Go.,2 who found it to have the following characters : —
Acid value 2-1
Ester 16-4
(after acetylation) 63*3
2
Berichte, 44 (1911), 3325. Bericht, October, 1906, 83.
The oil contains methyl-eugenol and a crystalline paraffin melting at 80*
to 81°.
OIL OF BOEONIA.
The herb Boronia polygalifolia, a plant found in most of the Australian
colonies, yields an essential oil which has been examined by J. C. Umney.1
It is described as having a specific gravity 0*839 (is this a misprint?),
and an optical rotation 4- 10°. On fractional distillation the following
fractions were obtained :—
150° to 170° 31 per cent.
170° „ 180° 88 „
180° „ 190° 15
Above 190° . 16
OIL OF EUE.
The genus Euta comprises about fifty species inhabiting the Medi-
terranean region and Eastern and Central Asia. The oil is distilled from
the herb Euta graveolens, yielding the French oil, whilst Algerian oil is
distilled from Euta montana, the summer rue, and Euta bracteosa, the
winter rue.
The various oils of rue have the following characters :—
FEBNCH OIL (EUTA GEAVEOLENS).
Optical rotation . . .' - 0° 50' to + 3°
Solidifying-point 5° ,, 11°
ALGERIAN OIL (EUTA MONTANA).
Optical rotation 0° to + 1°
Solidifying-point + 7° „ + 10°
This oil, which is soluble in 2'5 to 3 volumes of 70 per cent, alcohol,
is known as " essence figeable " (congealing oil) in Algeria.
ALGERIAN OIL (EUTA BRACTEOSA).
Solidifying-point below - 5°
This oil is known as " non-congealing oil" in Algeria. It is soluble,
often with turbidity, in 3 volumes of 70 per cent, alcohol.
SPANISH OIL.
Solidifying-point - 3° „ + 8
1
Imperial Inst. Jour., 2 (1896), 302.
EUTACE^ 455
SYRIAN OIL.
Solidifying-point - 1-9°
A sample of the oil from Ruta montana, which had the following
characteristics—
Melting-point . 10-5°
was fractionated at ordinary pressure,1 with the following results :—
i
Boiling-point. Refractive Melting-
Specific Gravity. Index 20°. point.
\
20 per cent. . 219-5° to 224° 0-834 1-4307 11°
3 0 . . . „ 226° 0-832 i 1-43 14°
2 5 . . . „ 227° 0-832 1-4297 14-5°
1 5 . . . „ 228-5° 0-836 1-4305 14°
10 „ . Res. above 228-5° — 1-4471
The characteristic constituents of the oils of rue are the ketones methyl-
nonyl-ketone, CH3 . CO . C9H19, and methyl-heptyl-ketone. Of these
methyl-nonyl-ketone predominates in the French oil and in the oil of
Ruta montana, whilst methyl-heptyl-ketone is present in the oil of
Ruta bracteosa.
Schimmel found traces of a basic substance present in the oil, which
is probably the methyl ether of methyl-anthranilic acid, and would
account for the fluorescence of the oil. Van Soden has examined all
Algerian oil of rue, and found it to have a specific gravity 0*84:2 and
optical rotation - 5°. It did not solidify even at - 15°. Its principal
constituent was found to be methyl-heptyl-ketone, whilst only a small
quantity of methyl-nonyl-ketone was present. This is evidently the oil
of Ruta bracteosa. A German oil investigated by Houben was found to
contain both ketones, the methyl-nonyl-ketone predominating. Traces of
caprylic acid and of a phenyl were detected. Power and Lees have ex-
amined an oil, probably of Algerian origin, and found present a basic sub-
stance having an odour of quinoline, traces of methyl salicylate and of
salicylic acid. They also found valeric acid (as esters?), laevo-pinene,
limonene, and cineol. The alcohols corresponding to the ketones were
also found present.
Bergaptene has also been found in traces in the oil.
The characters of the ketones above mentioned are as follows :—
METHYL-HEPTYL KETONE.
Boiling-point . . . . 194-5° to 195-5° (763 mm.)
Specific gravity . . . . d **! 0-8296
Melting-point of the semi-carbazone 119° to 120°
1
Evans' Analytical Notes (1912), 65.
METHYL-NONYL KETONE.
Boiling-point 229° to 233° (759 mm.)
Boiling of the ketone regenerated from
t h e semi-carbazone . . . . 231'5° t o 232-5° (761 mm.)
Specific gravity d ?^° 0-8263
Melting-point of the semi-carbazone . . 122°
Methyl-nonyl ketone is capable of being estimated quantitatively by
the phenyl-hydrazine method (see under lemon oil), and the same applies
to methyl-heptyl ketone. It should be remembered that in rue oil both
the ketones are always present in varying proportions. Hence the quantity
of phenyl-hydrazine which has been used only affords an approximate
estimation of the quantity of the ketones, and it must at the same time be
ascertained, by determining the solidifying-point, which of the two ketones
predominates in the oil, and whether it will bj more practicable in esti-
mating to use as a basis the molecular weight of methyl-nonyl ketone
(170) or that of methyl-heptyl ketone (142).
OIL OF BUCHU.
Several species of Barosma are known by the name B acini, and from
the leaves of these the oil is distilled. The chief of these are, Barosma
serratifolia, Barosma betulina, and Barosma crenulata. The yield of oil
is from 1 to 2 per cent. The recent researches of Kondakoff 1 and
Bialobrzeski 2 have proved that the oil contains several constituents.
These are diosphenol Cj0H16O2, the chief optically inactive compound in
the oil; the terpenes limonene and dipentene, and a ketone G10H18O
which is probably laevo-menthone. Diosphenol is a crystalline solid,
melting at 83° and boiling at 232°. It occurs only to a very small extent
in the oil distilled from the leaves of Barosma serratifolia, whereas that
from Barosma betulina contains so much that crystals separate at ordinary
temperature.
The ketone C10H18O is a slightly laevo-rotary liquid boiling at 206° to
209°, of specific gravity *902, of agreeable peppermint like odour, and is
probably identical with menthone. Pure diosphenol can be obtained from
the oil by extraction with soda solution and decomposition of the alkaline
liquid with an acid, and recrystallising the crude diosphenol from a
mixture of alcohol and ether. Buchu oil is often adulterated with turpen-
tine and possibly other oils. It is used to a small extent in medicine.
The oils have the following characters :—
11 (i1'<>,s*ma Bet id in <t.

Specific g r a v i t y 0'935 to 0-970
Optical rotation . . . . . . . . 15° ,, — 48°
Kefractive index 1-4740 „ 1-4H65
Diosphenol (by NaOH absorption) . . . 17 to 30 percent.
Baroxmci Crenitlata.
Specific gravity . . . . . . . . . 01(J36
Kefractive index 1*4800
1
Jour. fr. Chem., ii. 54 (1896), 41-33.
* Pharm. Zcit. Itu-ss., 35 (1896), 417, 433, 441).
BDTACEJE 457
Barosma Serratifolia.
In addition to the varieties of Barosma which are used in the prepara-
tion of buchu leaf oil the leaves of other species have lately been met
with lon the London market on several occasions. Some years ago,
Sage reported on leaves of Diosma succulentum var. Bergianum, known
as Karoo Buchu, which are reputed to yield an oil equalling that of
Barosma betulinum in value. In other quarters, however, leaves have
also been noticed of which the oil, by its odour, betrays a composition
differing materially from that of the ordinary buchu leaf oil. The leaves
of Barosma pulchella belong to the latter category. The leaves of Barosma
pulchella have an odour resembling that of citronella oil. The shrub is
a native of Cape Colony.
The leaves, on distillation, yield 3 per cent, of essential oil, having the
Acid number . 18-5
Ester ,, 27-2
„ ,, (after acetylation) 237
The oil contains citronellal, methyl heptenone, d-menthone, d-citron-

ellol, and a phenol in traces.
The leaves of Barosma venusta yield, according to Jensen,2 1*1 per
cent, of an oil, having the following characters :—
Specific gravity. 0-8839
Acid value 2-4
Ester „ . 13-4
,, ,, (alter acetylation) 52-8
Phenols . . . . 16 per cent.
The oil contains about 35 per cent, of a terpene, boiling at about 66'5°
at 15 to 18 mm., and having a specific gravity O790 and refractive index
1-4778.
On fractional distillation using a four pear-head, at a pressure of
15 mm., the results were as follows :—
No. Per Cent. Boiling-point. Optical Rotation. Refractive Index. Specific Gravity.
1 10 to 66-5° - 0° 25' 1-4785 0-796

2 [ 20 ,, 73° - 0° 45' 1-4815 0-817
3 20 „ 90° + 0° 30' 1-489 0-848
4 20 „ 96° + 2° 20' 1-508 0-945
5 30 over 96° 4- 0° 30' 1-5135 0-964
Separation was here not very successful, but the extremely low
density of the first fractions (portions being as low as O79), together
with similar boiling-point and optical inactivity, its instability, and the
1 8
Chemist and Druggist, 65 (1904), 506, 717. Pkar. Jour., 90 (1913), 60.
fact that its composition by combustion is equivalent to C10H16, all form
a very strong presumption that the olefine-terpene myrcene has here
been isolated, and that it in fact almost entirely constitutes the first 50 per
cent, of the oil; although it is much more prone to polymerization and
oxidation than when similarly obtained from bay oil. In the higher
fractions evidence was obtained of the presence of the allied alcohol
myrcenol and its acetate; also of methyl chavicol, anethol, and chavicol
or similar phenol, with sesquiterpenes.
No indications whatever of diosphenol were observed.
The oil of1 Barosma venusta has recently been examined by Goulding
and Eoberts.
The oil examined had the following characters :—
Specific gravity (15°) 0-865
Optical rotation . . . . . . . . . + 0° 47'
Acid value . . . . . . . . . . 5*6
Ester , , . . . 6-2
Corresponding with 2'2 per cent, of esters.
Ester value after acetylation 55
Corresponding with 15*7 per cent, of total alcohols, or 14-3 per cent.. of free
alcohols and 2*2 per cent, of esters.
On distillation, under atmospheric pressure, some decomposition oc-
curred, but when distilled under 60 mm. pressure a hydrocarbon having
the properties of myrcene was obtained, showing a great tendency to
resinify and combining with four atoms of bromine.
A small proportion of aldehyde was separated by shaking the oil with
solution of sodium hydrogen sulphite, separating and washing with ether
and extracting the aqueous solution with ether, after making alkaline
with sodium hydroxide. The aldehyde was identified as anisic aldehyde,
being readily converted into anisic acid melting at 183° to 184°. The
presence of linalol was confirmed in the fraction boiling at 190° to 205°
by oxidation to citral. No diosphenol was obtained, and only 0*2 per
cent, of phenol was absorbed by solution of sodium hydroxide after wash-
ing with sodium carbonate solution and sodium bisulphite solution to
remove acids and aldehydes. The small quantity of phenol extracted
gave no coloration with ferric chloride. Methyl chavicol was identified
in the fraction boiling at 213° to 218° byconversion into anethol, melting
at 22°, and confirmed by determination of the methoxyl group.
The residual fraction contained sesquiterpenes together with poly-
merides and decomposition products of myrcene.
The approximate composition of the oil is as follows :—
Percent.
Hydrocarbons, chiefly or entirely myrcene 43*0
Aldehydes, chiefly or entirely anisaldehyde 0*5
Phenols 0'2
Phenol ethers (methyl chavicol) . . . . . . .21*4
Alcohols partly linalol 14'3
Esters calculated as C10H17O .Ac 2-2
Sesquiterpenes loss, etc. (by difference) 18'4
The only important difference from the results of Jensen's investiga-
tion is the almost complete absence of phenols, which occurred in Jensen's
oil to the extent of 16 per cent., and gave a dark green coloration with
ferric chloride. This was presumed to be impure chavicol, although not
definitely proved. It should be pointed out, however, that Jensen's oil
1
Jour. Chem. Soc. Trans. (1914), 2618.
EUTACEJE 469
had a higher specific gravity (0*8839), and might, therefore, be expected
to contain more phenols.
Jensen's results were as follows :—
Per Cent.
Hydrocarbons (myrcene) 35
Phenols 16
Phenol ethers . . . . . . . . . . . 15
Alcohols . . . . . . . . . . . .1 5
Esters calculated a s linalyl acetate . . . . . . . 4
Aldehydes and ketones 4
Sesquiterpenes, etc. . . . . . . . . . . 11
l
J. C. Umney has recently received from Grahamstown a sample
of small leaves stated to be those of Barosma scoparia.
An examination of the leaves showed that they correspond very
closely with the leaves of Barosma venusta, which has already appeared
in commerce. The leaves are very small, about £ in. broad, and a little
longer, elliptical, obtuse in a few cases, but mostly obovate. They
certainly do not belong to the typical form of Barosma scoparia.
The essential oil possesses a characteristic, decidedly pleasant odour,
somewhat similar to Barosma serratifolia, and the oil shows no separation
of diosphenol. It has this feature in common with the oil of Barosma
venusta and also Barosma serratifolia, and for that reason may have less
medicinal value than the official buchu, Barosma betulina.
WEST INDIAN SANDALWOOD OIL.
This oil is not a true sandalwood oil, the misnomer having largely-
contributed to the substitution of this oil for the genuine sandalwood oil,,
and to its use as an adulterant of the latter.
It is distilled from the wood of Amyris balsamifera, which yields from
1*5 to 4 per cent, of oil. It is a thick, viscid yellow oil of pleasant odour
recalling that of cedarwood oil, with a secondary odour of true sandal-
wood oil, and has the following characters :—
Alcohols as G15H26O 30 to 55 per cent.
It is soluble in an equal volume of 90 per cent, alcohol.
It contains an alcoholic body which has been named amyrol, of the
formula C16H2fiO, or, according to Van Soden and Kojahn,2 a mixture of
two alcohols, having the following characters :—
1. 2.
Formula C16H26O C^HÔ
Specific gravity about 0'987 —
Optical rotation „ + 36° 0°
Boiling-point 299° below 299°
The oil also contains a lactone, amyrolin, of the formula CuH1203r
melting at 117°, d-cadinene, and /?-caryophyllene.
ANGOSTURA BARK OIL.
The bark of Galipea cusparia (Cusparia trifoliata) yields between 1
and 2 per cent, of essential oil. The tree is found in abundance on the
mountains in Venezuela, and it is especially plentiful in the country round
1
P. atid E.O.R. (1914), 373. « Pharm. Zeit.,46 (1900), 229.
about the Gulf of Santa Fe. The name angostura appears to have been
given to it on account of its having been found first in the district bear-
ing that name, situated on the Orinoco. The oil has the following
^characters:—
Acid value 1-8
Ester 5-5
It has been investigated by Beckurts and his pupils.1 In their
earlier investigations they obtained 1*5 per cent, of oil from the bark, of
specific gravity -956. More recently they obtained the same yield of oil
of specific gravity '941 at 20°, of optical rotation - 50°. The oil decom-
poses partially, when distilled under ordinary pressure, with the forma-
tion of water. A small portion was obtained boiling at 160°, and having
an odour resembling pinene. A small quantity of a terpene is thus
probably present. The main portion of the oil, however, distils between
260° and 280°. and consists of a sesquiterpene and a sesquiterpene
alcohol. The sesquiterpene, which is laevo-rotary, was originally de-
scribed under the name galipene, but has now been shown to be identical
with cadinene. The alcohol C16H16O is termed galipol ; it is a liquid of
specific gravity '927 at 20°, and is optically inactive. By the action of
dehydrating agents this body gives up water and yields cadinene. In ad-
dition to these bodies there is also present a small quantity of an inactive
sesquiterpene, and traces of a crystalline stearoptene. The oil is used to
a small extent, chiefly for the preparation of liqueurs, etc.
JABOBANDI LEAF OIL.
The leaves of Pilocarpus Jaborandi yield about 5 per cent, of an
essential oil having the following characters : —
Specific gravity ........ 0'8G5 to 0-895
Optical rotation . . . . . . . -f 1° ,, + 4°
It is soluble in 2 volumes of 80 per cent, alcohol. Its composition
is not well known, but the terpene dipentene has been identified, and
also a crystalline hydrocarbon, belonging to one of the unsaturated series.
The latter body sometimes occurs to so great an extent that the oil solidi-
fies on cooling. It also contains methyl-nonyl ketone.
OF EVODIA EUT^CARPA.
The essential oil distilled from the fruit has been examined by
Asahina and Kashiwuki.2 The authors have isolated from it a ter-
pene which they believe to be different from any of the known terpenes,
and which they have named evodene. It is a colourless liquid boil-
ing at 67° (20 mm.), with a sharp odour, and has the characters of an
aliphatic terpene of the formula C10H16. It has a specific gravity of
0-799 and refractive index 1*4843. On treatment with plantinum
black it is converted into dimethyl-octane. It resembles the olefinic
terpenes myrcene and ocimene, but differs from them in forming a
liquid tetrabromide after reduction to dihydro-evodene. A crystalline
substance melting at 278° has also been isolated from the fruit, which the
1
Arch, der Pharm., 237 (1897), 518 and 634 ; 236 (1898), 392 ; 229 (1891), 612.
- Jour. Pharm. Soc. Japan, November, 1915.
ZYGOPHYLLACEÊ 461
authors have termed evodiamine. On heating with alcoholic potash it
yields a base C11H10N2 and methyl-anthranilic acid. Its formula is
stated to be C19H17N3O.
In reference to the name " evodene," it should be mentioned that
Semmler and Schorsberger had previously used the same name for a
terpene which they isolated from the oil of Xanthoxylum aubertia.
OlL OF TODDALIA.
Toddalia aculeata (Toddalia asiatica) is a tree growing wild in the
Nilgiri mountains, and is also found in the Philippine Islands. It is
known as the wild orange tree. The leaves yield O08 per cent, of es-
sential oil, which, according to Brooks,1 has an odour of camphor and
lemon-grass. Its characters are as follows : —
30°
Specific gravity ........ 0-9059 at — 0
Refractive index ........ 1-4620 „ 30°
It contains linalol to a considerable extent, and about 18 per cent.
of a substance resembling camphor and melting at 97°.
OIL OF PELEA MADAGASCARICA.
The leaves and fruits of Pelea Madagascar 'ica, a Malagasy shrub,
yield about 4 to 5 per cent, of essential oil having a powerful aniseed
odour.- It is yellow in colour and has the following characters : —
Specific gravity . . . . . . . . . 0*953
Optical rotation . . . . . , . . + 32° 22'
Refractive index ......... 1 '51469
It contains anisic aldehyde, but not much anethol, since it does not
congeal even at - 18°.
OIL OF CLAUSENA ANISUM-OLENS.
The leaves of Clausena Anisum-olens, a plant growing in the Philip-
pines, yield about 1-2 per cent, of an essential oil having a powerful 2odour
of Eussian aniseed oil. The oil has been examined by Brooks, who
found it to have the following characters : —
30°
Specific gravity at —— ........ 0 963
30
Optical rotation . . . . . . . . . . 0°
Refractive index at 30° ........ 1-5235
Saponification value . . . . . . . . .3-6
The oil contains 90 to 95 per cent, of methyl-chavicol.
ZYGOPHYLLACEyE,
GUAIACUM WOOD OIL.
This oil is identical with that which used to be offered in commerce
under the name of champaca wood oil. As a matter of fact neither name
can be regarded as correct. The wood from which the oil is distilled was
formerly believed to be that known as Palo balsamo or guaiacum wood.
It was originally believed to be the product of Guaiacum officinale, but it
is now clearly settled that it is the product of Bulnesia sarmienti, and is
1
Philipp. Jour. Sc. (6), 333. 2 /^^ 6 (ign), 344.
462 THE GHEMISTEY OF ESSENTIAL OILS
known as Palo santo (holy wood) to the natives. It appears to be indi-
genous to Argentine and Paraguay, and is especially plentiful along the
•course of the river Eio Bermejo, a tributary of the Eio Paraguay. The
wood yields from 4 to 8 per cent, of essential oil, which is practically solid
at ordinary temperatures. This oil has an exceedingly delicate tea odour,
and is well suited both for soap perfumery and for blending with stronger
perfumes for ordinary scents. The oil, which is of a hard semi-solid con-
.sistency, has the following characters :—
Specific gravity 0-965 to 0*975 at 30°
Optical rotation . - 3° to - 8°
Refractive index 1*5030 to 1-5050 at 30°
Acid value . . . . . . . . 0 to 2
Ester „ 0 „ 5
,, „ (after acetylation) . . . . 100 „ 150
The oil is soluble in 3 to 5 volumes of 70 per cent, alcohol. It melts
at from 42° to 50°.
The only constituent yet ascertained has been examined by Wallach
and Tuttle.1 It is a crystalline alcohol of the formula C15H26O, which is
termed guaiol. This body is identical with that found by Merck and
named by him champacol, believing that the wood was really champaca
wood. Guaiol melts at 91°, boils at 288° under ordinary pressure, and at
155° under a pressure of 13 mm., and is laevo-rotatory. By heating it
.with zinc chloride it yields a blue oil, of specific gravity *910 at 20°, and
which appears to be a sesquiterpene. An acetate of the alcohol has been
prepared, which boils at 155° under a pressure of 10 mm. In addition to
its legitimate use as a perfume, it is sometimes used as an adulterant of
otto of roses. It is usually mixed with geranium oil, so as to have the
same congealing-point as otto of roses, and is then used under the name
•" essence de la gai'ac & la geranium ".
ANACARDIACE/E,
OIL OF MASTIC.
The resin from Pistacia lentiscus, the mastic tree, an inhabitant of
Southern Europe, North Africa, and the Levant, which is known as
mastic, consists of a mixture of resins and resinoids, with about 1 to 3 per
cent, of volatile oil. This oil, which has a characteristic, pleasant odour,
Specific gravity . . ^ 0*850 to 0'903
Optical rotation . .' -f 22° „ + 35°
Acid value 0 „ 5
Ester „ 3 „ 19
The oil contains d-pinene as its principal constituent, with a small
amount of fc-a-pinene.
OIL OF CHIAN TURPENTINE.
This oil is the product of distillation with water, of Chian turpentine,
the resin of Pistacia terebinthus, an inhabitant of Syria and the Greek
archipelago. The yield is about 15 per cent, of an oil of the following
characters:—
1
Annalen, 279 (1894), 395.
ANACAKDIACEJE 463

Optical rotation . . + 12° „ + 20°
It consists almost entirely of a-pinene.
OlL OF SCHINUS MOLLE.
Schinus molle is a native of America and is widely distributed in
^Bolivia, Chili, Peru, New Granada, and Mexico. It is very commonly
known as the American pepper plant.
^ It is also met with in Uruguay and the southern regions of Brazil,
the provinces of San Paulo and Eio Grande do Sul.
It is extensively cultivated in Senegal, in Teneriffe, and in the whole
of the Mediterranean regions. It ornaments numerous gardens in Pro-
yence in the neighbourhood of Nice, and is also much cultivated in Algeria
where it is very widely distributed.
Eoure-Bertrand Fils1 have examined two essential oils of Schinus,
obtained from Algeria (Saint-Denis du Sig) in order to compare their con-
stants with those of an essential oil prepared from the plant cultivated at
Grasse. One of the Algerian oils was obtained by the distillation of en-
tire branches, leaves, wood, and fruits, and the other by the distillation of
the leaves only.
Schinus molle is a tree of small dimensions with small dioecious
flowers, carried on articulated peduncles disposed in bunches. The calix is
small, with five lobes more or less cut off, with quincuncial praefloration.
The corolla has five petals, much longer than the sepals, inserted on a
disc; they are erect at first and spread out later on.
Samples of the oil distilled in Mexico have been examined by
Schimmel & Co.2
These oils had the following characters:—
Algerian Oils. French Oils Mexican Oils.

from Grasse.
Entire Leaves. Entire Leaves. Fruit. Unknown.

Branches. Branches.
d16o . 0-8634 0-8658 0-8696 0-8583 0-8600 ! 0-8492

ao + 50° 54' + 65° 20' + 46° 13' + 44° 50' + 42° 30' j +56° 27'
'Ml>200 ~ 1-47665 1-47909 i 1-47616
Acid Number . 0-7 2-1
Ester Number 5-5 3-4 8-2 7-2 25-2 —
Ester Number after 56-5
Acetylation . 29-4 40-4 43-4
— with absolute; alcohol
Even —
Solubility in 90 perl 10 vols.
5 vols. 5 vols. with the solution, at first clear,
cent. Alcohol j turbidity becomes turbid when more
alcohol is added
The oil contains a-pinene, Z-phellandrene, caroacrol, a crystalline

body melting at 160°, and possibly a sesquiterpene.
OIL OF EHUS COTINUS.
This oil was first obtained from the young twigs of the tree by Perrier
and Fouchet,3 who obtained 0*1 per cent, of the oil, which was known
as "oil of fustic ". The oil had the following characters :—
1
Bulletin, April (1909),
s
29. * Report, April (1908), 121.
Bull. Soc. Chem., iv. 5 (1909), 1074.
Acid number . . . . . . . . . . 6*1
Ester value 28-2
A sample examined by Schimmel & Co.1 had the following characters :—
Acid value O'J
Ester „ 20-4
The oil consisted almost entirely of terpenes, of which /?-pinener
limonene, and dipentene were detected with certainty. No other con-
stituent has been identified.
OIL OF HEERIA PANICULOSA.
The berries of Heeria Paniculosa, a plant indigenous to Zuzuland r
known to the natives as Isifeku, yield from 4*5 to 6 per cent, of essen-
tial oil, which has been examined by Juritz.2 A sample examined in
the Imperial Institute Laboratories had the following characters :—
Ester value 4'2
Acid value 1-6
,, , , (after acetylatioii) . . . . . . . 14*8
The oil consists mainly of terpenes.
BURSERACLVE.
OIL OF MYRRH.
Myrrh is an oleo-resinous substance obtained as a secretion in the
parenchyma of the bark of various species of Commiphora. The so-
called true myrrh, or Herabol myrrh, is collected principally in Arabia
and Somaliland, whilst Bisabol myrrh, or bdellium, occurs as an ad-
mixture of true myrrh, especially when collected in Somaliland, and is
identical or closely related to Indian bdellium.
Herabol Myrrh is chiefly derived from Commiphora myrrha, and
yields from 3 to 10 per cent, of a thick, yellow essential oil, having the
Acid value 1 „8
Ester „ 15 „ 45
It is soluble with, at most, slight turbidity, in 10 volumes of 90 per
cent, alcohol.
Lewinsohn 3 emphasises that the composition of myrrh oil differs
according to the origin of the resin, the method of production, and the
age. He believes that distillers add small quantities of alkali to tlê
1 2
Report, April (1913),
3
86. Chemical News, 1920, 120, 277.
Arch, der Pharm., 244 (1906), 412.
BUESEKACE^l 465
resin after no more oil passes over for the purpose of obtaining a larger
yield, and the distillation is then continued. The constituents of myrrh
oil identified by him are : cuminic aldehyde, C10H12O (up to 1 per cent.),
boiling-point 116° (12 mm. pressure); oxime, melting-point 56°; semi-
carbazone, melting-point 201°.—Acids: Of these, only acetic acid and
palmitic acid (melting-point 62°) were detected with certainty. Both are
present in old oils in the free state, whilst freshly distilled myrrh oil
contains the acids as esters.—Phenols (about 1 per cent.): eugenoll
(about 0*23 per cent. ; benzoyl compound, melting-point 69°), and a
small quantity m-cresol were detected.—Hydrocarbons: Fractional dis-
tillation over sodium yielded four hydrocarbons (terpenes) of the formula
C10H16 (all of which, however, were not found in every oil examined), of
which three were identified ; pinene (nitrosochloride, melting-point 103°;
nitrolbenzylamine and nitrolpiperidine) ; dipentene (tetrabromide, melt-
ing-point 124°); limonene (tetrabromide, melting-point 104°); the fourth
hydrocarbon probably belongs also to the limonene group (ao + 80°,
tetrabromide, melting-point 115°, and monohydrochloride, melting-point
6°) but could not be identified. Sesquiterpenes : probably cadinene is,
present, and a second sesquiterpene of specific gravity 0'911 at 21°, and
optical rotation -f 30*4°.
Friedrichs l distilled an oil from picked myrrh, which had the follow-
ing characters:—
Refractive index 1-5359'
Acid number 6-15
Ester ,, . . .
No eugenol could be detected, but meta-wesol was present. Cumic
and cinnamic aldehydes were also found to be present. A sesquiterpene
having the following characters was also isolated:—
Molecular refraction 64-98
To this body he assigns the name herabolene.
Traces of formic and acetic acids were also found, and a non-volatile
acid melting at 159°, and an acid of the formula C16H21O3 . COOH,
melting at 236°, which he names myrrholic acid.
Bisabol Myrrh.—The principal plant yielding this resin is probably
Commiphora 2erythraea.
Tucholka has extracted the essential oil from a Bisabol myrrh coming
from the interior of the Somali country, by removing it from the alcoholic
solution of the resin by means of petroleum ether. The oil was purified
by steam distillation, and then had a light yellow colour, specific gravity
•8836, and optical rotation - 14° 20'. It boiled at ^20° to 270°. The
yield was 7*8 per cent. By means of dry hydrochloric acid gas, a crys-
talline hydrochloride was separated, which, on treatment with boiling
acetic solution of sodium acetate, set free a hydrocarbon which the above-
named investigator terms bisabolene. This hydrocarbon had a specific
gravity -8914 and boiled at 260°. The same chemist suggests the unlikely
formula C50H9(3O for the residual portion of the oil.
1 2
Arch, der PJwrm., 245 (1907), 427. Arch. Pharm., 235, 289.
VOL. i. . 30
OIL OF OPOPANAX.
The oil from the true opopanax has not been investigated, and the
botanical source of the gum-resin is unknown. It is almost certainly
derived from an Umbelliferous plant—but not Opopanax chironium as
usually stated. The commercial product known as oil of opopanax is
derived from the exudation of Commiphora erythrcea, var. glabrescens,
which is possibly identical with bisabol myrrh. Samples of the oil have
Specjfic gravity 0-870 to 0'905
Optical rotation 1-4890 „ 1-4940
Acid value 0 ,, 3
Ester „ 7 „ 20
,, „ (after acetylation) 40 ,, 55
The oil is soluble to an almost clear solution in 1 to 10 volumes of 90 per
cent, alcohol.
The only constituents so far identified are the sesquiterpene bisabolene,
and a sesquiterpene alcohol boiling at 135° to 137° at 2 mm. pressure.
OIL OF FRANKINCENSE.
This oil is distilled from the resinous exudation of various species of
Boswellia, principally Boswellia Carterii. The yield of essential oil varies
from 5 to 10 per cent.
It is a colourless or pale yellow liquid of balsamic odour, having the
Specific gravity 0*875 t o 0-894
Optical rotation . • . . . . . . .4-15° , +30°
Refractive index . 1-4725 , 1-4825
Acid value . . . . . . . . . 0 , 4
Ester „ 5 , 20
,, , , (after acetylation) . . . . . 40 , 50
It is soluble in 4 to 8 volumes of 90 per cent, alcohol, sometimes with
-turbidity.
Up till about ten years ago, this oil was found to be laevo-rotatory,
flbut apparently the species of Boswellia from which it is obtained have
recently been varied, as the oil is almost always dextro-rotatory now.
'The laevo-rotatory oil contains a-pinene-dipentene, phellandrene, and
<cadinene.
The dextro-rotatory oil has recently been examined by Schimmel &
Co.1 The oil examined by them had the following constants : d150 0-8775,
«D + 19° 18', ^D2o° 1'47245, acid value 1*8, ester value 7*5, ester value after
acetylation 106*0, soluble in up to 2 volumes of 90 per cent, alcohol, the solu-
tion being clear at first, and turning turbid after two volumes. Of the ter-
penes, 92 per cent, boiled between 156° and 161°, about 5 per cent, between
161° and 163°, and about 4 per cent, between 163° and 181°. In the
fractions boiling between 156° and 157° (d15o 0*862 to 0*863 ; aD + 30° 58')
they established the presence of i- and d-a-pinene from the nitrosochloride
and the nitrol piperidide (melting-point 118°), as well as by oxidation into
pinonic acid (boiling-point 170° to 175° at 7 mm.; melting-point of the
active acid 69° to 70°; of the inactive acid 104°). The presence of cam-
phene in all the fractions boiling betwreen 158° and 164° was established
fey conversion into i'soborneol, melting-point 210° to 211°. Dipentene
1
BUKSEKACE^ 467
•was identified by its tetrabromide, and âra-cymene by oxidising with
potassium permanganate to ^-hydroxy-isopropyl benzoic acid.
Fromin and Antin l isolated from this oil a (ketonic ?) alcohol, of the
formula C10H16O, boiling at 210° to 211°. This body has been named
olibanol. Esters of borneol were also detected.
Bosivellia serrata, a closely-related plant, is a native of North-west
India, and yields a gum resin which is collected twice a year in the Punjab.
It is employed'by the natives in the treatment of rheumatism and nervous
disease, and is an ingredient in certain ointments. In Gujerat it is burnt
as incense in religious ceremonies. Experiments have been conducted at
the Forest Kesearch Institute, Dehra Dun, with a view to determining
the best method of treating the crude gum resin in order to obtain the
essential oil, resin, and other products. The gum and impurities were
first separated from the resin and oil by treating a quantity of the raw
product in a false-bottomed copper still and passing steam through the
mass. The resin and most of the oil passed through the false bottom,
leaving the gum and impurities above. The oil was then separated from
the resin by steam distillation, and the resulting oil fractionally distilled
up to 155° C. yielded an oil consisting almost wholly of dextro-pinene,
and a portion consisting mostly of limonene or flipentene. Samples of
these were examined at the Imperial Institute.2 The oil distilled princi-
pally between 153° and 160°, had specific gravity 0*8446, optical rotation
-h 31° 24', ester value 2*6, ester value after acetylation 36*4. It readily
dissolves resins such as colophony, dammar, sandarac, and soft copal, but
varnishes thus prepared dried more rapidly than those made with com-
mercial turpentine, and gave a rather less lustrous surface.
OIL OF ELEMI,
And other Canarium Species.
The elemi of commerce is the balsamic exudation of Canarium
luzonicum, the Manila elemi, which is produced entirely in the Philippine
Islands. Many other species of Canarium yield similar products, which,
however, are scarcely commercial articles.
Manila elemi yields from 15 to 30 per cent, of essential oil, whose
odour is largely that of phellandrene. The oil has the following char-
acters :—
Optical rotation 30° to + 55° (rarely + 4° to + 131°)
Acid value 0 „2
Ester ., 4 „ 10
The oleoresin is produced in a manner similar to that used for the
collection of turpentine, 3and is then steam distilled.
According to Clover, the oil is very variable in character and com-
position. He has examined twenty-one different samples of authentic
origin, and divided them into the following groups :—
1. Ten samples consisted of practically pure d-limonene.
2. Nine samples contained phellandrene, associated with either
pinene or limonene.
l
Annalen, 401 (1913), 253. * Bull. Imp. Inst., xiii., 3, 351.
*Amer. Chem. Jour., 39 (1908), 613.
3. Two samples consisted of (a) practically pure terpinene ; (b) prac-
tically pure terpinolene.
The presence of terpinolene had hitherto not been observed in nature,
and is remarkable as the oil containing terpinolene showed a very peculiar
behaviour. The crude oil boiled within one degree (Clover does not men-
tion the boiling-point), and had a rotation of + 4°. The reactions for
terpinene and phellandrene were negative, but a bromide of the melting-
point 116° to 117° was obtained in the form of brilliant scales. From
this the presence of terpinolene might be assumed. The oil containing
terpinolene was purified by treatment with potassium hydroxide, distilled
in vacuo, and had then the constants : specific gravity at ^Qo 0*8361; rota-
tion + 1-7°; 7iD30o 1*4701; boiling-point 173*5° to 175° (at ordinary
pressure); 80° to 81° (37 mm. pressure). The rotation decreased con-
siderably between the second and third distillation, although the oil had
been prepared only on the previous day from elemi. In order to accel-
erate a possible change in the principal constituent of the oil, a portion of
it was heated for three hours in a sealed tube on an oil-bath to 200°.
The distillate now showed a rotation of — 7*5°, and gave a phellandrene
reaction (nitrite, laevo-rotatory, melting-point 119° to 120°). Five days
later an attempt was made to produce terpinolene tetrabromide from the
purified oil, but instead of this there were obtained crystals of the melt-
ing-point 125°, which were dipentene tetrabromide. In the meantime
the rotation of the oil had also changed from + 1*7° to - 1*6°; after
a further six days it had increased to - 9*8°; after another month to
- 34'5°, a proof that a considerable alteration was proceeding spontane-
ously in the oil. After three more weeks the oil was distilled with steam ;
the distillate now had an optical rotation - 38°, and the conversion had
consequently probably come to an end. The tetrabromide produced in
various solvents melted at 125°. Phellandrene could no longer be de-
tected by the nitrite-reaction, probably owing to the presence of a large
quantity of dipentene. In Clover's opinion the almost pure terpinolene
present in the original oil (which had a particularly low boiling-point),
. had consequently been converted, by standing for several weeks, into
dipentene, a small quantity of ^-phellandrene, and an unknown laevo-
rotatory terpene.
The high-boiling oil portions had mostly a feeble laevo-rotation, and
their specific gravities fluctuated between 0-900 and 1*030; they were
chiefly mixtures of sesquiterpenes and oxygenated bodies. From a frac-
tion with the rotation + 71*6° a solid substance of the formula C15H26O
was isolated.
In the case of phellandrene, Clover observed that the a-modification
of this terpene occurs in elemi oil. The rotation of the phellandrene
diminished slowly if left standing at ordinary temperature. When the
phellandrene was left standing, crystals separated on the glass walls of
the bottle, the formation of which must be attributed to autoxidation of
the phellandrene; after purification from hot acetic ether they melted at
164-5° to 165*5°, and had a composition corresponding to the formula.
CioH18O2. l
Semmler has detected a small quantity of a sesquiterpene alcohol,
and a phenol ether to which he assigned the name elemicin. This body
has a specific gravity 1*063 at 20°, refractive index 1*5285, and boils at
144° to 147° at 10 mm.
l
Berichte, 41 (1908), 1768, 1918, 2183, 2556.
BUBSEKACEJE 469
Elemicin is allyl-trimethoxy-3'4:-5-benzene. Bacon1 has examined
numerous samples of the oil, and his results differ somewhat from those
of Clover, thus emphasising the variable character of the oil. He only
found two samples to contain <i-limonene out of sixty-two obtained from
the district of Calaoag, whilst six out of nine from Gumaca contained this
terpene. Bacon considers that /^-phellandrene is sometimes present in
the oil.
Semmler and Liao 2 have isolated the sesquiterpene alcohol of this oil
and find it to boil at 152° to 156° (at 17 mm.) and to have a specific gravity
0-9411 at 20°, optical rotation - 5°, and refractive index 1-5030. They
have termed this body elemol. It yields a sesquiterpene, elemene, on
dehydration.
An Elemi oil from Southern Nigeria has been found to contain much
phellandrene and to have a specific gravity 0*8686 and rotation -f- 50° 30'.
Uganda Elemi, from Canarium Schweinfurthii, yields about 11 per
cent, of essential oil of specific gravity 0-8451 and optical rotation + 79°
20'. It contains much phellandrene.
Mauritius Elemi, from Canarium Colophania, yields 16 per cent, of
essential oil of specific gravity 0*859, optical rotation + 3° 13', and re-
fractive index 1-4725.
Canarium villorum* another Philippine variety of elemi, yields an oil
of specific gravity 0*8627, optical rotation + 11° 3', and refractive index
1*47245. It contains much ^-cymene, and the terpenes a-pinene and di-
pentene.
Canarium micracarpum, from the Moluccas, is a very soft oleo-resin,
yielding about 80 per cent, of oil of specific gravity 0*920 to 0-930, and
optical rotation + 2° to - 52°.
Canarium euptoron is the principal species yielding " Lagam " balsam
in the Dutch Indies. The oil 4 has a specific gravity 0-905 to 0*912,
optical rotation about - 8°, and refractive index 1*4972. It consists5
chiefly of caryophyllene, with a little caryophyllene alcohol. Samples
distilled from a balsam of the same name, but obviously of different
origin, had specific gravities of 0-882 to 0*883 at 26°.
It is possible that Lagam balsam is not really the product of Canarium
euptoron, but of a Dipterocarpus species.
An oil from Cameroon Elemi6 has been found to have a specific
gravity 0*953, and is materially different from all other elemi oils ex-
amined.7
West Indian Elemi oil is distilled from Dacroydes hexandra, one of
the Burseracese. The yield of oil is about 16 per cent., the oil having
a specific gravity 0*8875 and optical rotation - 13° 20'. More found
a-pinene and Z-sylvestrene in the oil. The presence of the latter terpene
has been confirmed by Schimmel & Co.8
MEXICAN LINALOE OIL.

The linaloe oil of commerce is distilled in Mexico, and also in Europe,
from several species of Bur sera, mainly from the wood, but also to some
1 2
Philipp. Jour. Sc., 4 (1909), 93. Berichte, 49 (1916), 794.
3
Schimmel'8 Bericht, October (1907), 24. * Arch, der Pharm., 250 (1912), 199.
*Jaarb. dep. Land. Ned. Indii. (1909), 66, 81.
7
« Pharm. Zeit., 58 (1913), 774. Jour. Chem. Soc., 75 (1899), 718.
8
Report, April (1914), 51.
extent from the fruit. The principal species used for distillation are
Bursera Delpechiana and Bursera aloexylon. Possibly Bursera glabri-
folia and Bursera fagaroides are used to a small extent. The wood is
known locally as "Bois de citron du Mexique". The oil is not to be
confused with the so-called Cayenne linaloe oil, which is derived from an
entirely different species.
According to Dr. Altamirano,1 Mexican linaloe oil is obtained from the
districts Oaxaca, Puebla, Guerrero, Morelos, and Michoacan down to
Colima. The two trees which are or have been the principal source of
the oil are known as "Spanish linaloe" and " copal limon". The
former is now nearly eradicated, but the latter still flourishes abundantly..
The natives distinguish three kinds according to the external appear-
ance and odour : fine, common, and caraway linaloe. Fine linaloe has a
very delicate and pleasant odour, the common kind less so, and the third
resembles caraway. The wood of the linaloe tree is said to be more com-
pact than that of the copal limon, which is more spongy. The oil which
is met with in commerce is chiefly obtained from the wood of copal
limon. This tree is very hardy and grows even in very stony soil;
although it can most easily be propagated from cuttings, nobody thinks
of planting it. The young trees, however, can only be made use of for
oil production after about twenty years. It is said that during the last
few years oil has frequently been placed on the market which consisted
of a mixture of oils obtained from the wood and from the fruit. The
fruit is ripe in September, and forms fleshy, greenish to reddish berries
of the size of a Spanish pea (garbanzo}. The yield of oil from the fruit
(which is distilled from July to September) amounts to 3 per cent. The
fruit is gathered by stripping it off with a very sharp crescent-shaped
instrument, care being taken to damage the fleshy part of the berries as
little as possible ; the oil obtained in the distillation possesses a herbaceous*
odour, and resinifies very readily. For this reason it is not sold as such,
but is mixed with the oil obtained from the wood, which keeps better.
In order to increase the quantity and improve the quality of the oil, the
Indians used to submit the fruit before the distillation to a kind of fer-
mentation during which the herbaceous odour disappears, by placing the
undamaged fruit in cases well covered with sacks, and keeping it thus for
three to four days at a constant temperature so as to let the fruit mature..
The oil from the wood is best obtained from trees which are quite
old—forty to sixty years; in the case of young trees it is endeavoured to-
increase the oil-content by cutting notches in the tree, upon which an
increased formation of oil takes place, which may be regarded as a patho-
logical product. The tree is treated so that strips 16 ins. long and 8 ins,
wide are cut out of the bark and the wood, down to a depth of 2 ins., and
running parallel, or preferably slanting, to the direction of the trunk. If
it is now found that the tree has a " heart," i.e. yellowish, highly aromatic
wood, it can be used at once for distillation. If the tree has no " heart,"
it is left standing with open wounds so that it may develop "heart ",
With a view to this, the upper extremity of the notch is cut to a point,
in order that the rain water may run alongside, but,the lower edge is
bevelled off in such manner that no foreign material can collect there
which would set up decay. If, in spite of this, the wood should com-
mence to rot, the part is at once planed off, so as to arrest the injury
which otherwise would cause a cessation of the oil formation. If no
1
Report of the Inst. Med. Nac. Mexico (1904), Jan.-Mar., and Schimmel's Report.
BUKSEEACEÊ 471
interruption takes place, the change in the coloration of the wood be-
comes apparent already after a few days; after the lapse of a month a
large portion of the previously white and soft wood has been transformed
into yellowish, hard, and much more aromatic wood. The Indians were
led to this operation by the observation that cut-off linaloe roots frequently
contained so much oil that it could be pressed out with the fingers, and
that trees from which branches had accidentally broken off through gales,
formed much oil, and had changed after many years. The operation,
which has the effect of converting trees poor in oil into trees rich in oil,
is carried out in April and September. The April cut is not so effective
as the September one, as the individual trees in both cases only " mature "
(i.e. run to sap) in the month of January. In October to November the
trees drop their leaves. The distillation of the wood, for which only the
trunk is used, is carried on in the most primitive manner, chiefly from
December to June. The smaller distillers are partly still absolutely wild
Indians who do not speak Spanish; actual factories are not yet in ex-
istence, which is probably due to the difficult conditions of life in the
linaloe districts, where vermin abounds, and where among the Indians
contagious diseases such as leprosy, etc., prevail. The yield of oil ob-
tained in Mexico from the wood amounts at most to 2'5 per cent. The
production of Puebla is said to yield annually about 4000 to 5000 kilos.
The oil is put up in kerosene tins containing 35 to 37 lb., of which two
are packed in a case.
The still, arranged for heating by direct fire, is (according to Schimmel
& Co.), like the other parts of the apparatus, with the exception of the
copper conical head, made from galvanised sheet-iron; it is about 5 ft.
high, and has a diameter of 45 ins. At the lower part of the still an iron
tube has been arranged, which is closed with a wooden plug wrapped up
in banana leaves, and by means of it the water can be drawn off when
the distillation is completed. The removable head, which is provided
with means for cooling, is connected by two tubes with the condenser
proper; pails or kerosene tins serve as receivers.
The still is usually built near a mountain stream. The cut wood is so
filled into the still (about 5 cwt. of chips) that a space of about 10 ins. from
the top of the still is left empty. Water is then added so that the wood
is well covered, and a space of about 7 ins. from the top is left empty.
The wood when distilled in Europe yields from 7 to 9 per cent, of
oil, but whether this is due to better methods of distillation or to an after
development of oil in the wood is a matter of uncertainty.
The oil was investigated by Verneuil and Poisson, who stated that it
distilled almost entirely between 189° and 192°, and that it consisted1
mainly of an oxygenated body of the formula 2(C10H8)5H2O. Semmler,
however, was the first to discover the true odorous principle of the oil,
which he termed linalol. In addition to this alcohol, geraniol and d-ter-
pineol and the ketone, methyl-heptenone, have been found in the oil,
together with traces of a sesquiterpene and two terpenes. Barbier and
Bouveault give us the composition of an oil examined by them :—
Linalol 90 per cent.2
Geraniol . . . . . . . . . . 2
Sesquiterpene 3
Methyl-heptenone 0*1
Terpene (1) O'l
„ (2) 0-1
1 3
Berichte (1891), 207. This figure is too high.
Schimmel & Co. have isolated dextro-a-terpmeol from the oil, and
also an alcohol not previously found naturally, which they identified as
methyl-heptenol.1 This body has the following characters :—
Refractive index 1 -44951
Schimmel & Co. in 1908 isolated a body possessing the formula
C10H18O2 from this oil. They have since identified 2it as linalol monoxide,
Identical with the body prepared by Prileshaeff by the oxidation of
linalol by means of benzoyl hydrogen peroxide.
Linalol monoxide is somewhat viscous and is also clearly differentiated
from linalol by its mouldy odour, which recalls that of fenchyl alcohol
and of camphor. As its boiling-point is only 3° to 4° lower than that of
linalol, it is impossible, in view of the very small extent to which it occurs
in the oil, to prepare it in the pure form by fractionation. It is, however,
possible to obtain ID pure, although at a considerable loss of material, by
repeatedly oxidising the fractions containing linalol of high specific gravity
ivith 0*5 per cent, permanganate solution at ice temperature, each time
driving off the unattacked oil with steam. It also appears to be possible
io accumulate the compound by treating the fractions in question with
glacial acetic-sulphuric acid at 40° to 50° for several hours. From the
formation of esters, it is clear that the body C10H18O2 is an alcohol. Its
acetic ester, of which the odour differs altogether from that of linalyl
acetate, boils between 60° and 65° (4 mm.), and its benzoic ester between
157° and 160° (3 to 43 mm.). These chemists have also isolated the
hydrocarbons octylene (previously found in bergamot oil by Burgess and
Page 4) and nonylene from the oil. An oleginic terpene is also present,
possibly identical with myrcene.
Linaloe oil is a colourless or pale yellow oil of sweet, soft odour, that
of linalol predominating. It has the following characters:—
Optical rotation . - 3° to - 15° (sometimes dextro-rotatory to + 8°)
Refractive index . 1-4590 to 1-4655
Acid value . 0 ,, 6
Ester ,, 5 „ 75
The oil is soluble in 3 volumes of 70 per cent, alcohol, or in 4 to 5
volumes of 60 per cent, alcohol.
Occasionally pure oils will be found which vary outside these limits.
Thus, oils with a high content of linalol oxide may have a specific gravity
of 0*900 or even a little over. Oils with a high ester value naturally
contain less free linalol.
The amount of free linalol is the most important feature of the oil.
Its actual determination is difficult, if not impossible, on account of the
ease with which it decomposes under the action of acetic anhydride.
Boulez's modification of the usual acetylation process, however, yields
approximately correct results.
A fractional distillation is most useful, and will give a good indication
of the amount of linalol present. The following results were obtained on
fractionating four pure samples, by the author and C. T. Bennett :—
2
iBerichte,
3
October, 1908, 78. 4
/6id.,
42 (1912), 4811.
Schimmel's Report, April, 1909, 67. Jour. Chem. Soc., 85 (1904), 1327.
BUBSEBACEJE 473
No. 1.
No. Specific Gravity. Optical Rotation. Refractive Index.
1 10°/0 0-868 - 11° 1-4580

2 20% 0-870 - 11° 30' 1-4590
3 20°/ 0 0-871 - 13° 1-4605
4 20% 0-872 - 13° 1-4612
5 20% 0-876 - 12° 1-4620
6 10% 0-913 — 1-4750
(residue)
No. 2. No. 3. No. 4.

, No.
Specific Optical Specific Optical Specific Optical
Gravity. Rotation. Gravity. Rotation. Gravity. Rotation.
1 10% 0-870 - 10° 30' 0-872 - 11° 40' 0-871 - 12°

2 20% 0-870 - 10° 20' 0-871 - 11° 30' 0-871 - 13°
3 20% 0-871 - 10° 40' 0-873 - 12° 0-873 - 13° 20'
4 20% 0-873 - 10° 10' 0-874 - 11° 50' 0-874 - 11° 50'
5 20% 0-877 - 9° 40' 0-876 - 11° 10' 0-876 - 10° 30'
6 (residue) 0-909 — 0-914 — 0-912 —
The characters of the original oils were as follows :—
No. Specific Gravity. Optical Rotation.
1 0-882 - 11°
2 0-882 - 10°
3 0-877 - 11° 30'
4 0-879 - 12° 10'
Schimmel gives the following figures for two dextro-rotatory oils : —

Oil I. : d15o 0-8816 ; ad + 6° 3' ; acid number 1-7 ; ester number 20'0 ;
1*46209 ; soluble in 1*6 and more volumes 70 percent, alcohol, On
distillation in vacua there passed over :—
No. Pressure. Temperature. Per Cent. Optical Rotation. Remarks.
1 4 mm. up to 66° 8-5 ad + 6° 30'

2 4 „ 66 , 67-5° 23-5 Od + 8° 18'
67-5, 68° 32-1 ad+ 9° ) linalol
3 4 „ [ fraction ;
4 5 „ 73 , 76° 17-0 aa+ 7° 30'
5 5 „ 76 , 82° 2-1 ad+ 3° 20'
6 5 „ 82 , 96° 8-7 ad - 10° 5'
Oil II. : dl5o 0*8783 ; ad + 8°; acid number 1*4 ; ester number 3*5;
nd2QO 1*46149 ; soluble in 2'0 and more volumes 70 per cent, alcohol. On
distillation in vacuo the following passed over:—
No. Pressure. Temperature. Per Cent. Optical Rotation, i Remarks.
1 10 mm. 60 to 86° 4-5 ad + 5° 24'

2 10 86 90° 9-0 ' ad + 8° 50' | lina]ol
3 10 90 91°
4 14 95 97° fraCti n
51-0 £ + 11° 15'' [ °
5 14 97 100° 5-0 arf + 8°
6 14 100 110° 3-0 ad - 11°
7 14 110 120° 3'0 ad - 18° 20'
The oil is sometimes adulterated with fatty oils, which raise the
specific gravity, yield a high ester value, and are not volatilized on a water-
bath.
Shiu oil, an oil distilled in Central Formosa, has been found as an.
adulterant of this oil, which it somewhat resembles in odour. As this,
oil always contains camphor, which is absent from pure linaloe oil, the
adulterant can be detected as follows:—l
1. By preparation of the semi-carbazone. The sample is steam dis-
tilled to remove any fixed residue, and 25 c.c. are treated with a mixture
of 1 gram of semi-carbazide hydrochloride, 1 gram of sodium acetate and
25 c.c. of 90 per cent, alcohol. After standing for twenty-four hours, 1
gram of sodium bicarbonate is added, and the whole is steam distilled.
The distillation residue is heated on a water-bath and then cooled. The
semi-carbazone of camphor separates, if camphor be present, possibly con-
taminated with hydrazodicarbonamide, which is removed by dissolving
the crystals in a little alcohol, which does not dissolve this impurity. On
dilution of the alcohol, the semi-carbazone separates, and on treatment with,
dilute sulphuric acid a marked odour of camphor is perceived.
2. By oxidation of the other constituents by means of permanganate
of potassium. Into a 2 litre flask, 300 c.c. of water and 50 grams of per-
manganate of potassium are placed, and after standing in ice for 30
minutes 10 grams of the oil are added drop by drop. Heat is developed,
and the oxidation products are entirely soluble. When the reaction is-
over (in about two hours) 200 c.c. of water are added, and the unaltered
camphor can be steam-distilled off.
As little as 1 per cent, of camphor in the oil can be detected by these
methods.
J. C. Umney has described two interesting samples of Mexican linaloe
oil,2 which are unquestionably natural oils, but which may be derived
from a different species of Bursera from those which are usually distilled.
The oils are entirely different in odour from the normal oil, and one
would describe them as a blend of lavender and petitgrain rather than
the normal linaloe (lily of the valley) odour.
On examination it was found that these oils have a very high ester
value, and by this alone are distinguished from the normal oil. The-
following figures were obtained :—
Optical rotation . - 2° 30' - 2° 30'
Refractive index (20°) 1-4600 1-4610
Esters . 52*4 per cent. 48*7 per cent.
Total linalol . 54-8 57-6 „
1 2
Schimmel's Bericht, October, 1913, 69. P. and E.O.R. (1916), 62.
LEGUMINOS^ 475
Particular attention is directed to this oil, because it may be that it
would be well to develop the distillation of this particular wood for its
content of linalyl acetate and for the purposes for which the oils contain-
ing that ester are used, rather than for linalol and the purposes for which
oils containing that alcohol are employed.
Roure-Bertrand Fils l have described the oil distilled from linaloe
seeds. It had the following characters :—
Optical rotation . + 1°30'
Linalyl acetate (esters) 10-2 per cent.
They have detected the following bodies in the oil: Z-linalol, Z-ter-
pineol, nerol, and geraniol. They consider that this dextro-rotatory seed
oil is present in the dextro-rotatory linaloe oils of commerce above re-
ferred to.
LEGUMINOSÊ.
OIL OF COPAIBA.
This oil is obtained by the distillation of the oleo-resin (balsam) of
copaiba, which is the product of several species of Copaifera. The trees
yielding this valuable commercial product are principally found round
about the Amazon and its tributary streams, as far north as Guaiana,
Venezuela, and Columbia. The principal varieties of the balsam are the
following :—
Bahia, Cartagena, Maracaibo, Maranham, Para, Cayenne, and Angos-
tura. The following are probably the sources of several of these
(Umney) :—
Bahia, C. coriacea.
Cartagena, C. officinalis.
Maracaibo, C. officinalis.
Maranham, C. landsdorffii.
Para, C. multijuga.
Cayenne, C. guyanensis.
But there is no doubt that there is very little balsam in commerce

which has been obtained entirely from one species, and it must be empha-
sised that genuine commercial balsam or oils may well vary somewhat
outside the limits quoted for a comparatively small number of specimens
examined. The following figures are, therefore, to be accepted subject to
the above limitation.
The average yields of oil from the various types of balsam are as.
follows :—
Maracaibo balsam 38 to 55 per cent.
Maranham 35 55
Para . 58 78
Cartagena . 40 60
Bahia 40 60
Angostura . 45 55
Maturin 40 55
Surinam 40 72
1
The essential oils have the following values :—
MARACAIBO OIL.
Refractive index . . 1-4955 „ 1-4980
MARANHAM OIL.
PARA OIL.
Optical rotation — 4° — 33°
Refractive index 1-4930 " 1-5020
BAHIA OIL.
CARTAGENA OIL.
MATURIN OIL.
SURINAM OIL.
ANGOSTURA OIL.
Refractive index . 1-4990 „ 1-5020.
The following figures are of value, since they are the results of the
'examination of forty-one samples, many of which were imported direct
by* the firm examining them,1 and of whose authenticity there is no
doubt:—
Essential Oil of Bahia Copaiba—
1 2 3 4 5 6
p. Gr. . 0-898 0'899 0'900 0*900 0-902 0-902
- 11° - 11° 26' - 10° 32' - 10° 30' - 8° 30' - 8°0'
Yield . 44 p. cent. 60 p. cent. 46 p. cent. 54 p. cent. 56 p. cent. 54 p. cent.
1
Evans, Analytical Notes (1910), 26.
LEGUMINOSÊ 477
Sample (1) was a consignment via New York, Sample (2) was a
direct import of undoubted purity.
Essential Oil of Carthagena Copaiba—
Sp. Gr. aD. Yield p. Cent. Sp. Gr. ao. Yield p. Cent,
0-894 - 19° 30' 40 0-903 - 6° 0' 52
0-8972 - 19° 30' 50 0*904 - 2° 30' 45
0-899 - 22° 30' 40 0-905 - 7° 30' 45
Q
0-901 - 7° 30' 45 0-905 - 10 30' 50
The abnormally low optical rotation of several of these oils indicates

probably some change in the botanical source, with possibly a wider
collection than in former years, no adulteration being detected. Some
samples contained from 1*2 to 10 per cent, of admixed water.
Essential Oil of Maracaibo Copaiba—
Specific gravity 0-900 ; aD - 6°; yield, 48 per cent.
Essential Oil of Maranham Copaiba—
Sp. Gr. Yield p. Cent. Sp. Gr. D. Yield p. Cent
0-896 18° 30' 36 0-900 14C ' 30' 40
0-899 18° 30' 45 0-9005 16° 40
0-899 19° 0' 43 0-901 16° 45
0-8995 15° 30' 45 0*901 13° 20' 56
0-900 13° 30' 48 0-9016 12° 18' 50
0-900 14° 0' 52 0-902 13° 30' 50
Essential Oil of Para Copaib
Sp. Gr. Yield p. Cent. Sp. Gr. aD. Yield p. Cent.
0-886 - 29° 0' 52 0-8916 27° 30' 50
0-891 - 25° 12' 5 0-8965 17° 30' 60
0-891 - 24° 0' 50 0-897 • 21° 20' 70
0-891 - 23° 0' 45 0-97 • 18° 44' 64
0*8912 - 24° 14' 50 0-906 - 30° 0' 64
0-8915 - 24° 30' 50 0-908 - 29° 0' 72
Cocking * considers that the first 10 per cent, distilled in vacuo of a

copaiba oil should have a higher laevo-rotation than that of the oil itself,
and that a lower value indicates the presence of an adulterant. Although
the author dissents from Cooking's conclusions, the fact that the British
Pharmacopoeia has based an official test on it causes it to be of consider-
able importance.
Cooking's conclusions are as follows :— 2
To detect adulteration of copaiba with the African oleo-resin, the
sample is submitted to distillation either by steam, or in vacuo, and the
volatile oil so obtained is dried, then fractionally distilled to dryness in
vacuo. Ten equal fractions are collected, and the aD of each of these
determined in a 100 mm. tube.
If the sample be pure the figures obtained will all be negative, and
they will increase arithmetically from the first to the last fraction (that
is, each successive fraction is more strongly laevo-rotatory than the pre-
ceding one), although not regularly. If, now, the rotation of the first
fraction be subtracted from that of the tenth, a figure will be obtained
which varies very little for genuine samples, and is always a negative
quantity. This figure, the " difference value," will only vary - 3*7° to
- 7-6°.
] 3
Chemist and Druggist, 77 (1910), 119. Year Book of Pharmacy (1911), 128.
When African copaiba is examined in this manner, the rotations of
all the fractions are dextro-rotatory, and the rotations of the successive
fractions increase, but to a much greater extent than with the South
American copaiba, in consequence of which the difference value is much
greater than copaiba and is a positive figure. The figures also show a
curious feature in that the tenth fraction has a considerably lower rota-
tion than the ninth. As would be expected from the fact that the range
of boiling-points of the constituents of the volatile oils from the two
varieties are practically identical, a mixture of the two will distil over
containing proportional parts in each fraction, and the presence of
African balsam will be shown at once by the difference value being
positive. In some cases where only a small percentage of the adulterant
is present, all the fractions will be laevo-rotatory but the difference value
will be positive. When the same process is applied to gurjun oil, like
copaiba, it gives laevo-rotatory fractions, but, unlike it, they successively
decrease instead of increasing, and thus give a positive difference value,
similar to African copaiba.
With the true copaibas the rotation of the first fraction is in every
case lower than that of the original oil, but in the adulterated samples it
is higher. It is important that the distillation of the oil should be con-
ducted in vacuo, since, if carried on under ordinary pressure, the higher
temperature necessary causes some decomposition, which entirely alters
the optical rotation.
The principal adulterations of copaiba and its oil are the corresponding
balsams and oils known as African copaiba (probably obtained from
Oxystigma Mannii and gurjun balsam).
The author dissents from this view entirely, and considers that there
is considerable objection to fixing this arbitrary standard, based on the
examination of a few samples, and then jumping to the conclusion that
samples of a product of known variability to a very high degree'must
necessarily be adulterated. The table l on the opposite page illustrates
the behaviour on fractionation, and the general characters of a number
of samples of balsams and oils, of which samples 0 to 5 are stated to
be apparently genuine, whilst samples 6 to 12 are assumed to be
adulterated, and the remaining few being quoted as illustrations of the
difficulty of drawing an opinion on fractionating results
The last column in the opposite table, headed " difference value,"
indicates the optical rotation of the last 10 per cent, of the oil left as a
residue on distillation, minus that of the first 10 per cent, distilled, which
should show a minus figure if Cooking's deductions are correct. In re-
gard to this point the authors above quoted remark as follows :—•
" That generalisation which is conveniently referred to as Cooking's
(its most persistent advocate) for the detection in particular of admixed
African oil, whereby such dextro-rotatory substances become evident on
fractionation through their influence on the optical rotations of the first
and last 10 per cent.—the positions of maximum divergence owing to
opposite progressions—would appear to be under some suspicion.
" This method of analysis has again been of much service, and in the
experience of this laboratory, has been sufficiently reliable for deciding
commercially the purity of all balsams except that from Central America
(Maracaibo), which variety, as pointed out a year ago, is at times subject
1
Evans, Analytical Notes (1912), 26.
FRACTIONALLY DISTILLED COPAIBA^.
BALSAM VALUES. ESSENTIAL OIL AND VACUUM FBACTIONATION FIGURES.
1 Acid Optica Rotations.
Acid Value Ref. Ind. Per S.G. Optical B. Pt. of 90 °/0
of Cent.
Value. 15°. Oil. Ref. Ind .Rotation. At Pressure 10°/0 Difference
Resin. ! 10 °/0. 40 %. 20 %. 20°/0. Residual. Value.
Para— 0*8893
0 . . 72-1 148-1 1*5132 52 -30° - 25° 30' - 27° 14' - 29° 20' - 32° 4o - 34° 50' -9° 20'
1*4935 at 15 mm.
j 7fl
0*9052
70 1 .JQQO 28° 30' 5° 10'
1*50 at 10-12 mm.
2 toe. 7 0*90
1 .CAOO R1 00
1*498 at 15 mm.
Bahia— 0*9055
3 . . . 51 121 1*5095 58 -14° 133°- 135° - 10° 55' 12° 16' - 14° 4' - 17° 40' - 6° 45'
1 *4952
0-899
106 + 0° 15'
1*4949
Maranham — 0-900 j
5 . 82-6 140-1 1*5168 41 -17° 18' 128°- 133 -5° - 13° 48' - 14° 20' -
1*4971
(30 °/0) (20 °/0) Q
Maturin —
A(\
0*912 _L 070 Q/V
d
91 1*5008 — 0° 48' 133°-146-5° — 9° 40' - 8° 5' — 3° 36'
at 15-20 mm.
Via Hamburg- 0*912 1 19O W
70 1 -4985 4- 0° 50' - 2° 58' - 2° 15' + 0° 48' + 4° 15'
Central American at 12 mm.
(Maracaibo)—
0*90 I t/\o
84 1*4972 — 8° 20 128°-137° - 9° - 9° 20/ - 9° 40'
0-9005 at 20 mm. (40 °/0)
9 . . . 89-6 144-5 1-515 38 - 7° 30' 125°-134° - 9° 56' - 9° 10' -9° - 8° 55' -4° -f 5° 56'
1 -4985
0*903 at 15 mm.
10 81*2 — 7° 40° 132°- 141° - 9° 10' - 8° 50' - 8° 10' - 6° So' — 4° 30'
1*498
0-904 at 20 mm.
11 . . . 84 140 1-519 40 - 10° 22' 130°. 139° - 11° 23' - 11° 33' - 12° 30' - 7° 30' + 3° 50'
1*498
0*90 (40 °/c)
12 91 151*6 1*518 40 + 4°
1 *4975
0*917 at 25 mm.
13 . . 86*4 132*5 1*5168 35 - 9° 30' 120° - 9° 30'
1*495 (Balsam + 6°)
(S. G. 0*985) 0-8991 at 12 mm.
13A 85-8 141*6 1*5072(40°) 39*4 -8° 36' -9°
S. G. 0*9838) 1*4933
14 84 161*5 1*518 48 0*899 i no ARf too g'
1*4975 123°-125°
at 15-20 mm.
14A at 40 mm. -13° - 13° 30' - 13° 30' - 14° 55' - 10° 58' -
0*8988 191O toco
15 84 142*4 1*5176 41 too c.
1 *4978 Balsam + 35°) at 12 mm.
to inexplicable changes under such treatment. The decomposition effect
of a slightly too high boiling-point is made clear in the comparison 14,14A,
these figures being from the same sample.
" On the contrary, the temperatures at which portions of sample 3 and
many further samples of Maranham and other types were distilled rose
still higher without any such changes (owing to accidental increase of
pressure). Sample 4, also a Bahia variety (as 3), was moreover further
anomalous since the rotation of the first 10 per cent, came within Cocking's
abbreviated criterion of purity, whereas on complete distillation to obtain
the difference value, this became positive owing to the marked drop in
rotation of the highest fraction, an unpublished feature for any standard
genuine oil—certainly with the correct mean rotation—confirming the
absence of decomposition changes."
In examining this essential oil, it appears certain that the optical
rotation should always be laevo-rotatory, and very rarely below - "4° or
— 5°.
African copaiba oil is always dextro-rotatory, and gurjun balsam oil is
always very highly laevo-rotatory, usually about - 80° or more. Gurjun
oil may be detected with certainty by adding five or six drops of the oil
to 10 c.c. of glacial acetic acid containing five drops of nitric acid. In
the presence of gurjun oil a purple violet colour is developed within a
minute or so. Fatty oils are indicated by a high ester value, the adult-
erant being recognisable by separation of the products of saponification.
The oil consists principally of sesquiterpenes. The early investiga-
tions are 1quite unreliable, the first authentic investigation being that of
Wallach, who stated that the principal2 constituent of the oil was the
sesquiterpene caryophyllene. Deussen and his colleagues have, since
then, assisted in the elucidation of the chemistry of this oil, and found
that the sesquiterpenes present consisted principally of the inactive
a-caryophyllene, but Z-cadinene and a little /2-caryophyllene are ' also
present. Deussen3 has described a sensitive test for caryophyllene.
When /3-caryophyllene nitrosite is heated with petroleum ether there
results, in addition to dehydrocaryophyllene nitrosate, a body which is
distinguished by its insolubility and which can be purified by dissolving
it in acetone and precipitating with light petroleum. It crystallises in
the pure state in white needles, melting-point 159°. The same body is
generated when nitrous acid gas is passed into an ethereal solution of
caryophyllene. A blue coloration quickly results, and when the gas is
continued for some time a voluminous yellowish-white body is precipitated,
while the blue colour disappears. Careful recrystallisation from acetone
yields white, silky needles, melting at 160°. This body is optically active :
[OLD] - 133° 50'. Combustion established the formula C12H19N3Og.
Owing to its insolubility in most organic solvents, this compound is-
excellently adapted for the detection and determination of /3-caryophyllene.
For this purpose from 2 to 3 grams of the oil under examination are treated
in a 10 per cent, ethereal solution with nitric oxides, the reaction-mixture
(which should be protected from light) not being cooled, and the passage
of the gas being stopped as soon as the separation of the body in question
ceases. The precipitate is washed with ether and weighed. Deussen
claims that by this method Para copaiba oil shows the presence of 5'15
1 2
Annalen, 271 (1892), 294. Chem. Zeit., 34 (1910), 873 ; 36 (1912), 561..
*Annalen, 388 (1912), 136.
LEGUMINOSÊ 481
per cent,, and Maracaibo oil 2 per cent, of /2-caryophyllene. African
copaiba oil contains only O87 per cent, of this hydrocarbon.
Several investigations have established the presence in African
copaiba balsam oil of considerable proportions of a dextro-rotatory
sesquiterpene, possessing the properties of cadinene, but affording a
laevo-rotatory hydrochloride. Schimmel & Co.1 have examined the first
runnings of the sample, and submitted 600 grams thereof to careful
fractionation. They obtained the following principal fractions with
more or less constant boiling-points ;—-
1. 119° to 120° (10 mm.) ; 246° to 248° (750 mm.) 10 per cent.; o n _ 1307 ^
248° „ 250° ( „ „ ) 70 „ „
250° „ 251° ( ,, „ ) 10 ,,
2. 123° „ 125° ( ,, „ ) ; 258° „ 263° ( „ „ ) — ; aD _ 6° 52'.
3. 130° „ 133° ( „ „ ) ; 267° „ 270° ( „ „ ) 20 „ „ ; aD + 50°.
270° „ 273° ( „ ,, ) 70 „
The principal fraction (No. 3) had the same boiling-point as cadinene.
The other characters of the " cadinene-fraction " isolated from the oil were :
tf15o 0-9261, [a]D + 60° 40', ?iD2o° 1-51112.
Fraction 2 (20 gr., ao - 6° 52') was tested for caryophyllene. With
glacial acetic and sulphuric acids it afforded no caryophyllene alcohol, but
when nitric oxide was passed into the ethereal solution according to
Deussen's method described above they obtained 2*33 per cent, of a nitro-
genous body, derived from ^-caryophyllene (melting-point 155° to 156*
from acetone).
Fraction 1 (100 gr., d15o 0-9077, [a]D - 13° 21', nD2o° 1-48943) only
afforded the smallest traces of the nitrogenous body from /3-caryophyllene,
and can therefore have contained next to nothing of this sesquiterpene.
It i yielded neither a solid nitrosochloride nor a nitrosite, but it afforded
30 per cent, of a solid hydrochloride, melting-point 117° to 118° and [<X]D
- 36'38° in a 5*09 per cent, chloroform solution. These characters, as-
well as the fact that no depression in the melting-point was obtained by
admixture with Z-cadinene hydrochloride, showed it to be identical witht
this body.
When treated with sodium acetate in a glacial acetic acid solution the
hydrochloride yielded a cadinene possessing the following properties :
boiling-point 273° to 275°, dl5* 0-9229, [a]D - 116-73°, nô 1-50651; when
treated with hydrochloric acid gas cadinene hydrochloride, melting-point
118, was again formed.
The liquid chlorides freed by suction from the cadinene hydrochloride
of fraction I were examined for the presence of other chlorides. As they
could not be distilled in vacuo they were boiled with their own weight of
sodium acetate in glacial acetic acid solution, for the purpose of eliminat-
ing the hydrochloric acid, and the resulting oil was fractionated in vacuo.
Of three equal fractions thus obtained—
(a) 111° to 121° (7 mm.), (b) 121° to 130°, (c) 130° to 135°,
(b) and (c) afforded copious proportions of cadinene hydrochloride, melting-
point 117-5° and 118J, only fraction (a) failed to yield a solid product.
The liquid chlorides of fraction 1 were practically identical in character
with the solid chloride, and must therefore have consisted in the main of
cadinene hydrochloride.
1
Report, April (1914), 48.
VOL. I. 31
The investigation showed that the first runnings of African copaiba
balsam oil contain a laevo-rotatory sesquiterpene, which, although differ-
ing materially from cadinene in regard to its physical properties,
Boiling-point. c?l5o> [o]a nD200.
Sesquiterpene . . 246° to 251° 0*9077 - 13° 21' 1-48943

Cadinene . . 271° „ 273° 0-9215 -105° 30' 1-50647
yet affords cadinene hydrochloride. It is probably closely related to

cadinene.
So far, three sesquiterpenes are known which, when treated with
hydrochloric acid gas, afford laevo-rotatory cadinene hydrochloride;
namely:—
1. ^-cadinene proper.
2. The d-sesquiterpeae of West Indian sandal wood oil and of African
copaiba balsam oil.
3. The Z-S3squiterpene, boiling-point 246° to 251°, of African copaiba
balsam oil.
For the following reasons this result is considered by the investigators
to be of considerable interest : in by far the great majority of instances
the identification of cadinene in essential oils has not been achieved by
isolating the body as such, but by preparing its hydrochloride from frac-
tions of which the boiling-point usually lay between 250° and 270°, or
frequently " from the sesquiterpene fraction ". It is therefore not im-
possible that in many cases cadinene has been assumed to be a con-
stituent of essential oils which possibly contained another sesquiterpene
which yield cadinene hydrochloride. Hence, the isolation of cadinene
hydrochloride by itself can no longer be regarded as proof of the presence
of cadinene.
The presence of gurjun balsam oil in copaiba oil may bs confirmed by
the preparation of gurjene ketone semi-carbazone. The oil is fractionated
under 10 to 12 mm. pressure. The portion boiling above 145° is rejected.
The lower fractions are oxidised with potassium permanganate in acetone
solution. The semi-carbazone melts at 234° C. and has a specific rotation
4- 317° in chloral hydrate solution.
Van Itallie and Nieuwland have identified a sesquiterpene alcohol,
C15H200> melting at 113°l to 115° in Surinam oil.
Semmler and Stenzel have examined the laevo-rotatory sesquiterpene
of African copaiba oil, which yields cadinene hydrochloride, and have
named it copsene. By oxidation with potassium permanganate it yields a
ketonic acid, which forms a ssmi-carbazone melting at 221°.
OIL OF AFRICAN COPAIBA.

The so-called African copaiba oil has been referred to somewhat fully
under oil of copaiba, so that only a few further details are necessary.
African balsam of copaiba is the product of a plant whose botanical origin
is not quite certain. It is probably Oxystigma Mannii, or Hardwickia
Mannii.
The balsam yields from 35 to 47 per cent, of essential oil having the
*Berichte, 47 (1914), 2555.
LEGUMINOSÊ 483
Acid value -5 ,, 10
Ester „ 0 „ 5-6
„ , , (after acetylation) . . . . . 10
It contains Z-cadinene and /2-caryophyllene.
For further details of this oil (which is not employed commercially
except in so far as the balsam is used as an adulterant of ordinary balsam
of copaiba, so that oil of copaiba may be found adulterated with the oil of
the African balsam) see under Oil of Copaiba.
OIL OF HARDWICKIA BALSAM.
Hardwickia balsam, the oleo-resinous exudation of Hardwickia pin-
nata, a tree found in further India, yields about 28 to 50 per cent, of
'essential oil, which has the following characters:—
Acid value 0-85
Ester „ 2-88
The oil consists principally of sesquiterpenes.
OIL OF CASSIE.
The perfume of cassie flowers, Acacia Farnesiana, has for many years
been well known in the form of a pomade. The essential oil is scarcely
a commercial oil, but has been prepared by the steam distillation of the
petroleum ether extract.
Acacia Farnesiana is found in the West Indies, tropical Africa, the
Soiith of France, Egypt, South America, and the Philippines. It is a
native of the West Indies, and was first naturalised in Europe in the
Farnesian gardens in Borne. In Cuba, where it is known as "Aroma
francesca," it has become a troublesome weed. In the Sandwich Islands
also it grows wild, and has proved an obstacle to cultivation owing to its
tough, firm roots and bristling spines. It is there known as " klu," and1
suggestions have been made for its employment for perfume extraction.
In India large quantities of cassia pomade used to be prepared and
exported to all parts of the world, including America, the South of France,
and Germany. The pomade was exceedingly fine and strong in odour,
improving with age. The production, however, gradually got less and
less with competition from other parts of the world.
In Syria a factory has been established for the manufacture of pomades
near Beyrouth, at the foot of Mount Lebanon, where there is quite a
forest of cassie bushes. The climate is temperate and admirably suited
for the development of the perfume of the flower, and Syrian cassie is
competing favourably with the product of the South of France.
In the South of France the tree flourishes best in the neighbourhood
of Grasse and Cannes, where it is known as "cassie ancienne," "cassier
de Levant," and " casillier de Farnese ". Another species, Acacia cavenia,
is known as " cassie romane ".
The flowering season is from October to January or February, and
the blooms open successively, some being ready for picking whilst others
are in course of development. The flowers are usually gathered twice a
*P. and E.O.R. (1914), 53 ; (1916), 71.
484: THE CHEMISTEY OF ESSENTIAL OILS
week during the day, and brought to the factories in the evening. Each
full-grown tree will produce about 2 Ib. of flowers.
The essential oil has the following characters :—
Solidifying-point . . . . . . . . About 1 8 °
Optical rotation 0° to - 1°
Acid value 25 ,, 42*5
Ester „ 114 ,, 229
The following substances have been detected in cassie oil: farnesol,.
geraniol, linalol, benzyl alcohol, methyl salicylate, decylic, cuminic and
anisic aldehydes, and a ketone having a violet odour.
OIL OF BALSAM OF PEKU.
Balsam of Peru is the balsamic, oleo-resinous exudation of the Legu-
minous tree Myroxylon Balsamum (var. p-Pereira}.
The essential oil obtained from the balsam is a highly aromatic,,
viscous liquid, having the following characters :—
Specific gravity . 1*100 to 1*125
Optical rotation . + 0° 30' to + 3°
Ester . . . 200 „ 254
This oil consists principally of benzyl cinnamate and benzyl benzoate,
with a small amount of free benzoic and cinnamic acids. Dihydro-
benzoic acid is also probably present in the form of esters. Cinnamia
alcohol, vanillin, and farnesol are also present in very small amoilnt.
Thorns has isolated an alcohol1 from Peru balsam oil, which he
termed peruviol. This body was stated to have powerful antiseptic pro-
perties, but has not been further investigated until Schimmel & Co. took
up the subject. The sample of oil upon which they have worked had the
following characters : Specific gravity, 1*1200 ; optical rotation, + 0° 55';
refractive index, 1*57177; acid value, 36*4; and ester value, 228*2. The
oil after saponification was fractionated, and after benzyl alcohol had
distilled over, a light oil with characteristic balsamic odour passed over.
It boiled at 125° to 127° at 4 mm., and had a specific gravity, 0*8987;
optical rotation, + 12° 22'; and refractive index, 1*48982. This body
appeared to be identical with Hesse's nerolidol, whilst in physical and
chemical properties it closely resembles Thorns' peruviol. The characters
of the various preparations were as follows :— i ,
Boiling-point. Specific Gravity. Rotation. Refractive Index.
Peruviol (Thorns) 140° (7 mm.) 0-886 + 13°

Schimmers body, 1 . 133° (7 „ ) 0*882 + 14°
,, 2 . 127° (4 „ ) 0-899 + 12° 1*4898
Nerolidol (Hesse) 129° (6 „ ) 0*880 + 14°
,, (Schimmel) 127° (5 „ ) 0*880 + 13° 1-4802
It proved that the impure alcohol isolated from balsam of Peru was,
in fact, identical with nerolidol. When allowed to stand for three to
l
Arch. der Pharm., 237 (1R99), 271.
LEGUMINOS^ 485
four weeks with phenylisocyanate both alcohols yielded a phenylurethane
melting at 37° to 38°. A mixture of the two bodies suffered no depres-
sion in melting-point. The alcohols have the formula C15H26O. The
alcohol from balsam of Peru is therefore mixed with a small quantity of
an alcohol of higher specific gravity, the nature of which is still un-
determined. Traces of benzyl alcohol were found in it, but not in
sufficient quantity to account for the differences observed. Oxidation
experiments did not throw any light on the question. It may therefore
be safely assumed that the peruviol of Thorns consisted in the main of
nerolidol, but contaminated with a substance of the same boiling-point to
such an extent that its combustion figures pointed to the formula C13H220
instead of C16H9fiO.
OIL OF BALSAM OF TOLU.
Balsam of Tolu is obtained from MyroxyIon Balsamum, var. genninum
It yields from 2 to 7 per cent, of essential oil having an odour re-
calling that of hyacinths, and having the following characters :—
Refractive index 1*5440 ,, 1-5600
Acid value 5 to 30
Ester „ . . 175 to 210
The oil contains a terpene (phellandrene ?), benzyl benzoate, benzyl
cinnamate, and farnesol.
Myroxylon Balsamum, var. punctatum, yields a similar essential oil.
OILS OF TRIFOLIUM.
The flowers of Trifolium incartiatum yield 0*029 per cent, of essential
oil, which, according to Kogerson,1 has the following characters :—
90°
Specific gravity ™ 0-9597
Power and Salway 2 obtained 0*028 per cent, of oil from the flowers
of Trifolium pratense, having the following characters :—
orvo
Specific gravity.~^6 0-9476
Optical rotation . . . . . . . . + 4° 10'
OIL OF AMORPHA FRUTICOSA.

The leaves and fruits of Amorpha fruticosa yield essential oils which
have been examined by Pavesi.3
The fruits yield 0*15 to 0*35 per cent, and the leaves 0*05 to 0*08 per
cent, of oils. The leaf oil has a refractive index, 1*5003 to 1-5008 at 17*5°,
and the fruit oil has the following characters :—
Specific gravity 0-9019 (unripe fruit)
0-9055 (ripe fruit)
Refractive index 1-4995 (unripe fruit)
1-5004 (ripe fruit)
Optical rotation . . . . . . slightly laevo-rotatory
1 2
Jour. Chem. Soc. 97 (1910), 1004. Ibid., 232.
*Ann. Soc. Chim., Milano, 11 (1904), 1 and 2.
The leaf oil contains a terpene not yet characterised. Cadinene is-
present, and possibly a second sesquiterpene not hitherto isolated, which
Pavesi has named amorphene.
Shinosaki and Hoshinol have more recently examined the oil obtained
by distillation of the fruits, from which they obtained a yield of 1*1 per
cent. The oil had a pepper-like odour ; its characters were as follows :—
Optical rotation . . . . ±0°
Refractive index . . . . 1-5032
Acid value 0
Saponification value after acetylation 40-5
The higher boiling fractions contain a sesquiterpene alcohol melting
at 118°.
The oil, distilled, apparently, from the fruits only, has recently been
examined by Shinosaki and Hoshino,2 who obtained a yield of 1*1 per
cent. The oil, which has an odour of pepper, has the following
characters:—
Acid value 0
Saponification value after acetylation . . . . . . 40*51
Cadinene and another sesquiterpene were detected, and a sesquiter-
pene alcohol melting at 118°.
OlL OF EOBINIA PSEUDACACIA.
The flowers of this tree yield an essential oil by extraction with a

volatile solvent. The oil has a specific gravity 1*050, and is fluorescent-
in alcoholic solution. It contains methyl anthranilate, indol, heliotropine,
benzyl alcohol, linalol, terpineol, and traces of nitrogenous bodies of the
pyridine series.
OIL OF DANIBLLA THUBIFEKA.
Lenz 3 has obtained from the oleo-resin of Daniella thurifera 23 per
cent, of essential oil, having a specific gravity 0*9845 at 20° and optical
rotation 4- 6°. Cadinene was detected in the oil. An oil distilled by
Schimmel & Co. had the following characters :—
Acid value 0
Ester „ 1-9
GERANIACEjE.
OIL OF GEBANIUM.
True geranium oil is distilled from the fresh herb of several species of
pelargonium, chiefly Pelargonium odoratissimum, Pelargonium capitatumr
Pelargonium graveolens, and Pelargonium Radula, and its variety, roseum*
*J. Ch*m. Ind. Tokyo, 21 (1918), 774. *Jour. Soc. Chem. Ind.t 1919, 38, 27.
3
Berichte, 47 (1914), 1989.
GERANIACEÊ 487
As a matter of fact, however, the plants cultivated are varieties of these
descriptions, not corresponding exactly with the plant when cultivated
true to name in England. The plants are cultivated in open fields in
many parts of Algeria, notably at La Trappe de Staoiieli, Castiglione,
Sahel, and near Algiers and Constantine. It is also largely cultivated in
the South of France, in Spain (chiefly near Valencia and in the province
of Almeria), in Italy, Corsica, Reunion (Bourbon), and in Provence.
The plants are gathered a short time before the opening of the flowers,
when the rose-like odour commences to develop—the leaves at the same
time commencing to turn yellow. The odorous oil is contained entirely
in the green parts of the plant, the coloured petals being practically
odourless. The whole plant is, however, put into the still, and sometimes
rose petals are added, and the resulting fine oil is sold as oil of rose-
geranium.
According to Holmes l the plants actually used for distillation are not
only varieties of the above-mentioned species, but possibly hybrids also,
the particular varieties being kept as secret as possible by the growers,
Holmes states that most of the species of Pelargonium are natives of
dry rocky slopes in South Africa, and under these conditions the plants
are stunted in growth, but in order to obtain a more luxuriant growth and
a larger yield of oil, plantations in Southern Europe and North Africa are
mostly established on low-lying ground, kept moist by a system of irriga-
tion, which causes a luxuriant growth, the plants attaining a height of
about 2-£ ft., and the stems nearly an inch in thickness, so that three
crops of leaves can be distilled annually instead of only one. But although
the oil is thus obtained in larger quantity, it is inferior in quality to that;
derived from plants grown on dry rocky hill-sides. The plant is usually
gathered a little before the opening of its flowers, when the citral-like
odour it possesses gives place to a geraniol or rose odour. The best time,
for distillation is recognised by the leaves beginning to turn yellow.
About 300 kilos of the plant yield a kilogram of the oil.
The plant used at Grasse, so far as can be judged from the leaf of the
plant, appears to be Pelargonium capitatum. Pelargonium Radida, var.
roseum, is apparently also employed there. That cultivated in Bourbon
is stated to be the same species, but the oil distilled there corresponds in
odour with the leaf of the nearly allied species, Pelargonium graveolens.
At Grasse the plants are propagated by cuttings, set in October in well-
sheltered beds, which in time of frost are protected by straw matting
placed over them. The cuttings are taken up in April and planted out
in rows in fields, or on terraces for facility of irrigation, and thus treated,
grow three or four feet high. At Nice they flower in August, but at
Grasse, and in cooler places, in October. For distillation, stem, flowers,
and foliage are cut down and put into the still.
Ducellier 2 gives the following interesting information in regard to the
culture of the geranium plant in Algeria. There are about 850 hectares
(1 hectare *= about 2*5 acres) devoted to the cultivation of the plant, Bovigo
having about 250, Chelbi about 210, Boufarik about 200, Bouinan about
160, and Mouzaiaville about 45 hectares. In addition to the above there
are plantations in Staou&li, Rivet, Bourkika, Cheragas, Oran, Morocco
and elsewhere. For the purpose of preparing oil only one species, viz,
1
P. and E.O.F. (1913), 239.
*Le Gtranium rosat, sa culture en Algeria, Algeria (1913).
Pelargonium graveolens, is grown. Pelargonium capitatum is usually

named in literature as the parent plant of " geranium rosat," but accord-
ing to R. Knuth this is an error, Pelargonium capitatum being a hybrid
of Pelargonium graveolens.
The geranium is propagated in Algeria by cuttings, but it is not neces-
sary to renew the plantations every year, as is done in the South of
France, for the climate of Algeria is rather warmer, and the plants are
therefore not killed by frost in the winter. It is said that in Mitidja the
plant sometimes attains an age of twelve years. It often happens, as for
instance in 1911-12, that the plant is in leaf throughout the year, but
there are occasions in Algeria when the geranium plantations suffer
severely from frost. In the South of France the geranium is treated as
an annual; that is to say, every spring the fields are planted with fresh
cuttings, which have been taken during the autumn and left to winter
in protected spots. In the South of France there is only one crop yearly
(in the autumn), but in Algeria three crops are gathered every year.
In the South of France it is necessary to have recourse to intensive cul-
ture by irrigation and rich manuring, in order to make the single crop
pay. In Algeria the flowers are cut for the first time in early spring;
the second cut is in June, and the third, if any, in October and November.
In addition to suffering from the ravages of insects, the pelargonium
plants are frequently attacked by Cuscuta, a parasitic plant belonging to
the family of the Convolvulacece. It is also said that species of Orobanche
(N.O. Scrophulariacece) thrive upon the geranium plants. On the other
hand, according to Ducellier, the O^mm-species, which afflicts garden
geraniums, has neither been observed in Algeria nor in other districts
where the geranium is grown for distilling.
The oil yield varies according to the conditions of the soil. The
average estimate in Algeria is from 20 to 30 kilos per hectare, of which
the first cut yields 20 kilos and the second (and eventually also the third)
from 10 to 12 kilos. Yields of 40, and even of 50 kilos oil per hectare,
have been recorded.
Holmes has examined the following well-marked species. The
odours have been classified by Umney and Holmes as under :—
Species Examined. Description of Odour.
Pelargonium capitatum . . . Rose and diphenyl ether
,, Abbotsbury Seedling Similar odour
Rose Unique . Fine rose odour
Rollison Unique Rose
Attar of Rose Strong rose
Shrubland Pet . Rose and faint strawberry
Radula " Syon " Strong diphenyl ether and rose
,, var. roseum ,, rose and faint ladanum
,, var. majus ,, geranium and faint pepper-
mint
Blandfordianum Paint rose
odoratissimnm Tansy and faint rose
fulgidum Butyric
graveolens . Rose and rue, slight peppermint
Little Gem . Peppermint, no rose
Lady Plymouth »» )»
denticulatum Rose and ladanum, slight butyric
var. Sandbach Gitronellal,
quercifolium . . Ladanum
,, Clorinde Pepper and southernwood
,, (unnamed
var.) . Parsley
GEEANIACEÊ 489
Species Examined. Description of Odour.
Pelargonium quercifolium minus Southernwood and Tarragon
,, fylutinosum Ladanum
Lady
Lumsden ,, (slight odour)
pumilum ,, and citral
• cucullatum . »
ovale, var. Blattaria . Slight ladanum
albescens Ladanum and weak citronellal
vitifolium . Citronellal and caproic ester
abrotanifolium Diphenyl ether and butyric ester,
with trace of southernwood
Zonale Diphenyl ether
cri&pum, var. maxi-
mum Citral and melissa
,, crispum9 var. mini-
mum Strawberry
.„ Lady Scarborough Citral
,, citriodorum, var., du-
mosum . Weak citronellal and rose
.,, citriodorum, var. maxi-
mum Strong ,, ,,
,, citriodorum, Prince of
Orange . Lemon
.„ tomentosum Peppermint.
,, exstipulatum Pennyroyal
,, tetragonum Indefinite, fruity
Gharabot and Laloue l have published an important contribution to
that portion of the chemistry of essential oils which Dr. Charabot has
so especially made his own. To study the evolution of the various or-
ganic bodies found in the essential oils, a study which may eventually
lead to the possibility of favourably modifying the odour of oils by arti-
ficial means, it is necessary to have an accurate conception of the actual
distribution of these bodies. The paper in question deals with the distri-
bution of the organic constituents in the geranium.
In determining the free volatile acids present, they find that the
amount diminishes as one proceeds from the leaves down to the stem, the
leaves themselves containing 50 per cent, more than the stems. A care-
ful examination of the different portions of the flowering plant shows
that the terpenic compounds (by which the authors evidently mean the
geraniol compounds as well) are found to be entirely absent in the
petioles and in the stems, being found only in the leaves. It is therefore
olear that the odorous substances are elaborated in the leaves themselves.
This at once explains the unusual circumstance of the complete absence
of essential oil in the flower; for the oil does not at any time traverse the
stems, and therefore has no opportunity of reaching the flowers.
The essential oil obtained by separation from the distillation waters
was examined in comparison with that extracted from the water itself,
.and with the whole of the oil yielded by the plant. The following results
were obtained :—
Separated Oil. Oil from Water. Total Oil.
Specific gravity . 0-8979 0-8930 0'8971
Rotation - 11° 2' - 5° 13' - 10° 6'
Acidity 47 16-5 24
Saponification No. 63-6 23-2 57
Ester No. . 16-6 6-7 15
Alcohols as geraniol 70*7 per cent. 77-5 per cent. 71-8 per cent.
Esters (geranyl tiglais) 7-0 „ 2-8 „ 6-3
1
Bull. Soc. Chim. Paris (1903), 838.
Geranium oil differs to a certain extent in character according to the
locality in which it has been produced, and the difference in odour value
is even more marked than the differences in physical characters. The
principal types of oil have the following characters :—
Bourbon Geranium Oil.

Acid value 1*5 ,, 10
Ester ,, 50 to 78 (rarely below 55)
„ „ (after acetylation) . . . 205 to 230
Algerian Geranium Oil.

Ester „ 40 to 70 (rarely as low as 36)
,, „ (after acetylation) 200 to 230
French Geranium Oil.

Acid value 5 to 10 i
Ester , , . . . 50 to 68 (rarely as low as 46)j
„ „ (after acetylation) 210 to 230
Spanish Geranium Oil.

Acid value 2 to 10
Ester „ . . . 60 „ 100
Corsican Geranium Oil.

Ester „ 56 „ 63
Sicilian Geranium Oil.

Specific gravity . 0-894=
Optical rotation . - 11°
Ester value . . . . 84
,, „ (after acetylation) 218
According to Puran Singh l the geranium plant growing wild in the-

Nilghiris is Pelargonium graveolens. An experimental distillation of 500
1
Indian Forest Records, vol. v., pt. viii.
GEBANIACE.ZE 491
Ibs. of the plant, consisting of the entire stems with leaves and flowers,,
yielded 0'044 per cent, of oil having the following characters :—
„ „ (after acetyl tion 226-08
Total geraniol 74-79 per cent.
Combined geraniol 28-19 „
Free 46-60
Esters as geranyl tiglate 40-12
1
According to Furukawa, three varieties of geranium, Pelargonium
graveolens, P. radula, and P. denticulatum, have been cultivated on the
Oi experimental farm near Tokyo. Of these only P. denticulatum re-
sembled closely the geranium oil of commerce. This had a sp. gr.
0-886 at 20° C.; acid value, I'll \ ester value, 12-8; free alcohol as
geraniol 60 per cent.; total geraniol, 63*5 per cent. The yield of oil
was 5 per cent. The oil of P. graveolens had a sp. gr. 0-9178 at 20° C.;
<XD + 4° 6'; acid value, 183'6 ; ester value, 4*8 ; total geraniol, 22*1 per
cent.; free alcohol (as geraniol), 22 per cent. The yield of oil was from
1*75 to 2 per cent. The oil was found to contain a comparatively
large amount of an organic acid, identified as dextro-citronellic acid.
Laevo-menthone and laevo-citronellol were also isolated, by fractional
distillation. P. radula yielded 1*5 per cent, of oil, having a sp. gr.
0-9234; aD + 3°; acid value, 5'6; ester value, 31'7 ; total geraniol, 26'3
per cent.; free alcohol (as geraniol), 17'26 per cent.
Geranium oil is soluble in 2'5 to 3 volumes of 70 per cent.
alcohol.
The relative proportions of the two alcohols, geraniol and citronellol,
in oil of geranium oil is a matter of considerable interest, and the de-
termination is frequently of importance. The only method available in
practice for this purpose is the combination of the acetylation process,
which gives the measure of the total alcohols and the formylation pro-
cess, by which the geraniol is decomposed, and the citronelloL
estimated.
This method has been referred to under Otto of Eose, but has been
more critically studied by Simmons 2 in reference to geranium oil.
Simmons has shown that the determination of citronellol in the presence
of geraniol by the formylation process is not strictly accurate, but the
results are exceedingly useful for comparative purposes.
The formylation process, as recommended by MM. Jeancard and
Satie, consists in heating 10 c.c. of oil with 20 c.c. of 98 to 100 per cent.
formic acid, in a flask attached to a reflux condenser for one hour on a
sand-bath. It may be mentioned that the addition of 2 grams anhy-
drous sodium formate per 10 c.c. oil, while it enables the mixture to be
boiled steadily on a sand-bath, does not affect the result.
To prove whether the results obtained represent the true citronellol-
content Simmons determined the " total alcohols " by acetylation, and
the " citronellol " by formylation of (1) pure geraniol, (2) pure citronellol,
and (3) a mixture of (1) and (2) in equal proportions, with the following
results:—
l
2
Jour.Ghem. Ind. Tokyo (1919), 22, 83.
Total Alcohols as Citronellol.

Geraniol.
1. Geraniol 1
99-6 per cent. 13*7 per cent.
2. Citronellol 100-4 83-4
3. Mixture of 1 and 2 in equal proportions 47-3
Formylation of a sample of Palmarosa oil also gave an apparent

citronellol-content of 14 per cent. From these results it is evident that,
assuming the above samples to represent 100 per cent, geraniol and 100
per cent, citronellol, formylation does not do either of the things it is
assumed to do, i.e. it does not completely convert geraniol into terpene,
and it does not completely esterify citronellol.
To ascertain the value of the process as a comparative test a number
of African and Bourbon geranium oils have been examined by the two
processes, with the following results :—
Total Alcohols as Citronellol. Percentage Composition of

Geraniol. Alcohols.
Per Cent. Per Cent. Geraniol. Citronellol.
f
72-8 40-0 45 55
70-0 42-8 39 61
African \ 79-5 33-4 58 42
69-3 32-0 54 46
69-6 34-8 50 50
I 76-8 33-6 56 44
73-0 50-2 31 69.

Bourbon J 71-7 44-0 39 61,
70-4 46-8 34 66
I 69-7 51-0 27 78- •
These results may be tabulated as follows :—
Percentage Composition of Alcohols.

Citronellol,
Per Cent, on Oil.
Geraniol. Citronellol.
African 32 to 43 39 to 58 42 to 61
Bourbon 44 „ 51 27 „ 39 61 „ 73
Compared with the following figures given by MM. Jeancard and

-Satie:—
I
0r calculated as citronellol, 101*6 per cent.
GEBANIACEÊ 49$
Percentage Composition of Alcohols.

Citronellol.
Geraniol. Citronellol.
African . . . . 37 to 43 40 to 50 50 to 60
Bourbon . . . . 50 „ 65 20 „ 40 60 „ 80
The following results are obtained from other varieties of geranium

oil:—
I
| Total Alcohols Citronellol. Percentage Composition of
as Geraniol. Alcohols. !
1
Per Cent. Per Cent. Geraniol. Citronellol.,
Asian
Corsican
Trappe de Staoiieli
68-4
69-8
71-5
63-9
30-3
27-9
~« r 57
61 i
1
93-4
43
39
Umney 1 gives the following values for a number of geranium oils :—

Frencji 72-7 39-8
Algerian 74-1 32-9
Bourbon 73-0 44-3
Corsican 73-7 45-9
Asian (1) 72-1 51-0
„ (2) 69-1 62-3
It would appear from these results that the citronellol-content of the

Asia Minor oil is undoubtedly the highest, whilst that of Algerian oil is
the lowest. These observations are confirmed by the odour, indicating
that the determination of citronellol-content is not only a useful factor,
but closely follows the nose in judging the value of a particular oil.
The constituents of the various geranium oils are practically identical,
the differences observable being almost entirely of a quantitative nature.
The principal compounds present are the alcohols geraniol and citro-
nellol, together with esters of these two bodies. The term reuniol was at
one time applied to alcohols present in this oil, but it has long been shown
to be merely an impure form of one or other of the two alcohols men-
tioned. Linalol, borneol, terpineol, phenylethyl alcohol, and probably
amyl alcohol are also present in small amounts. The esters present are
principally those of tiglic acid, but small quantities of esters of acetic,
butyric, valerianic, and caproic acids are also present. It is usual to
express the esters of geranium oil in terms of geranyl tiglate.
IJ-a-pinene and /2-phellandrene have been isolated from the oil, as
well as menthone and traces of citral.
The oil is often adult srated with artificial esters which can be searched
for as described under Oil of Bergamot.
1
P. and E.O.R. (1913), 328.
TROPÊOLACEÊ.
OIL OF TBOPÔLUM.
The Nasturtium (Tropaolum ma jus) yields about -04 per cent, of a
strongly smelling essential oil, when the green plant is distilled with
steam. The vessel should be well tinned inside, on account of the sul-
phur contained in the oil. Hofmann investigated this oil in 1874, prob-
ably distilling it without previous crushing. In the oil he found benzyl
cyanide. Gadamer l distilled the plant, first; well minced, with steam,
and extracted the small quantity of oil from the distillate with ether.
He found that it contained 86 per cent, of benzyl-thiocarbimide. He
considers this is due to the fact that there is in the plant an enzyme
which decomposes the glucoside present, with the formation of this body.
He suggests that by not crushing the plant the enzyme is destroyed before
it can decompose the glucoside which is distributed all through the cells,
and that the benzyl cyanide obtained by Hofmann was a product of
decomposition of the glucoside through the distillation.
MELIACE/E.
CEDRELA WOOD OILS.
One of the most useful woods in Jamaica is that obtained from
'Cedrela odorata, an immense forest tree. It is a native of the Caribbee
Islands and the Barbadoes. Its timber has a pleasant odour of cedar,
hence it is frequently spoken of as Jamaica or Honduras cedar, and from
the wood most of the ordinary cigar boxes are made. The wood yields
from '5 to 1 per cent, of oil of a light blue colour, and having the follow-
ing characters :—
Optical rotation very variable
Acid value 2 to 4
Ester ., . 40 ,, 45
The cedar-wood oils from La Plata and Punta Arenas (Costa Eica),
which have been referred to under true cedar-wood oil, are probably
obtained from closely related trees of this order. The oil from La Plata
is of a light blue colour, has a specific gravity -928, and is optically in-
active. That from Punta Arenas is yellow, of specific gravity -915 and
optical rotation — 6°. It consists chiefly of cadinene.
Corinto cedrela wood yields an oil of specific gravity 0*906 and optical
activity - 17. A Cuban wood gave an oil of specific gravity 0*923 and
optical activity + 18°, consisting largely of cadinene.
An oil has also been distilled from the Brazilian cedrela wood (Cedrela
brasiliensis), which yields about 0*5 per cent, of oil of a pale bluish colour,
of specific gravity 0*9348 and optical rotation - 0° 22'. There is also a
cedrela tree in Brazil, Cedrela Velloziana, which yields a small amount
of essential oil having an odour recalling that of asafcetida, but whose
characters have not been investigated.
1
Arch. Pharm. (1899), 237.
CEUCIFEE^l 495
CRUCIFERÊ,
OIL OF MUSTABD.
The essential oil of mustard is obtained by distilling the seeds of
several species of Brassica with water. Brassica nigra is the principal
species employed, but there is no doubt that the mustard seeds of com-
merce contain a substantial amount of the seeds of Brassica juncea and
Brassica rapa. The seeds contain the glucoside potassium myronate,
which, under the influence of a ferment, myrosin, also present in the
seeds, in the presence of water, is decomposed according to the following
equation :—
C10H16NS2KO9 + H2O = C6H12O6 + SO4KH + OS . N . C3R5.
Potassium myronate. Glucose. Mustard oil.
The chief product of the reaction is thus allyl iso-thiocyanate (allyl
thiocarbimide), a pungent and disagreeable liquid. A small quantity of
the normal allyl thiocyanate is also formed, together with traces of allyl
cyanide and carbon disulphide. As mustard oil consists almost entirely
of allyl iso-thiocyanate, and the latter body is easily prepared artificially,
there is an artificial oil on the market. This is made by distilling allyl
iodide or bromide with alcoholic solution of potassium thiocyanate—
a molecular rearrangement to the iso-thiocyanic radicle taking place.
Thus—
CN . SK + C3H5I = OS . N . C3H6 + KI.
Pure allyl iso-thiocyanate is a liquid of specific gravity 1*017 at 10°,
boiling at 151°.
Essential oil of mustard is an unpleasant smelling liquid of great
pungency, having the following characters :—
Specific gravity 1-015 to 1*025 (rarely 1*030)
Optical activity 0°
It boils almost entirely between 148° and 155°.
A sample believed to be distilled from the seeds of Brassica juncea
•only has been examined by Schimmel & Co.,1 and found to have the
Specific gravity . . . . . . . . . 0'995
Optical rotation . . . . . . . . . 4 - 0 ° 12'
The greater part of the oil at above 160°.
Seven hundred and fifty grams oil, being fractionated three times,
gave:—
From 40° to 150° 53 grams or about 7 per cent.
,, 150° „ 160° 200 „ „ 30
„ 160° „ 174° 160 „ „ 20
„ 174° ,, 178° 290 „ ,, 40
The above figures by themselves are sufficient indication that the oil
is not a uniform body. The fact that the thio-urea obtained from it,
which solidified very slowly, had no clearly defined melting-point (67° to
70°) pointed to a mixture of several substances.
1
Dimethyl sulphide, CH 3 . S. CH3. The first drops of the initial
fraction (boiling-point 40° to 119°) contained small proportions of a,
highly volatile sulphur compound of a disagreeable sweetish odour, which
is probably dimethyl sulphide, from the fact that it ga,ve precipitates with
solutions of mercuric chloride and of platinum chloride, as well as because
of its very low boiling-point.
Allyl cyanide, CH3 . CH : CH . ON. The analytical values of a frac-
tion amounting to a few grams, which passed over between 120° and 123°,
and which also contained sulphur (d15o 0-8570; saponification number
47*7) pointed to the probable presence of allyl cyanide.
This suspicion was confirmed by the formation of an acid boiling at
about 184°, with an odour recalling that of fatty acids. This acid was
generated during the process of saponification with alcoholic potash. It
was oily, and when left to stand in the cold for several days it solidified
in crystals ; melting-point 70°. Unfortunately, the quantity available was
too small for repeated purification and for the positive identification of
the substance as crotonic acid, of which the melting-point is 72°.
Allyl iso-thiocyanate, CH 2 : CH . CH 2 . NCS, was found to form the
principal portion of the fraction, boiling between 150° and 163°. The
proportion present did not exceed 40 per cent.
About 50 per cent, of the oil was found to consist of a crotonyl iso-
thiocyanate, C4H7NCS. This substance has the following characters :—
Boiling-point 175° - 176°
Optical rotation . + 0°3'
The thio-urea prepared from this substance melts at 69° to 70° and
has the formula C4H7. NH . CS . NH2.
Grimme 1 records the following percentages of essential oil in the
mustard and allied seeds set out below :—
Brassica oleracea acephala vulgaris 0-079
„ quercifolia 0-051
, ,, crispa 0-103
, gemmifera 0-144
, sabanda . 0-129
, capitala alba 0-258
„ rubra 0-259
gongylides 0-142
botrytis . 0-104
, asparagoides 0-119
Rapa oleifera annua 0-085
,, ,, hiemalis 0-093
„ rapifera . 0-166
,, teltoviensis 0-132
Napus oleifera annua. 0-097
,, ,, hiemalis 0-071
„ ,, flora alba 0-056
„ rapifera (" Erdkoh rabi 0-062
„ ("Wruke') 0-012
Baphanus sativus albus 0-164
niaer 0-108
Badiola 0-106
oleiferus 0-133
Numerous methods for the determination of " mustard oil," that is, of
the thiocyanate compound, in the essential oil, or in preparations thereof,.
1
Pharm. Zentral., 53 (1912), 733.
CRUCIFER^ 497
or in the seeds, have been proposed. The following are amongst those of
the greatest accuracy. Dieterich has proposed the following method : —
Three grams of the oil and 3 grams of alcohol are shaken in a flask
with 6 grams of a 10 per cent, solution of ammonia. It should become
clear after standing for a few hours, or rapidly if warmed to 50° C., and
deposit crystals of allyl thio-urea (thiosinamine)
. C3H6
\NH 2
To determine the quantity, decant the mother liquor and evaporate it
slowly on the water-bath in a tared capsule, adding fresh portions slowly
as the smell of ammonia disappears. Then add the crystals from the flask
to those in the capsule, rinsing the flask with a little alcohol, and heat
the capsule on the water-bath to a constant weight. Three grams of
oil should yield between 3*25 and 3*5 grams of thiosinamine, which
should melt at 70° to 74°. One hundred and sixteen parts of thiosina-
mine correspond to 99 parts of allyl iso-thiocyanite.
Gadamer l recommends the following process. The mustard oil is
dissolved in alcohol to form an exactly 2 per cent, solution. Five c.c..
(4*2 grams) of this solution are allowed to remain with 25 c.c. of deci-
normal solution of silver nitrate and 5 c.c. of ammonia for twenty-four
hours in a well-stoppered 50 c.c. flask. It is then made up to 50 c.c. with.
water and filtered from the precipitated silver sulphide ; 25 c.c. of the
filtrate are mixed with 4 c.c. of nitric acid and a few drops of ferric sulph-
ate solution, and titrated with deci-normal ammonium thiocyanate solu-
tion, until the characteristic red colour of the ferric thiocyanate appears.
From 4*1 to 4*5 c.c. of the solution (corresponding to 1*85 to 2*0 per
cent, of allyl 2thiocyanate in the alcoholic solution) should be required.
Griitzner converts the thiocyanate into thiosinamine, which he oxi-
dises with peroxide of sodium, and weighs the resultant sulphuric acid as
barium-sulphate. From the figures obtained in his analysis, Griitzner
concludes that a mustard oil containing 28*60 per cent, of sulphur
(equivalent to 88*48 per cent, of iso-thiocyanate) may be regarded as pure.
P. Eoeser3 proposes to modify Gadamer's method for the determination
of the sulphur content of oil of mustard so as to determine the excess of
silver nitrate, in an ammoniacal solution, instead of an acid solution
according to Volhard's method, as is usually done. According to this,
the process should be as follows : When the conversion of the thiosin-
amine with silver nitrate, after twenty-four hours' standing, has taken
place, an excess of one-tenth normal solution of potassium cyanide is
added to 50 c.c. of the clear filtrate, and the excess of potassium cyanide
titrated back with one-tenth normal solution of silver nitrate, in the
presence of a few drops of a weak ammoniacal solution (5 per cent.) of
potassium iodide.
Schimmel & Co. recommend the following method : About 5 grams
of a solution of 1 gram mustard oil in 49 grams alcohol are mixed in a
measuring flask of 100 c.c. capacity with 50 c.c. deci-normal solution of
silver nitrate and 10 c.c. of solution of ammonia (dl5o 0*960) ; the flask is
then closed, and with frequent agitation left standing for twenty-four
hours with the light excluded. The flask is then placed for half an hour
in water at 80°, during which time it is again repeatedly shaken, then
1 2
Arch. Pharm. (1899), HO, 237. Ibid., 195.
-Jour. Pharm. Chim., vi. 15 (1902), 361.
VOL. i. 32
cooled down to the temperature of the room, filled up with water to the
mark, shaken up, and filtered. Fifty c.c. of the filtrate are titrated with
one- tenth normal solution of ammonium sulphocyanide, after adding 6 c.c.
nitric acid (d15o 1*153) and a small quantity of solution of iron alum, until
a change of colour from white to red takes place. In order to ascertain
the whole quantity of silver solution which has entered into reaction, the
number of c.c. of ammonium sulpho-cyanide solution used up is doubled,
and the product subtracted from 50. The percentage of allyl iso-thio-
cyanate in the mustard oil is obtained by means of the following formula : —
Per cent. CSNC3H5
a — number of c.c. of deci-normal solution of silver nitrate used up, b =
spirit of mustard used, in grams. Mustard oil determinations carried out
by them in the manner described showed in the case of natural oil a con-
tent of about 94 per cent, allyl iso-thiocyanate, whilst in artificial oil about
98 per cent,l was determined.
Kuntze has examined the differences to be observed in the results
obtained by the gravimetric and the volumetric processes above described,
those of the gravimetric process being higher than those of th 3 volumetric
processes.
Kuntze finds that the precipitate of silver sulphide, which is formed
by both methods under the same conditions, is always contaminated with
more or less silver salt of allyl-thiocarbaminic acid ester.
c=s
\NHC3H5
•so that the ester which is always present even in freshly-prepared alcoholic
solutions of mustard oil does not decompose quantitatively with ammonia-
<cal silver solution, with formation of sulphide of silver, but is partly pre-
-cipitated as a silver salt of the above-mentioned ester. Whilst this
admixture, owing to its molecular weight 252, which differs but little from
that of silver sulphide 248, cannot cause an appreciable error in the
gravimetric determination, it caus s a considerable difference in the volu-
metric estimation, because in the formation of this ester salt only 1 atom
of silver corresponds to 1 molecule of mustard oil, whereas for the con-
version into silver sulphide, 2 atoms of silver are required, so that the
titration results are obviously too low.
Kuntze has found that the separation of the ester salt can be avoided
by immediately heating the alcoholic mixture for one hour, because the
salt is unstable at a high temperature, and proposes the following volu-
metric method to deal with this difficulty : —
Five c.c. of the alcoholic solution of mustard oil are mixed in a graduated
tube of 100 c.c. capacity with 10 c.c. of solution of ammonia and 50 c.c.
deci-normal silver nitrate solution, and the whole is immediately heated
for one hour on a briskly boiling water-bath under a reflux condenser.
After cooling to 15°, and filling up to the mark with distilled water, add-
ing nitric acid until a feeble acid reaction takes place, and 1 c.c. ferri-
ammonium sulphate solution, deci-normal ammonium thiocyanate solu-
ti'on should be added to the clear filtrate, until a red coloration is produced.
1
Arch, der Pharm., 246 (1908), 58.
CRUCIFEBJE 499
Brioux 1 describes a method of estimating allyl and crotonyl iso-sul-
phocyanate in oil-cakes and mustard-flours. He places 25 grams of the
finely crushed oil-cake in a flask of one litre capacity, adds 500 c.c. of
distilled water, 2 grams of sodium fluoride dissolved in a little water,
then heats in the water-bath at 37° to 40° C. after having closed the flask
with a cork. If the oil-cakes or flours are derived from foreign varieties,
it is advisable to prolong the duration of heating to three or four hours.
To the same flask are then added 20 to 25 c.c. of 95 per cent, alcohol,
and the liquid is distilled on the sand-bath ; 150 c.c. of the distillate are
•collected in a 250 c.c. marked flask, previously containing 10 c.c. of pure
ammonia; then 25 to 50 c.c. of deci-normal silver nitrate solution are
Added and the flask is heated for an hour under a reflux condenser in a
water-bath maintained at about 85° C. After cooling, the volume is made
up to 250 c.c. the liquid is shaken and filtered, and finally 125 c.c. are
•taken for the estimation of the excess of silver by means of deci-normal
ammonium sulpho-cyanate. Before making this latter titration care must
be taken to add 10 c.c. of pure nitric acid and 10 c.c. of a 10 per cent,
solution of iron alum. From the quantity of silver necessary for the
formation of the precipitate of silver sulphide, the percentage of crotonyl
or allyl mustard oil is readily calculated.
Huber and Van der Wielen 2 determine the volatile oil (thiocyanate)
in mustard seeds as follows. Their experiments were directed towards
determining to what extent the time of maceration of the crushed seeds
in water influences the result. Five gram samples of the mustard were
macerated for 1, 2, 4, 18, and 20 hours respectively, with 100 c.c. of
water, after which were added 20 c.c. of alcohol and 2 c.c. of olive oil.
Of the mixture about 50 c.c. were distilled into a 100 c.c. measure con-
taining 10 c.c. of ammonia, taking care that the delivery tube was im-
mersed in the ammonia. After adding 20 c.c. of deci-normal silver
nitrate solution the whole was heated over a water-bath until the silver
•sulphide had aggregated and the liquid was clear. The liquid was then
•cooled and made up with water to 100 c.c., the excess of silver nitrate
was determined by titration with deci-normal ammonium thiocyanate,
using iron alum as an indicator.
The following results were obtained :—
After 1 hour of maceration 0'9 per cent, and 0*9 per cent.
„ 2 hours „ 1-15 „ „ 1-15
4 „ „ 1'03 „ „ 1*03
„ 18 „ „ 0-7 „ „ 0-7
„ 24 „ „ 0-77 „ „ 0-77
From the above table the ideal period of maceration is two hours.
Having once added the alcohol to arrest fermentation, the time the liquid
is allowed to stand before distillation seems to have no influence upon
the results; after the two hours' maceration and addition of alcohol, it
was allowed to stand overnight.
White mustard seeds, from Brassica alba, contain the glucoside
sinalbin, C30H42N2S2O15, which on decomposition in the same manner as
the glucoside of black mustard yields glucose, sinapine sulphate, and
the evil-smelling oil, acrimyl-thiocarbimide (p-hydroxy-benzyl-iso-thiocy-
.anate). The reaction takes place as follows:—
C3UH42N2S2016 + H20 = C6H1206 + C16HMN06.H2S04 + C7H7O.NCS.
'Ann. Chim. Anal. Appliquie, 17, 3. *Pharm. Weeicblad (1915), 39.
Acrimyl iso-thiocyanate, or " white mustard oil," is a yellowish oily
liquid of pungent odour and unpleasant hot taste. It is prepared synthe-
tically by treating |)-hydroxy-benzylamine with carbon disulphide, and
the resulting compound with mercuric chloride.
OIL OF SPOON WORT.
Cochlearia or spoonwort oil is distilled from the fresh-flowering plant
Cochlearia officinalis (scurvy grass) which yields a very small quantity of
the essential oil. The specific gravity of the oil is about 0*940 to 0*960, and
it is dextro-rotatory to the extent of + 70° or thereabouts. Its refrac-
tive index is about 1'4900. Hofmann showed many years ago that the
principal constituent was secondary butyl-iso-thiocyanate, of the formula,
/C2H5
OS . NCH( .
\CH3
Gadamer l has shown that if the dried plant without flowers is cut
up, and some white mustard flower is added, the yield of oil is much in-
creased. From 28 kilos of the dried plant, which is known as scurvy
grass, 66 grams of essential oil were obtained. The oil boiled at 150° to
162°, and the bulk of the oil was found to be secondary butyl-iso-thiocy-
anate. A little benzyl-iso-thiocyanate is also present. The amount of
iso-thiocyanate was estimated by dissolving a weighed quantity of the oil
in alcohol, adding excess of deci-normal solution of silver nitrate, allow-
ing the whole to remain for twenty-four hours in a well-stoppered bottle,
filtering from the precipitated silver sulphide, and titrating the excess of
silver with ammonium thiocyanate solution. The fractions of the oil of
. higher boiling-point (156° to 162°) had a lower specific gravity and higher
optical rotation than the earlier fractions. They possibly contained a
little limonene.
In order to determine the purity of the oil a quantity may be heated
on the water-bath with 10 per cent, of its weight of ammonia for a few
hours under a condenser, and the liquid evaporated to dryness. The
mass is then extracted with alcohol and the liquid filtered and evaporated
on a watch glass; the resulting crystals of crude secondary butyl-thio-
urea melt at 125° to 135°. Pure secondary butyl-thiourea melts at 136° to
137°. An artificial cochlearia oil exists, but appears to consist of iso-butyl
iso-thiocyanate. The crystalline thiocarbimide yielded by this melts at
93*5°. The usual adulterants can be thus detected, as the thiocar-bimides
(thioureas) formed from them melt at the following temperatures :—
Allyl (mustard oil) 72° to 74°
Normal buiyl 79°
Iso-butyl 93-5°
Tertiary butyl 165°
OIL OF WALLFLOWEB.
The flowers of the wallflower, Cheiranthus Cheiri, yield about 0*06
per cent, of essential oil by extraction with a volatile solvent and dis-2
tilling the extract with steam. This oil has been examined by Kumnest.
It is of a yellow colour, and in alcoholic solution has a blue fluorescence,
and has the following characters :—
1
Arch. Pharnt. (1899), 237. 2 Qhem. Zeit. (1911), 667.
MAGNOLIACEÊ 501
Distils at 3 mm. pressure from 40° to 150° C.
Acid value 0-35
Ester „ . . . 20-0
A very small amount distilled at 40°, and on analysis was found to
contain both sulphur and nitrogen. It is an evil-smelling compound, and
is probably related to the alkaloid cheiranthin.
Crystalline semi-carbazones were prepared, which, when decomposed
by oxalic acid, yielded aldehydes and ketones, having odours recalling those
of the ketone, irone, and of anisaldehyde. The oil, freed from these bodies
and saponified, was then treated by the phthalic acid method, and a mixture
of alcohols separated. Crystalline diphenyl-urethanes were obtained,
which melted sharply at 50° and at 82°, thus proving the presence of
nerol and geraniol. The presence of benzyl alcohol was proved by the
preparation of a phthalic acid ester melting at 106°. Linalol is also
probably present in traces. From the saponification residues traces of a
phenol (probably para-cresol) lactone (of coumaric acid ?), acetic and
salicylic acids were obtained. Indol and methyl-anthranilate were also
isolated in a state of purity.
MAGNOLIACE^,
STAR-ANISEED OIL.
The aniseed oil of commerce, imported from the Far East, is distilled
from the fruit of Illicium verum, and is known as star aniseed oil. A
certain amount of aniseed oil is also distilled from Pimpinella Anisum,
one of the Umbelliferse, and is described here as a matter of convenience.
Pimpinella anisum is indigenous to Asia Minor and Egypt, and is also
cultivated in Eussia, Spain, Malta, Greece, Bulgaria, Chili, India, and
several other parts of Europe. Eussia produces the greater part of the
anise fruit used for distillation, after which Asia Minor comes chiefly into
consideration.
In Eussia, from which country most of the fruit used for distillation
is obtained, farmers in the districts of Walcysk, Birjutschensk and
Ostrog, and to a less extent Podolia, Kursk, Charkow, Tauria and
Cherson, cultivate the plant, a portion of the fruit being distilled on the
spot, or used for domestic purposes, the remainder being exported. The
commercial centres of the anise trade are Krassnaja and Alexejewskaja.
The yield of oil varies from about 2 to 3 per cent., rarely, a little higher.
The star anise (Badiane) is chiefly found in Southern China and
Tonkin. The earliest reliable information as to the actual habitat of this
plant was furnished by Mr. Piry in his report on the trade at Pakhoo for
the years 1878-79, in which he states that the fruit is brought for export
to Kin Chow and Pakhoi from Kwang-Si, chiefly from Lung-chow on
the borders of Annam, and Po-S6 on the West Eiver close to Yunnan.
The oil is chiefly distilled by the natives, and sold to merchants who
transfer it to Hong-Kong, where it is bought by the exporters and sent
to Europe, sometimes in a grossly adulterated condition. According to
Simon, the adulteration is practised not by the distillers, but by the
" Bande Noir," as he terms the Chinese merchants who combine to buy
the oil from the native distillers, keeping them more or less under their
dominion, by means of money advances in the early part of the season.
European merchants, however, now have their agents both in the Kwang-
Si and Tonkin districts, who collect the oil immediately it is distilled and
transport it either to Hong-Kong, Pakhoi, or Haiphong, from where it is
shipped to Europe. The greatest care is necessary in purchasing this
oil on account of the heavy adulteration, especially with petroleum,
practised by the Orientals. In Annam the process of distillation is as
follows. About 20 Ib. of the fruit are placed in an iron pan and covered
with water. Upon this is placed, bottom upwards, so as to form a cover,
a second iron pan pierced with a circular opening, over which is placed
an earthen vessel with three small orifices in the lower part, which allow
the access of vapour into this vessel. These orifices are covered on the
inside by small ear-shaped hoods which cause the vapour to be spread
over to the sides of the vessel. This earthen vessel is covered with an
iron pan, which performs the part of a refrigerator, and into which a con-
tinuous current of cold water is admitted. The joints of the first two
iron pans are luted and the earthen vessel and the refrigerator are jointed
with rag bandages. The vapour reaches the earthen vessel and is con-
densed when it strikes the bottom of the refrigerator, and falls into a
circular trough at the bottom of the vessel, whence it escapes through a-
small pipe. The average annual production of oil is as follows :—
District of Po-Se 90,000 kilos.
Lung-Chow 30,000 ,,
,, Lang So 30,000 ,,
The Chevalier d'Hanoi gives the following account of the tree as
grown in the Tonquin districts:—
" The particular species producing the oil belongs to the N.O. Magno-
liacea, the Illicium verum (Hooker), also named by Loureiro, Illicium
anisatum, but this must not be confused with the Illicium anisatum of
Linnaeus and Gaertner. This latter, which grows wild in Japan and
China, and has been met with also in Tonquin by Eberhardt, yields an
essence, not only useless, but, according to certain writers, actually
poisonous. There are also other species of Illicium equally valueless^
notably Illicium Griffithii, of India, and its Tonquin variety, Illicium
Cambodianum.
" Illicium verum is a little tree from 8 to 15 metres high. The trunk,,
frequently bifurcate atorthe base, is about 25 to 30 centimetres thick, and
rises to a height of 1£ 2 metres without branches. The branches are
much subdivided, and have very heavy foliage, giving to the tree a pyra-
midal appearance like the cypress.
" The leaves are evergreen, the flowers appear twice a year, and the
young fruits are star-shaped, giving to the tree the name of ' star anise \
The various species may be distinguished by the appearance of the fruits.
Those of Illicium anisatum are covered with hairs, those of the other
species above named, and notably Illicium verum, are smooth, but while
the fruits of Illicium Griffithii and its varieties have stars of ten to thir-
teen points, Illicium verum has stars of eight points (rarely seven or nine).
The last named—the only one of interest to us—has certain variations
which it might be desirable to study in view of a possible selection. For
instance, we have observed in the neighbourhood of Langson certain rare
specimens producing exclusively fruits of nine carpels, and another form
which has unusually fat carpels, presumably richer in essence.
" In Tonquin the natives cultivate it in the north-east on the Chinese
frontier, chiefly within a radius of 20 to 30 kilometres of Langson."
MAGNOLIACEJE 503
The yield obtained is from 2'5 to 5 per cent. In Europe the oil
distilled from the following growths of true anise yielded the following
results (Schimmel):—
Chilian . . 1-9 to 2-6 I Italian . . 2'7 to 3'5
Macedonian . 2 * 2 | Moravian . . 2'4 ,. 3-2
Mexican . . 1-9 „ 2-1 East Prussian . 2-4
Russian . . 2*4 ,, 3-2 Spanish . . 3-0
Syrian . . 1-5 „ 6-0 | Thuringian . . 2-4
The following interesting account of the Eussian anise seed trade is
due 11to the Handelsgesellschaft Anis :—l
In Russia anise is grown in the county of Voronetz, in the districts
of Biriutch, Ostrogojsk, and Valuiki. The seed was originally introduced
from Spain by a Prince Tcherbatoff, and experimentally cultivated by
him on his estate at Krasnoie (district of Valuiki), whence its cultivation
gradually extended until it covered a radius of about 200 versts, within
which, it has remained restricted for many years. Experiments in anise
growing further north and south have been unsuccessful owing to climatic
conditions; in the north because of the long time which anise requires to
reach maturity (about four and a half months in the climate there pre-
vailing), and in the south because there the anise will not develop fully
owing to the great heat and drought. It is therefore only possible to
grow the plant within certain zones where the climatic conditions ap-
proximate to those of the county of Voronetz (average temperature about
15° C. in April, 18° in May, 20° in June and July, and 18° in August).
" The seed begins to sprout about three or four weeks after sowing, the
plants developing very slowly; when they have gained some little strength
the field is carefully weeded, a second weeding taking place a fortnight
later, when the plants must be thinned out where necessary. The central
umbel is the first to make growth, the branch umbels only developing
later; hence the former flowers first. The all-round flowering begins
about two months after the germination of the seed and lasts two or three
weeks. During the flowering time the anise plants are exceedingly sensi-
tive, and most of the crop failures are traceable to unfavourable weather
conditions during this period. Powerful sunshine following quickly after
rain or dew causes the flowers to dry up, and the same result is brought
about by the cold east and hot south winds (the latter being known as
1
viuga,') which are particularly frequent in the first- half of July, just
when the plants are flowering. These winds only prevail locally, but
scarcely a season passes in which they do not cause some damage. In
the year 1903, for instance, a ' viuga ' at the beginning of July destroyed
almost all the anise fields, and the estimate of the crop fell within a few
days from 250,000 to 87,000 poods. The seed harvested in that year was
mostly that of the central umbels, very dark, light in weight, and poor in
oil. After the flowering is over about one month passes before the seed
is ripe; the seed sets first, then it develops, and finally it matures. As
soon as the seed is ripe its apex turns a greyish-green colour.
" Within a week after the gathering the ripening of the fruit is com-
pleted, and the seed is then threshed upon a flat floor, which has
previously been prepared from clay mixed with water. The seed is
mostly threshed with flails, less frequently by running a cart over it.
The threshed anise is then mechanically freed from stalk, chaff, and the
1
Schimmels' Report, October, 1913, 22.
larger particles of earth in a winnowing machine. The average yield of
seed is from 40 to 50 poods per dessiatine.
" The seed is of a greyish-green colour. Quite green seed is obtained
when the anise is harvested in an unripe state. It is extremely rare to
find anise of a quite uniform colour, some proportion of dark seed, more
or less, being generally present; this seed is usually that of the central
flowering-head which has ripened first, or of plants which have been
affected by the conditions of the weather. For even after the fruit has
set the anise plant is still greatly affected by the weather, being liable to
damage by rain or dew immediately followed by hot sun; where such
damage occurs the colour of the seed changes quickly from green to
yellow, brown, and deep blackish-brown.
" The seed is rarely cleaned effectively, owing to the great cost of clean-
ing (1*50 roubles per pood on an average). It is invariably admixed with
some immature seed (from the branch-umbels), chaff, particles of earth
(either the remains of earth adhering to the roots or collected on the clay
threshing floor) and the seed of various weeds, especially of coriander, a
plant which cannot be entirely eradicated from an anise field.
" Apart from these»natural admixtures (about 7 to 8 per cent, of foreign
substances), deliberate adulteration of anise is much practised by the
farmers. Not only do they add earth-particles of a size and colour corre-
sponding with those of anise, but also the seeds of different weeds which
are indistinguishable from anise at the first sight. Eecently the seed of
another umbelliferous field-plant has also been added, and this form of
sophistication is no doubt the .most dangerous, because this seed closely
resembles anise in its colour, and is extremely difficult to recognise even
by the most careful examination. This seed has a faintly bitter taste.
" In order to form an estimate of the coming crop it is necessary to
make two journeys through the anise country, the first at the beginning
of July, with the object of collecting particulars of the area sown from the
' volostines ' (district administrators). These figures are generally readily
supplied by the officials for a small consideration. When all the figures
have been collected it is most important to form a correct estimate of the
fields in the various districts, and to do this, practical experience is neces-
sary. The particulars relating to the sowing cannot be gathered before
July, as they are not prepared until then, and the second journey must be
made when the harvesting is in full swing, because then the anise crop is
no longer subject to any further dangers. Moreover, the evaluation of
the seed while the crop is standing is a safe guide, in particular because
it is also possible then—that is to say at gathering time—to find out the
number of bundles to a given superficial area, and to see the size, weight,
and colour of the seed. When the latter has been good, and the prices
also have been satisfactory, the farmers usually increase their sowings in
the following season, and vice versa."
The two oils are practically identical, except that the true aniseed oil
has a rather more delicate odour and flavour than the star aniseed oil.
The oils have the following characters :—
Star Aniseed Oil.
Optical rotation . 0° to - 2° (rarely slightly dextro-rotatory)
Congealing-point 15° „ 17°
Melting-point 16-5° „ 19°
MAGNOLIACEJE 505
True Aniseed Oil.

Specific gravity at 20° 0'980 to 0*990
Optical rotation 0° to - 2°
Refractive index . . . . . . . 1-5560 to 1*5590
Congealing-point 16° ,, 18°
Melting-point 17° ,, 20°

The usual adulterants are petroleum, fennel oil, or its stearoptene,
and the waste liquid portion of the oil obtained in the manufacture of
anethol (the solid odorous constituent of the oil). In addition, spermaceti
has been said to be added, but the author has never met with a sample
adulterated with this body. The value of the oil depends on the quantity
•of anethol it contains, and as this melts at 21° to 22° and boils at 232°,
the melting-point and the behaviour on fractionation of the oil yield most
valuable information as to its purity. With regard to the latter, the
frac ion obtained between 225° and 235° should not be less than 80 per
<5ent.—usually varying from 80 to 85 per cent.—corresponding to prac-
tically that quantity of anethol. Anethol has a great tendency to exist in
a state of superfusion, so that the oil can be easily cooled down, if not
agitated, below its normal solidifying-point, consequently it is necessary
•either to solidify the oil in a very thin test-tube, and taking its melting-
point, or to determine its solidifying-point in Beckmann's apparatus.
Schimmel & Co. describe the method they adopt in the following
terms, and the author considers it yields very concordant results:—
" For the determination of the point of solidification of essential oils,
ithe well-known Beckmann's apparatus for the determination of the
molecular weight from the decrease of the freezing-point may well be
used. A few small modifications make it particularly suited for the ex-
amination of anise and star-anise oils. These slight alterations consist
mainly in the removal of the cork-connections, by which the full view
of the mercurial column of the thermometer is impeded. The lateral
branch of the freezing tube of the Beckmann's apparatus, serving for
the introduction of the substance to be examined, can also be omitted.
The battery jar serves for receiving the refrigerating fluid. The test tube
suspended in the metal cover serves as aircover around the freezing tube,
preventing the premature solidification of the oil to be examined. This
tube is wider at its top, narrowing down at the junction where it rests on
the rim of the lower tube. In order to support the freezing tube, three
glass protuberances are affixed on its inside about 5 c.c. below its upper
rim. The thermometer, divided into •£ degrees, is supported in a metallic
cover by three small springs, permitting a ready displacement both up-
wards and downwards.
" For making the determination for anise and star-anise oils, the jar
is filled with iced water and broken ice, for fennel oil with a freezing
mixture consisting of broken ice and common salt. Then the sample of
oil to be tested is introduced into the freezing tube, reaching to a
height of about 5 cm., and the thermometer is inserted into the oil with
the precaution not to touch the wall of the tube in any place. During
the cooling process any concussions have to be avoided, as they tend to
cause a premature solidification of the oil. When the thermometer has
reached about 10° below the point of solidification, this being at 6° to 8°
for anise and star-anise oils, the solidification is induced by gentle fric-
tion with the thermometer upon the wall of the tube holding the oil.
Should this simple procedure fail in its object, a minute crystal of solidified
oil or of anethol may be introduced into the fluid, whereupon the crystal-
lisation sets in at once, disengaging considerable heat. It may be ac-
celerated by constantly stirring with the thermometer, whose mercurial
column rapidly rises, soon reaching the maximum height, called the
solidification-point of the oil."
The solidification point taken in this way, or the melting-point, should
not be below 15°. It usually varies in pure samples between 15° and 18°,
according to the percentage of anethol. A quite satisfactory method of
determining the solidifying-point is to carefully supercool a small amount
in a test tube—say to 10°, add a crystal of anethol and stir with the ther-
mometer, which will now rapidly rise to the correct solidifying-point.
Small quantities of petroleum do not bring this point below the lowest
limit for a pure oil, but even 2 or 3 per cent, greatly interferes with the
solubility in alcohol. The pure oil is soluble in 3 volumes at most of
90 per cent, alcohol, whereas an oil adulterated with 5 per cent, of
petroleum will not dissolve in 10 volumes. On keeping for any con-
siderable time, the oil becomes partially oxidised, with the formation of
anisic aldehyde and anisic acid with a lowering of the melting-point and
raising of the specific gravity. A few years ago some samples of aniseed
oil appeared on the German and London markets, which possessed an
abnormally low melting-point. No adulterant could be detected in these,
although the melting-point varied from 8° to 11°. Two views have been
taken on this point. Umney has examined a sample of star-anise leaf
oil, which, according to Simon, is largely distilled in the Po-Se district.
He finds its specific gravity to be *9878, its rotation 4- 1°, and its solidi-
fication-point below that of the ordinary fruit oil. A larger percentage of
anisic aldehyde was also indicated by its behaviour on fractionation, and
towards the usual aldehydic reagent—fuchsine decolorised by sulphurous
acid. Possibly the oil in question was distilled from leaves and fruits.
The other view is that the flowers, or very early fruits, are distilled and
yield an oil with a much lower anethol content. It is believed that some
of the flowers of very young fruits are removed in order to allow the re-
mainder to develop to the best advantage, and instead of being thrown
away, these are distilled. Some oil from Tonkin, said to be oil of this
description, absolutely free from petroleum and apparently quite authentic,
Specific gravity . -9916
Rotation + 0° 23'
Solidifying-point 12°.
Gross adulteration with up to 40 per cent, of petroleum oil was found

in a number of samples a few years ago, but the great alteration in the
physical characters of the oil render this easy of detection.
The following figures represent samples of this type :—
Congealing-point 8°
Melting-point 10°
MAGNOLIACEÊ 507
Petroleum oil separates in a nearly pure condition on shaking the
oil with 10 volumes of 90 per cent, alcohol.
As indicating the effect of anise-leaf oil, Umney l gives the following
comparative figures for the leaf and fruit oils:—
Leaf Oil. Fruit Oil.
Specific gravity at 15*5° 0-9878 •975 to -990
Optical rotation + 1° 0 „ - 2°
Fractionation:—
Below 225° C. 10 per cent. 20 per cent.
From 225° to 230° C. 60 65 „
Above 230° C. 30 15
The author 2 and J. C. Umney 3 have examined a number of commer-
cial samples, which had abnormal characters, and which had either been
adulterated with fractions of camphor oil, or had had part of the anethol
abstracted.
The samples examined by the author had the following characters :—
Melting-point . 12° „ 15°
Congealing-point 10-5° „ 12°
Optical rotation + 0° 15' „ 0° 35'
It will be noticed that the specific gravity is abnormally low, and!
does not correspond with pharmacopoeial requirements, while the melting;
and congealing-points are also very low. The refractive index is lower
than has ever been found for pure aniseed oil, which has a value betweent
1*5530 and 1-5565, or thereabouts. The slight dextro-rotation indicates-
nothing, as some samples of pure star-anise oil are faintly dextro-rotatory.
A large sample from one shipment was examined more fully, and
finally a bulked sample made from a number of the above-described
samples, and fractionally distilled, side by side with a pure anise oil-
The results of this distillation are embodied in the following table :—
Adulterated. Pure.
Specific gravity at 20° 0-9720 0-982
Optical rotation 0° - 1° 10'
Melting-point 13° 18°
Gongealing-point . 11° 15°
Refractive index of 1st 10 per cent. 1-5160 1-5346
Melting-point ,,10 ,, - 3° (partial 8°
solidification)
Refractive index of 2nd 10 ,, 1-5308 1-5496
„ „ last 20 ,, 1-5403 1-5560
All the immediate fractions had lower refractive indices and lower
melting-points than the corresponding fractions of the pure oil, and the
amount distilling between 225° and 235° was only 69 per cent., against
87 per cent, for the pure oil. The residue of 20 per cent, was less
soluble in alcohol than the corresponding fraction of pure aniseed oiL
The odour of the adulterated oils was characteristic, and quite different
from that of pure oil. These figures proved conclusively that these
samples were not genuine anise oil, and, taken in conjunction with the
peculiar odour and taste, indicate strongly that the adulteration took the
form of the addition of some foreign oil. The most probable adulterant
is some fraction of camphor oil.
1 2
P. and E.O.R. (1914),
3
73. Chemist and Druggist (1910), 687.
P. and E.O.R. (1910), 236.
The following bodies have been detected in star aniseed oil: Dextro-
a-pinene, phellandrene (in several* modifications), cymene, cineol, di-
pentene, Z-limonene, a-terpineol, methyl-chavicol, hydrokinone ethyl
ether, safrol, a sesquiterpene, anise ketone C6H4(OCH3)(CH2. CO . CH3),
and anethol.
True aniseed oil has not been so fully investigated, and the only bodies
so far detected in this oil are anethol, methyl-chavicol, anise ketone, and
traces of acetic aldehyde.
The fruit of a plant, Seseli Harveyunum, known in Victoria (Australia)
as aniseed, but which more closely resembles fennel, yields an oil which
has been examined by Umney, who found its specific gravity to be '914
and its rotation + 14°. It was still liquid at 4°. The oil thus resembles
fennel more than anise oil.
A false aniseed, also belonging to the N.O. Magnoliacece, is found in
Japan under the name " Shikimi no Ki". It is the Illicium religiosum,
and its oil is known as Shikimi or Japanese star-anise oil. This oil has
Specific gravity 0-980 to 20
Optical rotation 0° to - 4° 30'
It contains eugenol, cineol, and safrol, and a terpene, probably limonene,
with some sesquiterpene. The oil from the leaves has a specific gravity
1-006, and optical rotation - 8*6°. It contains eugenol, safrol, and a
terpene. The so-called anise bark oil, from the bark of Illicium parvi-
florum, is an oil of spicy taste, and odour recalling sassafras and tarragon.
It has a specific gravity -969 and optical rotation - 0° 46'. It consists
chiefly of methyl-chavicol, containing very little anethol.
OIL OF MAGNOLIA KOBUS.
The oil obtained from the fresh leaves and branches of the Kobushi
tree (Magnolia Kobus D.C.) to the extent of about 0*45 per cent., has a
bright yellow colour, and possesses the following characters :—l
Acid number . . . . . . . . . . 1-5
Ester „ 8*87
It is soluble in 1'2 volumes 80 per cent, alcohol; the greatly diluted
solution shows opalescence. The odour of the oil reminds of sassafras
oil, and gives rise to the presumption that it contains a large proportion
of safrol; the oil also contains among others small quantities of citral.
The species of magnolia which yields this oil occurs chiefly in the central
districts of Japan; the distillation of the oil takes place from July to
September.
A sample examined by Charabot and Laloue 2 had a specific gravity
0-943 and optical rotation - 1° 20'. These chemists detected citral.
(about 15 per cent.) and anethol,' with small quantities of alcohols and
esters. Methyl-chavicol is also probably present. Cineol is also, accord-
ing to Schimmel, a constituent of the oil.
OIL OF CHAMPACA FLOWERS.
The so-called champaca wood oil, commonly known as guaiacum
wood oil, must not be confused with the true champaca oil. The first-
J 2
Schimmel's Report, October, 1903, 78. Compt. Rend. 146 (1908), 183.
MAGNOLIACEJE 509
FIG. 48.—Young Champaca tree growing in a garden of Manila.

\Eour e-Bertr and Fih.
-510 THE CHEMISTKY OF ESSENTIAL OILS
named is the product of an entirely different plant. The true champaca
oil is distilled from the flowers of Michelia Champaca, a plant cultivated,
and also growing wild, in the forests of the Himalayas, from Nepul and
Kumaon eastwards ; and also in the Nilghiris and Travancore, Java and
the Philippines. The flowers, which are of an exquisite odour, are not
unlike a double narcissus. The essential oil distilled from the flowers is
known in India as Pand or Champa-ka-utter. The oil is known as
Yellow Champaca, whilst that from Michelia longifolia is known as White
Champaca.
The following interesting account of the plant is due to Professor
Perrot,1 director of the laboratory of Materia Medica at the Higher
.School of Pharmacy of Paris :—
" Michelia Champaca L. (Michelia rufinervisD.C., Michelia aurantiaca
Wall, MicheliaRheedi Wight, Magnoliaceae) is a native of India. It is found
there in all parts of the country more or less plentifully, but it occurs chiefly
in tropical India : in Nepaul, Assam, and Bengal. In the South and in the
Himalaya district it still exists in the wild state, but is less generally
-distributed. The tree is applied to numerous uses and is known by
different names according to the district: Champaca, Champaka in Ben-
gal, Tita-sapa in Assam, Oulia Champ, in Nepaul; it is also known
in other parts of the country under the names of Shampang, Shimbu,
Sempangam, Sampige, Champakam, Saga, Sapu, etc. It is also cultivated
in the Philippine Islands. This large tree, which is an evergreen, prefers
sandy soils. It is of fairly large size, since a man can scarcely encircle
the trunk with his arms.
" The flowers, of a yellow colour, are produced at the tops of the
branches and are carried by stout peduncles of a yellowish-green colour,
polished and erect. The number of flower heads may vary slightly ; in
.general there are eight heads to the verticillaster.
" There are two flowerings annually, and the tree only yields fruits
after some years.
" The numerous applications of the Michelia Champaca make it a
valuable plant, which is regarded in some districts as sacred.
The flowers adorn the turbans of the men and the hair of the women.
The natives of Malaya, Java, Macassar, and the Philippines use them in
a like manner. They wear the flowers in their clothing, and employ
them for the decoration of their nuptial beds.
" These flowers likewise serve as offerings in the Hindu temples. The
trees also are frequently found in the vicinity of the temples.
" The perfume of the flowers of the Philippine Champaca is stronger
:and sweeter than that of the Singapore, Penang, Colombo, and Pera-
-deniya flowers. It would appear that it is the same with this tree as
with the ylang, which does not yield the same essential oil in Java, the
Straits, or Ceylon, as in the Philippines."
It is doubtful whether the commercial oil is ever distilled from the
yellow flowers alone, so that the champaca oil of commerce is probably
the product of the flowers of Michelia Champaca and Michelia longifolia.
Oils produced by maceration of the true champaca flowers from
Java plants in petroleum oil and distillation by steam at very low pressure
found by Bacon 2 to have the following characters :—
1
2
Roure-Bertrand Fils, Bulletin, April, 1909, 24.
Philip. Jour. Sc. (1909), 181.
MAGNOLIACE^ 511
qrjo
Specific gravity *£- 0 954 to 1*020
Refractive index a t 30°. . . . . . . . T4550 „ 1-4830
Oils distilled in Manila were found by Brooks l to have the following
•characters :—
30
Specific gravity ° 0-904 to 0-9107
The oil distilled from the white flowers of Michelia longifolia have
Ester value 180
Commercial oils are therefore to be expected to have characters inter-
mediate between the above, the white flowers probably being employed
to a greater extent than the yellow in distillation.
Champaca oil contains benzyl alcohol, linalol, geraniol, esters of
methyl-ethyl acetic acid, methyl anthranilate, isoeugenol, ben zoic acid,
methyl eugenol, and a crystalline body melting at 165° to 166°, of the
formula C16H20O5.
Brooks states that this substance reacts quantitatively with bisulphite
solution, but that it cannot be recovered from the bisulphite compound.
This renders it probable that the group CH : CH . CO is present in this
body. The fact that the substance is a ketone is proved by its behaviour
iowards ammoniacal silver solution and magenta solution. The phenyl-
hydrazone melts at 161°. The ketone does not react with acetanhydride,
-and with acetyl chloride it resinifies. When heated with an excess of
alcoholic potash solution it gives rise to neutral succinate of potassium.
It would seem that the succinic acid occurs in the ketone-molecule in
the form of a neutral ester. In order to identify the alcohols which
were associated with the succinic acid, the ketone was saponified with
aqueous solution of caustic soda, but only ethyl alcohol could be de-
tected. It appears that one of the carboxyl groups of the succinic acid
is esterified with ethyl alcohol and the other with an alcohol C10H12O2. *
An oil has been distilled from champaca leaves in the Malay Penin-
sula. The yield was 0*04 per cent, of an oil having the following
•characters:—
Acid value 1-9
OIL OF WINTER'S BARK.

The bark of Drimys Winteri yields between '5 and 1 per cent, of this
oil. This plant was originally discovered by Captain Winter in the
Straits of Magellan, and is now found in various countries from Mexico
to Cape Horn. The oil, which has been examined by Avata and Can-
.zoneri,2 has a specific gravity of about -945. It consists of a mixture of
1
Philip. Jour. Sc. 6 (1911), 333 « Jahrt ft Pharmt (xggg), 70.
several bodies from which these chemists state that they have isolated a-
sesquiterpene. It distilled between 260° and 265° and had a specific
gravity '9344 and a rotary power [a](/ = + 11° 2'. They term this body
winterene, but its chemical identity cannot be regarded as settled.
ANONACE/E.
OILS OF YLANG-YLANG AND CANANGA.
Ylang-Ylang oil (" flower of flowers ") or oil ot Cananga is the product
of distillation of the flowers of Cananga odorata, a native of Ava and
Tenasserim, and generally distributed and cultivated throughout Southern
G. 49 — (Ylang-Ylang in the main street of Malabon).

Fila.
Asia. When wild, the tree grows to its maximum height, but its flowers
are said to be almost odourless. The cultivation of the plant reaches its
highest degree of perfection in the Philippine Islands, and the best
variety of the oil is distilled in Manila, where the industry is carried on
in a scientific manner. There is also a considerable industry in this oil
in the island of Beunion. A large quantity of oil also comes from Java
and the neighbourhood, but the oil is not nearly of so fine an odour as
that from the Bast Indies. How far this is due to climatic conditions,
and how far to the less scientific methods used in the distillation of the
oil, it is difficult to say, but there appears to be no doubt that, botanically,
the plant is the same in both districts. The oil is the most pronounced
example of the product of the same plant having entirely different values
according to the locality of production. The oil from the Philippine
ANONACEÊ 513
Islands is known as Ylang-Ylang oil, and is of the finest odour of all the
Cananga oils. The Beunion oil is also known as Ylang-Ylang oil, but is
of much lower value ; and the oil from Java and the neighbourhood is
known as Cananga oil commercially, and is of much lower value than
Ylang-Ylang oil.
The most recent and authentic account of the Ylang-Ylang industry
in the Philippine Islands is contained in a paper by E. F. Bacon,1 who has
made a special study of the plant and its essential oil :—
" In Manila, where the conveniences for careful distillation are greater
FIG. 50.—Cananga (in front of a Pagoda Bangkoh).

[Roure-fiertra
than in outlying districts, fine oils as well as second-class oils, which are
frequently known even there as ' Cananga ' oil, are produced, but in the
provinces the distillers, who are compelled to work with less scientific
apparatus, generally produce only a second-class oil. As the distillers,
usually do not possess any ylang-ylang plantations of their own, they
are compelled to purchase the flowers. In order to increase the weight,,
the blossoms, picked by the natives during the night and brought to the
distilleries in the morning, are frequently moistened as much as possible
with water and mixed with leaves and twigs. Moreover, quite three-
fourths of the blossoms delivered at Manila are green and unripe, although
the use of ripe yellow blossoms is of the greatest importance for the
yield and quality of the oil. In Manila the best blossoms are picked in
May and June, although in 1907 the trees blossomed so late that the dis-
1
Philipp. Jour. Sc., 3 (108), 65, and S^himmel's Report.
VOL. I. 33
tillation lasted from August to the following February. Of the provinces,
where the ylang-ylang tree is also found, the oil is distilled in the
Camarines, Mindoro, and Albay; the tree also grows in Bohol, but the
distillation has not yet been introduced there. The oil produced in the
provinces is generally considered in Manila as inferior, but this can only
be attributed to the primitive method of production. In most cases the
flowers are quite as good as those of the district round Manila, and a few
Manila houses also distil in the provinces an oil for which they obtain
FIG. 51—Ylang-Ylang (Malabon near Manila).

[Roure-Bertrand Fils.
just the same high prices as for their other make. There can be no
doubt that the installation of scientific distillation methods would bring
about a powerful advancement of the ylang-ylang oil industry in the
provinces.
- r" Aigood deal of mystery is made of the distillation of ylang-ylang oil
in Manila, and it is said that the manufacturers possess valuable trade
secrets. Bacon, who has visited several plants, and has himself carried
out distillation experiments, does not believe that there are any trade
secrets, although it is clear that not every one can distil first-class oil.
But with a little experience in the distillation of essential oils it will, in
ANONACEÊ 515
his opinion, not be difficult to find out the special small precautions which
have to be observed, provided proper apparatus is employed. The great
mistake made by the distillers in the provinces is in the wrong choice of
fractions and in burning the blossoms, owing to which the oil shows too
large a content of resin. A matter requiring special attention is, that the
oil, which, as a rule, only represents a fraction of the total oil contained
in the blossoms, is distilled slowly with steam. The provincial distillers
FIG. 52.—Cananga (environs of Batavia).

[Roure-Bertrand Fits.
usually make the mistake of distilling 1 kilo oil from only 150 to 200
kilos blossoms, so as to obtain a good yield, whilsi the average quantity
to be used for such purpose should be about 400 kilos. After distilling
out 1 kilo of fine quality oil, it is then still possible to obtain the same
quantity inferior oil. The distiller usually judges by the odour of the
distillate whether the time has arrived to change the receiver. The oil
itself is collected in Florentine flasks, of which two or more are connected
in series; the distillation-water is used for future distillations. It is
useful to tin the inside of the distilling apparatus, although some distillers
prefer to nickelplate it. The oil is very sensitive towards air and light,
and must therefore be kept in a dark place and in well-filled vessels.-
Experiments with steam distillation in vacuo should be made with proper
apparatus, and the blossoms should also be macerated beforehand; this
would no doubt favour a rapid production of oil.
• " The valuation of ylang-ylang oil by means of an analytical deter-
mination of the individual constituents is a matter of considerable diffi-
culty and doubt, as it owes its perfume to a large number of odoriferous
substances, and, as a matter of fact, the oil is judged in the trade chiefly
by the odour so long as analysis shows that it is pure."
The ylang-ylang tree was introduced into Eeunion about 1770, but it
was not exploited as a source of perfume material until about 1880.
According to Desruisseaux,1 the plant succeeds well in the island in all
porous and substantial soils which are met with in the tropical and
equatorial zones. It dreads above all the presence of stagnant water, as
also violent winds, which in some countries blow almost incessantly.
Consequently in Eeunion, below the 21st degree of South latitude, it has
been recognised that at an altitude of 400 metres and upwards, the ylang-
ylang did not flourish. But it is certain that in the equatorial zone the
tree may accommodate itself to higher altitudes and flourish there.
The ylang-ylang in Eeunion begins to produce flowers at the age of
eighteen months to two years. At the age of four years, a tree may yield
5 kilos of flowers if it is planted in a rich soil. Trees have been known
of ten years of age to produce, under the action of strong manuring, as
much as 10 and 15 kilos of flowers annually.
The flowers succeed each other on the tree continuously, so that it is
possible, so to speak, to pluck them all the year round. But it is during
the winter season that they are particularly plentiful, that is from Nov-
ember to March in the tropical countries of the Southern hemisphere.
The flowers do not all develop at the same time on the bunches ; only
those which are at the right stage should be plucked, with a portion of
their peduncle. For this purpose the gatherer should make use of his
nails or of a pair of small scissors. The flowers are placed in small
baskets or cloths.
When plucking is in progress, it is necessary to avoid shaking the
branches of the tree and the bunches of flowers too roughly, so as not to
spoil those which remain on the tree, and when the latter is too high, the
gatherers should not climb on the branches which break rather easily,
but should use a double ladder. Generally this delicate work is performed
by the women and children.
The flower should be delivered to the stills a short time after gather-
ing, otherwise its yield of essential oil will decrease and the fineness of
the perfume will be lost. The plucking should be made as far as possible
in the early morning, and it is necessary to avoid bruising the flowers.
Bruised, faded, and blackened flowers yield an essential oil of inferior
quality.
The distillation is carried out in presence of water, and may be per-
formed in a simple still. The type of still which provides for the return
of the waste waters of distillation is the most practical.
The flowers of ylang-ylang contain from 1*5 to 2'5 per cent, of their
weight of essential oil. They are richer when they are derived from lands
well exposed to the sun and not very moist, and when the plucking is
1
Bulletin du Jardin Colonial (1910).
ANONACEÊ 517
performed in dry weather. In Keunion they have succeeded in obtaining
a kilogram of essential oil per 40 kilos of flowers, and by simple but pro-
longed distillation.
This yield is too high and the oil which is obtained is then not of its
best possible value, and its value is much decreased.
In order to have a good essential oil it is necessary only to remove
from the flower 50 to 60 per cent, of its perfume, and in the island of
Eeunion a good product is obtained by only taking 1 kilo of essential
oil per 100 kilos of flowers. For this purpose, in practice, a still of one
hectolitre capacity is charged with 15 kilos of flowers which are distilled
only for nine hours, and yield 150 grams of essential oil.
The analyses which have been made show that if, with a distillation
of short duration a comparatively small yield is obtained, it is compen-
sated by the quality of the essential oil, which is the first condition neces-
sary for the commercial success of this product. It is probable that in
•order to obtain more satisfactory results, the distillation with water should
be replaced by distillation with steam, which not only gives a better pro-
duct but decreases the cost of the operation, and enables several operations
to be performed in a day with the same still.
The distillation conducted for a short time removes only the finest and
best essential oil. Some remains in the flowers, and the product which
is distilled in six or nine hours, once obtained, should be placed on one
-side. Then distillation may be continued in order to collect an inferior
or second quality essential oil, which will be worth rectifying for the pro-
duction of a medium quality which will still be commercially saleable.
The essential oil of good quality is amber-coloured. It is of lower
value if it is brown or whitish.
Immediately after distillation it should be filtered, then preserved in
•opaque vessels of glass, tin, or tinned copper. The vessels should if
possible be fitted with ground-in stoppers.
Attempts have been made to cultivate the ylang-ylang tree in Amani,
by the German colonists there, but from a commercial point of view the
experiments were unsuccessful.
Madagascar, the Seychelles, and various other places have produced
the oil, but so far not in any important quantities.
The characters of ylang-ylang and cananga oils are very variable,
not only on account of the variability in cultivation, climatic conditions,
etc., but also owing to the fact that the oil is prepared by a fractionation
process, the individual distiller stopping the distillation at such point as
he conceives to yield the best combination of quality and quantity.
The following values, which must be accepted with the above quali-
fications, cover most authentic samples of the types mentioned:—
MANILA YLANG-YLANG OIL.

Specific gravity . . . . . . . 0'908 to 0*967
It is soluble in 0'5 to 2 volumes of 90 per cent, alcohol.
Bacon has examined twenty-three samples of oils considered to be
of the best quality, and thirty-six samples of second grade, which he
found had the following characters :—
First Quality Oils. Second Quality Oils.
30°
Specific gravity ^- . . . 0-911 to 0-958 0-896 to 0-942
Refractive index at 30° . . 1-4747 „ 1-4940 1-4788 „ 1-5082
Optical rotation . . . - 27° to - 49-7° - 27-4° to - 87°
Ester number . . . . 90 „ 138 42 to 94
(in one case 169)
According to Bacon, in first-class oils the ester number is mostly 100

or more, the refractive index rarely above 1*4900, optical rotation rarely
above - 45°, but mostly between - 32° and - 45°. In the case of the
second grade or cananga oils, however, the ester number is rarely higher
than 80, the refractive index approaches 1*5000 owing to the larger
content of sesquiterpenes and resins, and the optical rotation amounts to
- 60° and more. Low values for optical rotation and ester number
usually point to second-class oils, which have mostly also a low specific
gravity. Oil with a low refractive index, low rotation, and a high ester
number can with a fair amount of certainty be considered as good, whilst
a high refractive index, high rotation, and low ester number point to oils
of lower quality. The figures for the specific gravity did not indicate
any special regularities, but in an oil with a high specific gravity and a
high ester-content (ester number above 100), the refractive index also
will usually be found high, and the oil can therefore be considered as
good.
Attempts made to arrive at oils of better quality by distilling inferior
oils in vacuo gave no favourable results, as the odour suffered distinctly,
and could only be improved by passing air through the oil—a process
which is also employed to remove the burnt odour caused when the
blossoms are allowed to be slightly burnt in the distillation. It appears
that the highest boiling portions of the oil fix the fragrant volatile con-
stituents, for the resinous distillation-residues always showed an odour
which lasted for a remarkably long time. It was further found that
first-class oils contained over 50 per cent, of portions boiling below 100°
at 10 mm. pressure.
KEUNION YLANG-YLANG OIL

Optical rotation . . . . • . . . . - 34° „ - 65°
JAVA CANANGA OIL.

Refractive index about 1-4900 to 1-5050
Ester value 10 to 60 (rarely above 35)
(after acetylation) 45 to 100
Four samples of ylang-ylang oil distilled in Amani (East Africa)

were examined by Schimmel & Co.1 with the following results:—
1
ANONACE^B 519
2 3
Condition 1 Faded Flowers Faded Flowers Faded Flowers
of the kept for 2 days kept for 4 days
after 24 hours' and
Material. Fresh Flowers. partly some- and dried in
keeping. what shrivelled. the shade.
d15o 0-9366 0-9190 0-9170 0-9382

ao - 17°.!' - 20° 4' - 19° 50' - 18° 46'
nD20° 1-48451 1-48431 1-48267 1-49394
Acid Number 1-1 I'l 1-9 2-8
Ester „ 136-3 103-8 96-9 114-2
Solubility . in 8 vols. in 1 vol. in 1 vol. in any prop.
70 °/0 alcohol 80 °/0 alcohol 80 °/0 alcohol 90 °/0 alcohol
with opales- dilute sol. dilute sol. dilute sol.
cence opal. turbid opalescence
Apart from the strikingly low rotation, which would correspond with
that of cananga oil, the general constants of the four samples agree with
those which have thus far been recorded for ylang-ylang oil, but some of
the samples in question are very much more soluble, which shows that
they contain very little sesquiterpene. That would be an advantage
rather than otherwise, but notwithstanding this, samples 2, 3, and 4 were
quite useless for perfumery purposes because their aroma was wholly
insufficient, and steadily deteriorated according to the age of the raw
material used.
Eoure-Bertrand Filsl record the following values for ylang-ylang oil
obtained from various sources :—
Oil of Ylang-Ylang obtained from
Reunion. Nossi-Be. Mayotte. Manila.
Density at 15° C. 0-9492 0-9673 0-9324 0-911 to 0-958

Rotatory Power -38° 8' -42° 12' - 47° 40' - 27° to - 49-7°
Solubility in 90 per Cent. £ volume, 1 volume, 1 volume,
Alcohol . . . . then cloudy then cloudy then cloudy »»
Acid Number . . . . ,, 1-4 1-0 »»
Coefficient of Saponification . 96-03 129-5 113-4 90 to 138
Esters, as Linalyl Acetate 33-6 °/0 45-3 <>/0 39-7 "A, »»
Coefficient of Saponification of
the Acetylated Oil 132-11 154-7 134-4 »»
Total Alcohols (as Linalool) . 40-3 «/0 42-7 °/0 41-0 °/0 »>
Combined Alcohols . 26-4 % 35-6 % 31-2 */0 24-7 to 38.°/0
Free Alcohols . . . . 13-9 % 7-1 °/0 9-8 °/0 »»
Three further samples from Mayotte were examined 2 and had the
following characters, the third sample being quite different from the other
two, and having a rotation — 4° 4':—
1
Bulletin, April, 1910, 61
2
Ibid., October, 19H, 40.
I. ir.
Density at 15° C 0-9594 0-9651

Rotatory Power - 53° 56' - 45° 16'
Solubility in 95 per Cent. Alcohol 1 volume, bhen cloudy
Acid Number . . . . . . . 1-3 1-4
Ester „ 129-7 131-6
„ Contents expressed as C10H17COOCH3 45-4 °/0 46-0 °/0
Coefficient of Saponification of the Acetylated Oil 167-0 180-8
Total Alcohols expressed as C10H18O 52-5 °/0 57-5 °/0
Ylang-ylang oil from the Seychelles has been examined by the

chemists at the Imperial Institute. Sample No. 1 was examined in
1913; No. 2 was examined in 1910, and No. 3 is the same as No. 2, but
kept for three years and then re-examined.
i- 2. 3.
Specific Gravity at 15° C 0-9567 0-9200 0-9250

15 C.
f - 28° 5' - 30° - 28° 36'
Optical Rotation ttD \at 20° C. at 21° C. at 24° C.
Acid Value . . . . 3-3 4-2 2-6
Ester „ 126-0 42-2 53-5
Saponification value . 129-3 46-4 56-1
„ ,, after
Acetylation 181 —
Solubility in 90 per Cent. —
Alcohol . . . Gives a clear Soluble in 1 Soluble in $
solution with vol. ; beco n- vol.; becom-
less than 0-8 ing turbid ing turbid
vol.; with 0*8 with a larger with 1 or
vol. or more quantity more vols.
becomes tur-
bid
A Madagascar ylang-ylang oil has been examined by Schimmel & Co.1

Acid number 1-8
Ester „ . . . . 113-2
„ , , (after acetylation) . . . . . 160-2
On fractionation it gave the following fractions :—
Per Cent. Saponifica-

<<«o. «D. tion No.
45 to 70° 10-7 0-9848 - 5° 20' 207-2

70 „ 100° 18-0 0-9572 - 49° 16' 166-5
100 „ 110° 27-0 0-9000 - 93° 6' 37-3
110 „ 125° 12-5 0-8932 - 72° 40' 28-0
Residue 31-8 1-0725 - 3° 45' 181-0
1
Report, November, 1908, 135.
ANONACEJE 521
Umney l gives the following figures for ylang-ylang oils, which are
*not intended to be exhaustive, but represent some oils examined, showing
the percentage of non-volatile matter when the oil (about 2 or 3 grams)
is heated on the water-bath for two hours:—
Manila. Bourbon. Madagascar. Mayotte.
Specific Gravity (15°) •927 to -969 •964 to -967 •961 to -981 •947
Optical Rotation -38° „ -51° -39° „ -41° -30° „ -42° -48°
Refractive Index (20°) 1-494 „ 1-505 1-5130 1-5122 1-5070
Ester Number . 99-6 „ 153-2 142-6 to 160-1 123-2 to 171-2 114-7
Non-volatile 4-3 to 16-4 °/0 25-1 to 40-3 °/0 16-9 to 29-3 °/0 14-0 to 19 °/0
It is doubtful whether these high non-volatile residues are due to

natural constituents of the oil, or to added substances, such as benzyl
benzoate. If the oil be heated at 110° to 120° until no loss in weight
•occurs, any residue above 5 to 7 per cent, should be regarded with sus-
picion and carefully examined. The saponification value of the non-vola-
tile residues (at this temperature) for normal oils is usually from 65 to 100.
If much fatty oil is present as an adulterant, this figure will be greatly
increased, and the residue should be examined for fatty acids, which
•can be separated from the saponification liquid, and the molecular
^weight determined by titration with alkali, when an indication of the
nature of the acids is obtained.
Umney finds that in the case of the finest Manila oils the residue
obtained by evaporation does not usually exceed 6 per cent., whilst
inferior oils frequently contain much more non-volatile matter. It should
be noted that the loss by evaporation on a water-bath is not constant
even after six hours, and that if a larger quantity of oil than 1 to 2 grams
be taken the rate of volatilisation is much slower.
Benzyl benzoate, one of the natural constituents of this oil, is very
slowly volatilised when heated on a water-bath, as shown by the follow-
ing experiment: 5 grams of pure benzyl benzoate heated in a flat bronze
'dish over a water-bath showed the following loss:—
After 3 hours the loss was 9*3 per cent.
6 30-9
9 45-4
12 59-3
15 72-3
18 85-7
21 98-3
It would appear, therefore, that the presence of benzyl benzoate in
^considerable quantity in ylang-ylang oil would be shown by heating the
oil on a water-bath for a limited time. This ester, which has a high
saponification value, is comparatively inodorous, and, as it might be
employed as an adulterant, the usual tests for ylang-ylang oil should be
•supplemented by a determination of the non-volatile matter to guard
against such sophistication.
A sample of pure ylang-ylang oil distilled in Mauritius had the follow-
ing characters:—
Specific gravity 0-9J3
Refractive index (25°) 1-5072
Saponification number . . . . . . . 180
Non-volatile residue 16-6 per cent.
1
P. and E.O.R. (1914), 37, 85.
Both the specific gravity and saponification number are high, and these
factors, together with the figure for non-volatile matter, indicate a high
proportion of benzyl benzoate. The odour was somewhat coarse, and
the value of the oil was considered inferior to that of the finest Manila
oils, thus showing that the odour value is not proportional to the saponifi-
cation value.
Petroleum is sometimes found as an adulterant, especially of the
cheaper cananga oils. This is usually detectable by its odour, but the
following are the figures for a number of samples examined during
1915-16 by the author, which all contained petroleum :—
Attempts have been made by Jahrling 1 and by Gibbs to value ylang-
ylang oils in a more or less absolute manner by means of their analytical
figures. Jahrling's classification is as follows :—
Quality. Extra. I. (a) l.(b) II.
<*D Below - 35° Below - 48° Below - 60° Over - 60°

"D „ 1-4900 „ 1-4950 „ 1-4990 „ 1-4990
Saponification No. Over 145 Over 120 Over 100 100 or less
Solubility In 80 per cent. In 90 per cent. In 90 to 96 per In 96 per cent.
Alcohol Alcohol cent. Alcohol Alcohol
This classification will not bear careful examination, and must only be
accepted in a very general way, the samples proving exceptions to it
being very numerous.
This oil contains a large number of aromatic compounds. The
earliest investigation of this oil was that of Gal, who showed the presence
of benzoic acid in the form of esters. Eeychler 2 has since shown that
linalol and possibly geraniol exist, together with the sesquiterpene cadi-
nene. Pinene, ^-cresol methyl ether, and a crystalline solid melting at
138°, probably a sesquiterpene alcohol, were also shown to be present.
Eugenol has been found in cananga oil, and iso-eugenol in ylang-ylang
oil. Both these bodies are probably present in the form of their methyl
ethers.
Methyl benzoate, methyl salicylate, benzyl acetate, benzyl benzoate,
and free benzyl alcohol are present in small3 amounts, as well as methyl
anthranilate and creosol in traces. Bacon has also recently identified
formic acid, and safrol or iso-safrol.
Elze 4 has also isolated the alcohols nerol and farnesol from Java,
cananga oil, but only in very small amount.
OIL OF POPOWIA CAPE A.

This plant grows in the Ivory Coast Colony, where it is known a&
"cap6". It has been examined by E. G. and A. Camus, who found
1
2
Comptes Rendus, 76 (1873), 1482.
Bull. Soc. Chim.t iii., 11 (1894), 407, 576,
4
1045; and 13 (1895), 140.
s . Jour. S c . 3 (1908), 65. Chem. Zeit., 3 4 (1910), 857.
ANONACEÊ 523
that it was a species hitherto unnamed, and they assigned its name to it,
Messrs. Boure-Bertrand Fils l give the following account of its essential
oil. Forty-two kilos of, the leaves were distilled with steam, with cohoba-
tion of the condensed waters, and yielded 246 grams of volatile oil, of
which 160 grams had collected at the bottom of the receiver and 86
grams floated on the surface.
The last water of condensation, when exhausted with petroleum spirit,
yielded to this solvent only a very small quantity of essential oil (less than
2 grams).
In all, the yield of essential oil from the dried " cape " leaves was
therefore O59 per cent.
They determined separately the constants of the heavy and light por-
tions, then those of a mixture of these two liquids, which they call the
complete essential oil, and which was prepared by uniting the first two in
proportion to their yields.
Below are the analytical characters of the complete essential oil of
Popowia Capea:—
Optical rotation . . . . . . +76° 56'
Solubility in 80 per cent, alcohol . . . 1 vol., then cloudy
q- / 0-5 vol., then a very
" '» " ' * ' • \ slight opalescence
Acid value 2*8
„ of the acetylated oil. . 239-9
By working separately with the heavy and the light component
portions of this oil, the following constants were found :—
Heavy Portion. Light Portion*
Specific gravity at 20° C 1-00808 0-99596
Op ical rotation . .. . . . . . + 90° 54' + 51° 26'
/ 1 vol., then 1 vol., then
Solubility in 80 per cent, alcohol . . . . J very strong strong
[ cloudiness cloudiness
I 1 vol.; after 3 0-5 vol., thei*
„ 95 ,, ,, . . . ^ vols. a distinct very slight
I opalescence opalescence
Acid value 1-5 * 3-7
Saponification number 192-3 123-2
„ „ of the acetylated oil . . 24S-3 218-4
The constituents of this oil have not been investigated, but there ap-
pear to be present one or more sesquiterpene alcohols or alcohols of the
benzene series. Sodium bisulphite solution absorbs 6 per cent, of the oil.
OlLS OF MONODORA.
The seeds of Monodora myristica, a tree 50 to 60 ft. high, found in

West Africa, but also growing elsewhere, notably in Ashanti and in the
West Indies, "where it is called " Calabash Nutmeg," yield au essential
oil. A small sample of the seeds from the Gold Coast yielded on steam
distillation 5-9 per cent, of a colourless volatile oil, possessing an agree-
able lemon-like odour and taste, and appearing to consist mainly of ter-
penes.2 A larger but poorer sample (also from the Gold Coast, obtained
to make a more thorough examination) gave only 2*2 per cent, of essential
1
Roure-Bertrand Fils, Bulletin, October, 1913, 4, 15.
. Imp. Instit.j July, 1915-
oil, the aroma of which was inferior, due probably to the low condition of
the seeds. The laboratory figures of the oils from the first and second
samples were :—
First Sample. Second Sample.
Specific gravity l~0-~ . . '849 *8592
Optical rotation - 44-7° at 20° C. - 57*8° at 25° C.
Acid value 1-2 1-4
Ester value—
Before acetylation 1-9 6-4
After . 52-9 33-50
Soluble in 90 per cent, alcohol In 6 or more vols. In 4'5 or more vols.
Thorns 1 obtained a yield of 7 per cent, of oil from the seeds, which
had a specific gravity of 0*896 and optical rotation - 58*5°. The oil,
from which traces of free acids and phenols were first removed, was
fractionated in vacuo.
The terpene fraction had the specific gravity 0*842 at 20° and consisted
chiefly of limonene ; boiling-point 74° to 76° at 16 mm.; aD = - 105*68°,
and [aJD = - 125*5°; melting-point of the nitrosochloride 103° to 105°.
In the third fraction, which represents 20 per cent, of the oil, and which
boils at 110° to 116° (at 16 mm.), a body C10H16O could be detected, which
is probably identical with myristicol.
Schimmel & Co. obtained 5*37 per cent, of essential oil from the seeds,
which had the following characters: dlbo = 0*859; aD = - 117° 40'; acid
number = 1*36 ; ester number = 3*4 ; ester number after acetylation
27*11. Soluble in about 4 volumes and more 90 per cent, alcohol. It
consisted chiefly of phellandrene.
Leimbach has examined the corresponding oil from the seeds of
Monodora grandiflora. This oil has the following characters :—
Acid value 3-9
Saponification value . . . . . . . . 7 to 12
It contains Z-phellandrene, camphene (?), j9-cymene, palmitic acid,
carvacrol (?), an uninvestigated compound of the formula C10H160 (specific
gravity 0*935; optical rotation - 9° 14'; and boiling-point 130° to 154°;
which suggests that the body is not a chemical individual) ; a sesquiter-
pene (specific gravity 0*9138 ; optical rotation + 24°; and refractive
index 1*5051), and a crystalline body melting at 160° to 163°.
PITTOSPORACEÊ.
OILS OF PlTTOSPORUM.
The fruit of Pittosporum undulatum, a plant indigenous to South-

east Australia, yields, according to Power and Tutin,2 0*44 per cent, of
essential oil, whose characters are as follows :—
The oil contains d-a-pinene, d-limonene, traces of palmitic acid, sali-
cylic acid, and a phenol, small quantities of esters of formic and valerianic
acids, and a sesquiterpene of specific gravity 0*910, and refractive index
1*5030.
1 2
Ber. deutsch. pharm. ges., 14 (1904), 24. Jour. Ckem. Soc., 89 (1906), 1083.
HAMAMELIDACEÊ 525
The fruit of Pittosporum resiniferum yields 0*5 per cent, of essential
oil, obtained by expression, having the following characters :—-
Refractive index 14577
According to Bacon,1 the oil contains heptane, and a dihydroterpene,
C10H18, having the following characters :—
3O°
Specific gravity at —0 0*8050
Refractive index at 30° . . 1-4460
HAMAMELIDACE/E.
OIL OF STORAX.
The oleo-resinous substance obtained from the bark of the tree Liqui^
dambar orientale, a plant found chiefly in Asia Minor, constitutes the
liquid storax of commerce.
The oleo-resinous balsam yields from O5 to 1 per cent, of essential oil
Specific gravity . . . 0-950 to 1-050 (sometimes lower)
Optical rotation . + 1° to - 35°
Ester „ . up to 130
The very variable characters of this oil are due to differences in dis-
tillation methods, as the further the distillation is carried, the more the
amount of slightly volatile, high gravity constituents corning over.
The principal odorous constituent of the oil is styrol, or phenylethy-
lene C6H6 . CH : CH2, an optically inactive hydrocarbon boiling at 146°.
The cinnamic acid esters of ethyl, benzyl, phenyl-propyl, and cinnamyl
alcohols are also present, as well as the free alcohols, and traces of
vanillin.
The oil is adulterated with artificial esters, notably benzyl benzoate.
The volatile oil from the leaves and twigs of Liquidambar Formosana
has been examined by Kafuku.2 A yield of about 0*05 per cent, was ob-
tained. It was greenish-yellow in colour, having a specific gravity of
0-8655 at 20° C., Optical rotation - 3'3°, refractive index 1-4755 at 20° C.,
acid value nil, ester value 5*9, ester value after acetylation 25'2. It con-
sisted principally of terpenes ; camphene, a-pinene, and dipentene were
identified with certainty, nopinene and phellandrene being also indicated.
Traces of aldehydes and ketones were found to be present.
OIL OF HAMAMELIS VIBGINIANA.
The oil obtained from Hamamelis Virginiatia has the following char-
acters :—
Specific gravity . . . . 0-900 t o 0-906
Ester value about 4
(after acetylation) „ 30
Philipp. Jour. Sc.t 4 (1909), 115. *Jour. Chem. Ind. Tokio (1916), 19, 516..
$26 THE CHEMISTEY OF ESSENTIAL OILS
Jowefct and Pyman l found the oil to contain a phenol having the
odour of eugenol, free fatty acids, and a sesquiterpene having the follow-
ing values:—
Specific gravity. . 0'897
Refractive index . . 1'4916
CISTINE/E.
OIL OF LADANUM.
Ladanum or labdanum resin is a secretion from the leaves of several
species of Cistus, especially Cistus creticus and Cistus ladaniferus. Cistus
creticus is the Cretan rock rose, a native of rocky ground in Macedonia,
Thrace, Greece, and the islands of Crete, Bhodes, Sicily, and Cyprus.
Its botanical relationships are hardly decided, as it is regarded by some
as being merely a variety of Cistus villosus Linn. In Cyprus the
ladanum (labdanum) is chiefly collected by the shepherds from the
fleeces of the sheep, who unconsciously collect it from the plants whilst
pasturing, the leaves becoming very viscid with the secretion.
There seems to be a considerable amount of confusion as to the exact
botanical relationships of Cistus ladaniferus, but this has recently been
cleared up by E. M. Holmes2 in dealing with the source of Spanish
ladanum. He finds that the plant used for collecting the oleo-resin in
Spain is Cistus ladaniferus, var. macellatus. There are about sixteen
species of Cistus known in Spain, and the name Cistus ladaniferus has
been applied by different botanists to at least four different species, so
that a few remarks on the distinctive characters of the true Cistus
ladaniferus may be useful.
The plant figured under this name in Curbis's Botanical Magazine,
tab. 1112, is Cistus Cyprius Lam. and is a native of Cyprus.
Cistus ladaniferus of Gouan is Cistus Ledon of Lamarch and the
Cistus glaucus of Poures, and is a native of the South of France.
Cistus ladaniferus of Stokes's Botanical Materia Medica, vol. iii., p.
209, is Cistus polymorphus Wilkoum, and the Cistus creticus of Limnoeus.
From all these the true Cistus ladaniferus of Limnoeus is distinguished
by the ovary having ten cells; in the other five only are present.
The true Cistus ladaniferus has been described in Stokes's Botanical
Materia Medica under the name of Cistus viscosus, and by Hoffmansegg
under the name of Cistus ladanosma.
The oleo-resin yields from 0*7 to 2*0 per cent, of essential oil having
Boiling point 50° to 185° at 15 mm.
On keeping the oil becomes oxidised somewhat rapidly and deposits a
considerable amount of crystals.
According to Masson,3 the oil contains acetophenone, a compound
not hitherto found naturally occurring in essential oils; a second ketone
of the formula C9H16O, and having the following characters:—
1
2
Pharm. Jour., 91 (1913), 129.
3
P. and E.O.R. (1911), 155.
Comptes Rendus, 154 (1912), 517.
BESEDACEJE 527
Boiling-point ......... 178° to 179°
Specific gravity at 0° ........ 0-922
Optical rotation . . . . . . . . . 0°
Refractive index at 23° ....... 1-4494
Melting-point of semi-carbazone ..... 220° to 221°
Alcohols, phenols, and esters are also present in the oil. Guaiol is
probably present.
The ketone C9H16O does not react with bisulphite of sodium. It
yields a monobromide, melting-point 41°, and a semi-carbazone, melting-
point 220° to 221°. With sodium and moist ether it is reduced to the
•corresponding secondary alcohol, which forms large crystals, melting-
point 51° (boiling-point 87° at 28 mm.). With cold 3 per cent, potassium
permanganate solution the ketone is oxidised into geronic acid (boiling-
point 190° to 191° at 31 mm. ; melting-point of the semi-carbazone 164°),
the latter, when oxidised with sodium hypobromite, giving rise to bromo-
iorm and a, a-dimethyladipic acid. This shows the ketone C9H16O to be
trimethyl-1, 5, 5-hexanone-6, a body which has not been described up to
present.
CH3 . CO . CH2 . CH2 . CH2 . C(CH3)2 . CO2H
Geronic acid.
CH3
CH
HC
CH2
Trlmethyl-1, 5, 5-hexanone-6.
Emmanuel * isolated a colourless crystalline substance to which he
assigned the formula C17H30O, and the name ladaniol, but it is possible
that it is an impure form of guaiol.
The essential oils from the following two species of Cistus have been
examined by Schimmel & Co. : —2
Oil from Cistus monspeliemis (Cistaceae). Yield 0*015 per cent.;
d150 =» 0-9786 ; aD » + 1° 40' ; acid number = 15*7 ; ester number =
31*51. The light brown oil separates off between 20° and 25° abundant
quantities of paraffin of the melting-point 64°.
Oil frpm Cistus salviifolius (Cistaceae). Yield 0*024 per cent. ; d150
« 0*9736 ; aD =» + 17° 20' ; acid number = 16*86 ; ester number = 22*73.
This oil is yellowish-green, and behaves like the one mentioned before
with regard to the separation of paraffin.
RESEDACE>£.
OIL OF MIGNONETTE.
The fresh flowers of the mignonette, Eeseda odorata, yield traces,
about *002 per cent., of an essential oil of exceedingly powerful odour.
This oil is semi-solid at ordinary temperatures, and its chemistry is not
understood, as the oil is in itself so very rare. Indeed, commercially,
•An ordinary floral extract is generally used in preference to any direct
l 2
Arch. der Pharm., 250 (1912), HI. Report, October, 1903, 77.
preparation of the oil. An oil obtained by extracting the flowers with
petroleum ether, and distilling the extract with steam (the water soluble
oil1 being recovered by ether) was examined by von Soden and found to
have the following characters:—
Optical rotation . . + 31° 20'
Acid value 16
Ester „ 85
The fresh roots of this plant yield from -01 to '04 per cent, of an un-
pleasantly-smelling oil recalling the odour of radishes. This oil contains
phenyl-ethyl-thiocarbimide, C2H4(C6H5)NSC, and is a liquid of specific
gravity 1-01 to 1-09 and optical rotation about + 1° to + 2°.
TURNERACE/E.
OIL OF DAMIANA.
The leaves of various species of the Damiana plant, principally
Turnera diffusa and Turnera aphrodisiaca, yield about O5 to 1 per cent,
of essential oil. The oil has the following characters :—
Saponification value 41'8
Another sample, distilled by Schimmel & Co., was found to have a
specific gravity 0'970 and to boil between 250° and 310°. By standing,
in the cold the oil deposits crystals which probably consist of paraffin
hydrocarbons.
CANELLACEÊ.
OIL OF CANELLA BARK.
The bark of Canella alba yields from f to 1 per cent, of essential oil.
In the drug trade this bark is known frequently as " wild cinnamon,"
and is found in the south of Florida, the Bahamas, Cuba, Jamaica, Mar-
tinique, Barbadoes, etc. The whole tree is very aromatic, especially the
flowers, which perfume the neighbourhood for a considerable distance,
although they seldom open. The bark is brought to Europe in the form
of long quills, rather thicker than those of cinnamon. The taste of the
bark somewhat resembles a mixture of cloves and cinnamon, being hot,
bitter and aromatic. Meyer and Eeichex investigated the oil, of which
they obtained '94 per cent, from the bark, so long ago as 1843, and stated
that they isolated four distinct bodies from it. The first was eugenol,
the second was described as being closely allied to the principal con-
stituent of oil of cajuput, and the other two were not closely investigated.
Fliickiger and Hanbury obtained *74 per cent, of oil from the bark, and
stated that it consisted of 2 parts of an oxygenated body mixed with
1 part of a hydrocarbon resembling a mixture of mint and cajuput oils.
Eugenol, however, remained as the only well-defined body yet ascer-
tained as a constituent of the oil, till 1890, when Schimmel & Co. showed
that the body referred to by Meyer and Eeiche as resembling the princi-
pal constituent of cajuput oil was actually identical with this, being the
now well-known cineol. Williams 2 has later examined the oil, and has*
l
Annalen, 47 (1843), 234. *Pharm. Bund. (New York), 12 (1894), 183.
DIPTEKOCABPACEÊ 529
identified pinene and caryophyllene in it. The specific gravity of the oil
ranges from -920 to *935 and the optical rotation from + 1° to + 3°.
OIL OF WABBUBGIA.
The wood of Warburgia stuhlmanni, a Zanzibar tree, yields about
0*6 per cent, of essential oil, having an odour recalling that of sandal-
wood oil. Its characters are as follows :—-1
Saponification value . . . . 11-2
,, „ (after acetylation) 100*3
The oil contains aldehydes and (sesquiterpene ?) alcohols, together
with esters and traces of free acids.
DIPTEROCARPACEjE.
OIL OF BORNEO CAMPHOK.
The wood of Dryobalanops aromatica, or Borneo camphor tree, yields
this essential oil. The tree is a native of Sumatra and North-West
Borneo, but its essential oil is rarely seen in commerce.
Optical rotation . • . + 11° 5
Acid value . . . . 5-6
Ester „ . . . . 0
,, „ (after acetylation) . 50-5
The oil contains a-pinene, camp!lene d-borne ol,0 pinene, dipentener
terpineol, and sesquiterpenes.
Schimmel & Co.2 have investigated the oil with the following results.
The terpenes have the following characters:—
Specific gravity ' . 0*8631
These figures indicate the presence of a-pinene.
A fraction posssssing the boiling-point of camphene gave the following
figures: d^0 0*8639; aD + 5°37'. On hydration with glacial acetic-sulphuric
acid it afforded a large proportion of ^soborneol, but in spite of repeated
purifications from light petroleum the melting-point of the last-named
body remained as low as about 208°. Small quantities of /3-pinene were
found in a fraction possessing the following physical properties : boiling-
point 163° to 167°; duo 0 8607; a D - 0° 20'; nD.20o 1-47102. When treated
with permanganate and alkali it yielded in the form of an oxidation-
product the characteristic leaflets of sodium nopinate, from which nopinic
acid, melting-point 124° to 126°, was obtained. Oxidation of the sodium
salt with permanganate in acid solution afforded nopinone, of which the
semi-carbazone had melting-point 186° to 188°.
^-Borneol was found to occur in the following fraction, which distilled
between 55° and 85° (5 mm.). When fractionated once more it congealed
in the condenser. Filtered by suction the crude product, when tested
1 2
Ber. Pharm. (1910), 20, 351. Report, April, 1913, 33.
VOL. I. 34
for camphor with semi-carbazide, proved to be camphor-free. The
borneol, after being purified by recrystallisation from light petroleum,
melted at 204°. Its chloroform solution was dextro-rotatory.
With the object of setting free the borneol from the higher boiling
fractions of the oil and from the mother liquors, these latter were benzoy-
lated with benzoyl chloride, with the aid of pyridine. The oil which was
driven off in the steam-current by this manipulation, and which was not
esterified, proved to consist substantially of Z-a-terpineol, melting-point
35°. A fraction gave the following constants : dl50 0-9379, aD - 8° 2'.
The resulting phenylurethane melted at 112°. After saponification of
the residue of steam distillation no alcohols other than borneol were
discovered. The highest boiling fractions, boiling-point 102° to 112° (4
to 5 mm.), consisted only of sesquiterpenes. None of them, when
warmed, reacted with strong formic acid; hence no sesquiterpene alco-
hols were present. One fraction was found to possess the following
constants: boiling-point 102° (4 to 5 mm.), 256° to 260° (ordinary
pressure) ; d150 0-9200; aD - 137° 12'; nD200 1-50111. This is probably
cadinene.
OIL OF GURJUN BALSAM.
The so-called " wood oil" or gurjun balsam oil is the product of the
distillation of the oleo-resin from several species of Dipterocarpus. Gurjun
balsam resembles copaiba in its general characters, and is often used to
adulterate the latter drug. On distillation from 45 to 70 per cent, of
essential oil is obtained, which has the following characters :—
Refractive index . . . . . . . . about 1-5050
Acid value 0 to 1
Ester „ 4 „8
This oil is not employed commercially to any extent, but is used from
time to time for adulteration purposes. For example, it has recently been
detected as an adulterant of palmarosa oil, and in otto of rose in traces,
due to the adulteration of the last-named oil with geraniol manufactured
from adulterated palmarosa oil.
It can be detected by dissolving 5 to 10 drops of the suspected oil in
5 c.c. of glacial acetic acid containing 5 drops of nitric acid. In the pre-
sence of gurjun oil a red-violet colour is developed, which appears within
a minute if more than mere traces are present.
The principal constituent of the oil is a sesquiterpene or mixture of ses-
quiterpenes. These have been investigated by Deussen and Philipp,1 who
showed that the sesquiterpene mixture consisted principally of two ses-
quiterpenes which they named a-gurjunene and /2-gurjunene. Semmler,
Spornitz, and Jakubowicz 2 have also investigated these sesquiterpenes,
and consider that both of them are tricyclic compounds. Deussen and
Philipp also showed that, by the oxidation of the oil in acetone solution
by means of potassium permanganate, a ketone, C15H24O, which they
named gurjun-ketone, is formed, and which yields a semi-carbazone
melting at 234°, which serves as a useful means of identifying the oil in
mixtures.
The following method of identifying this oil (for example in otto of
1 2
Annalen, 369 (1909), 56; 374 (1910), 105. Berichte, 47 (1914), 1029, 1141.
EANUNCULACEÊ 531
1
roses) has been described by Schimmel & Co. The fraction boiling at
95° to 96° at 4 mm., or about 255° to 260° at normal pressure, is treated
with sodium and again fractionated until the boiling-point is as nearly
258° to 261° as possible, and the laevo-rotation at its highest point.
The fraction is dissolved in about 200 c.c. acetone, diluted with 35
c.c. water, and to the clear solution 15 grams of powdered potassium
permanganate are gradually added. The unattacked oil, which boils at
104° to 105° (5 mm.) is removed by fractionation and the distillation-
residue treated with semi-carbazide. The reaction-product is left stand-
ing overnight, when, after the addition of water, it is deposited as an oily
precipitate, solidifying in part after prolonged cooling in ice when stirred
with alcohol. The semi-carbazone, repeatedly recrystallised from hot
alcohol, melts at 234°, and, with a semi-carbazone of the same melting-
point and constants, prepared from gurjun balsam oil for purposes of
comparison, suffers no depression of melting-point.
Two species of Dipterocarpus are mentioned by Pearson 2 as being
used for the preparation of gurjun balsam, namely Dipterocarpus turbi-
natus and Dipterocarpus tuberculatus. Both of these have been examined
by Schimmel & Co.,3 who report thereon as follows:—
" Dipterocarpus turbinatus is a large tree which is found throughout
tropical Burma, in Bengal, and on the Andaman Islands. Its balsam is
specially known there by the name of 'gurjan oil'. It is collected in
large quantities and is used as a paint for houses and ships, as well as
a preservative for articles of bamboo. The balsam is exported from
Chittagong (Bengal). The sample received by us consisted of a faintly
-acid, milky liquid; acid value 10*9 ; specific gravity 0*9811 (15°). When
allowed to stand, especially in the warmth, it separated out into a brown
oil which floats on the surface and a viscous, whitish-grey, emulsion-like
mass. The constants of the oily layer were as follows : d150 0*9706 ; a D -
10° 8'; wD20o 1*51200; acid value 7*3 ; ester value 1*9. By steam distil-
lation we succeeded in separating out from the total balsam 46 per cent,
of a pale yellow oil of a balsamic odour, possessing the following con-
stants ; dl50 0*9271; aD - 37°; ™D2001*50070; acid value 0; ester value
1*9; soluble in 7 volumes a.m. 95 per cent, alcohol.
"Dipterocarpus tuberculatus yields a balsam of very different appear-
ance. It is known in Burma as * in oil,' and plays a very subordinate
part compared with ' gurjan oil'. The balsam is of a pale-brown
colour ; its consistency is that of turpentine, and its specific gravity at 15°
is 1*029; acid value 17*8; ester value 0. The oil which was separated
out from it by steam distillation (yield 33 per cent.) was of a yellow-
brown colour, and dissolved in 6 volumes a.m. of 95 per cent, alcohol.
Its constants were as follow : d150 0*9001; aD - 99° 40'; wD2001*50070, It
•did not contain saponifiable constituents (saponification value 0). With
Turner's colour-reaction both the balsams and the oils gave the char-
acteristic violet colour. This test consists in dissolving 3 or 4 drops of
the balsam or oil in 3 c.c. of glacial acetic acid, adding to the solution 1
drop of freshly prepared 10 per cent, sodium nitrite solution, and pouring
the mixture very carefully on 2 c.c. of concentrated sulphuric acid."
1
2
3
Commercial Guide to the Great Economic Products of India (1912), 140.
THEACEjC.
OIL OF TEA.
The leaves of the tea plant, Thea chinensis, yields a minute quantity
of essential oil. Van Eomburgh l obtained 0'006 per cent. 6f oil which
had a specific gravity 0*866, and optical rotation - 0° 11'. The principal
constituent was found to be methyl alcohol, with possibly a little acetone
(which were recovered from the watery liquid, not forming a portion of
the oil proper). In the oil, methyl salicylate and a body of the formula
C6H12O, which appeared to be of an alcoholic nature, were detected.
The latter body yielded compounds with acetic and benzoic acids.
MALVACEAE,
OIL OF MUSK SEBD.
The seeds of Hibiscus abelmoschus yield from Ol to 0-6 per cent, of
essential oil of very aromatic odour. It is known as musk seed or am-
brette seed oil, and has the following characters:—
0-880 „ 0-885 „ 45°
Acid value 75 to 140
Ester „ 70 „ 130
It is semi-solid at ordinary temperature, the melting-point varying
according to the amount of free fatty acids present.
The oil contains the alcohol farnesol, together with free palmitic acid
and constituents not yet identified. A sample of Java distilled oil, how-
ever, was liquid at ordinary temperatures, and a French oil of specific
gravity -908 did not solidify at - 10°.
RANUNCULACEÊ.
OlL OF PÔNIA MOUTAN.
The root bark of this plant, which is found in Japan and China,
yields a small amount of essential oil, which at ordinary temperatures is
of a solid consistency. It has the following characters :—
Specific gravity (superfused) at 15° 1*500
Optical activity 0°
Refractive index (superfused) at 20° 1-5646
Acid value 12-6
Ester „ 24-5
„ „ (after acetylation) 220'7
The oil consists chiefly of paeonol, which, according to Nagai,2 forms
colourless glancing prisms, melting at 50°. It has the formula C9H10Oa
and the constitution C6H3(OH)(OCH3)(COCH3). It forms a phenyl-
hydrazone melting at 170°, and is^-methoxy-o-oxyphenyl-methyl-ketone.
OIL OF NIGELLA.
The seeds of Nigella damascena yield from 0*4 to 0'5 per cent, of a
fluorescent essential oil having the following characters :—
Specific gravity . . . . . . . . 0*895 to 0'915
Optical rotation + 1°4' „ - 7-8°
Refractive index . . . . . . . . 1*5582
1 2
Schimmel's Bericht, April, 1897, 42. Berichte, 24 (1891), 2847.
FLACOUKTIACEÊ 533
The fluorescence of the oil is due to a basic compound which was
isolated by Schneider: and termed by him damascenine. This body has
the formula C10H13NO3, and melts at 26°. It is probably the methyl
ester of methylamino-methoxybenzoic acid of the constitution.
C . OCH3
HC/\C . NHCH3
CH
The seeds of Nigella sativa* yield 1/4 per cent, of oil having the
Specific gravity ........ 0'875 to 0'886
Optical rotation ........ + 1° 26' to + 3°
Refractive index ........ 1-4836 to 1'4844
Acid value . . . ...... 0 ,, 2
„ .......... up „ 32
,, ,, (after acetylation ..... ,, ,, 73
FLACOURTIACEj€.
OIL OF PHOBEKOS COCHINCHINENSIS.
According to Eoure-Bertrand Fils 3 the green leaves and stalks of this
tree, found wild in Annam, yield a small quantity of an oil resembling
sweet orange oil in odour. It has the following characters : —
Specific gravity .......... 0*9042
Optical rotation . ........ . + 3° 2'
Acid value ........ ; . . 2'5
Ester „ ........... 51-1
„ ,, (after acetylation) ....... 127-9
2
. Central., 31 (1890), 173, 191.
Schimmel's Bericlit, April, 1895, 74.
3 Report, April, 1914, 7.
APPENDIX.
OlL OF CHENOPODIUM.1
THE distillation of chenopodium oil requires special precautions, because

the chief ingredient, ascaridole, is decomposed gradually on boiling with
water. Consequently the distillation must be carried on rapidly with
steam at a good pressure, the condenser kept warm, and the warm distil-
lation water separating from the oil in tha receiver, discarded. When
chenopodium oil is properly made, the residue on fractionation will be
small, but if it has been manufactured with low-pressure steam and
without the other precautions mentioned the percentage of ascaridole
and the specific gravity will be low, and an excessive distillation residue
will be found. The distillation residue appears to consist in part of
water-soluble glycol-like substances resulting from the riydration and re-
arrangement of the ascaridole molecule. This indicates that during a
protracted distillation with low-pressure steam a part of the ascaridole
must be decomposed and the soluble products in part pass away in the
condensation water. In the producing region of Carroll County, Mary-
land, there are at least seven distilling plants in operation during the
season. From five of these factories E. K. Nelson took authentic
samples last October, and on examination the highest distillation residue
was only 2 to 3 per cent., whereas in eight samples experimentally distilled
with very low pressure steam the distillation residues amounted to from
7 to 25 per cent., and the ascaridole content was very low. The amount
of fractional distillation residue, therefore, gives an idea of the care with
which the oil has been made. In carrying out a fractional distillation,
it should be remembered that ascaridole suffers a molecular re-arrange-
ment when heated to 150°, and therefore it is necessary to maintain the
bath at as low a temperature as possible, never allowing it to reach 150°.
Most of the author's distillations were at 3 to 6 mm. pressure. During
the distillation of the ascaridol fractions a bath temperature of 115°, and
during that of the terpene fractions one of 80°, was found sufficient to
maintain an even distillation. The first distillation gave a good
separation of the terpenes from the ascaridole, and only two fractions
were registered to yield ascaridole of constant boiling-point. A very
simple test of the purity of the ascaridole fraction was found in the
readiness with which a few drops will ignite when poured on an electric
hot plate heated to about 250°. It should be noted that the estimation
of ascaridole in the way just outlined gives results somewhat low, as it
is difficult to recover all of the ascaridole from the lower fraction. The
analytical results obtained by Nelson are presented below. They show
that his seven authentic samples of oil from Carroll County conformed
to the requirements of the U.S.P., and contained 60 to 77 per cent.
i P. and E. O. R. (1920), 247 ; see also page 121.
(534)
APPENDIX 535
ascaridole. An oil distilled in Buitenzorg, Java, was found to be very
similar to the oils of American origin, and the analysis of five American
oils returned from Brazil where they had been used by the International
Health Board, and which were at least one year old, exemplified the
keeping qualities of the oil under varying conditions: the distillation
residues, while higher than those found in fresh oils, were not excessive.
Ghenopodium oils distilled from wild plants collected around Orlando,
Florida, one from dried and the 1other from green plants (both oils being
produced under the supervision of Mr. H. L. Funk, of the Bureau of
Plant Industry) were found to contain less ascaridole than the oil
distilled from cultivated plants in Maryland, but the same constituents
were found in it as in the Maryland oil. Another sample examined was
from wild plants in the Eastern United States transmitted by the
International Health Board. The results of these analyses are given
below. It should be noted that the U.S.P. (IX.) specifies that the oil
should be soluble in 8 volumes of 70 per cent, alcohol, should have a
specific gravity of O955 to 0*980 at 25°, and an optical rotation varying
between - 4° and - 10° in a 100 mm. tube at 25°. An approximate
check on the ascaridole estimation was obtained by calculating the
ascaridole content of each oil from its density, assuming that the density
of the terpenes is 0*8466, and that of the ascaridole 1*005, and that no
other constituents are present. The resulting figure is influenced, of
course, by any variations in the density of the terpene mixture and by
the amount of distillation residue which consists, of course, neither of
terpenes nor of ascaridole. The figures thus obtained will be seen to
run roughly parallel with those of the direct estimation of ascaridole by
distillation.
0 Ascaridole (per ,2
Cent, by Vol.). '§
"o v- - > «u
.
£ 11
l§ '§ i
o
1
1
H
ft . >^
'"§ '~ >> 9
G
Sample. 3 r3 jg.tg G
1 a
^ I(N
' 2 *-%
a 03 -3
P
3g
oft 3
0 — o 1
K*» ""oS &
—'
i*
& Per
PQ O
Per
CJ
'•+2
1
1 Cent. Cent. 0*
Carroll 1 . 0-9758 -4-25° Complete. 74 81-5 — 2*1° 2-3

County 2 0-9792 -3-9° do. 77 83-7 -2-15° 1-1
3 . 0-9713 -5-5° do. 75 78-7 -3-05° 1-1
1
4 . . 0-9538 -6-2° do. 60 70-0 - 1-65° 1-7
5 . 0-9592 -6-2° do. 65 71-0 -2-5° 1-1
6 . 0-9783 -3-6° do. 76 83-1 -2-0° 0-9
7 . 0-9564 -6-5° do. 64 69-3 - 2-45° 1-4
Java . 0-9762 + 0-25° do. 70 81-8 — 1-3
Florida dry wild

plants 0-9148 -7-75° Not 41 43 — 2-2
completely
soluble.
Green wild plants 0-8940 -10-25° do. 26 30 — 2-4
Eastern (U.S.)
wild plants 0-8922 + 1-65° do. 20 28-8 - 4-0° («D —
of terpenes
+ 4-15°)
American origin,
returned from
Brazil —
1 . 0-9628 -5-0° Complete. 63 73-4 — 2-7
2 . 0-9645 -7-5° do. 61 74-4 — 7-8
3 . 0-9470 -6-45° Slightly 56 63-4 — 2-8
turbid.
4 . . 0-9589 -6-6° do. 62 70-9 3-1
5 . 0-9730 - 5-33° Complete. 72 79-8 — 9-1
1
Sample of first distillation of the season.
INDEX.
ABIES alba, 32. Alpinia alba, 100.
— balsamea, 32. — galanga, 98, 100, 101.
— concolor, 60. — malaccensis, 101.
— excelsa, 27, 56. — nutans, 101.
— magnifica, 59. — omcinarum, 99.
— Sibirica, 27, 54. Amaracus dictamnus, oil of, 269.
Absinthe, oil of, 287. Amaryllidaceae, 94.
Acacia cavenia, 483. Ambrette seed, oil of, 532.
— Farnesiana, 483. Ammoniacum, oil of, 320.
Acaroid resins, oils of, 93. Amomis Jamaicensis, oil of, 388.
Aceteugenol, 335. Amomum angustifolium, 106.
Acetophenone, 172, 526. — aromaticum, 105.
Aeetovanillone, 284. — danieli, 104.
Achasma Walang, 106. — globorum, 106.
Ache des marais, 316. — medium, 100.
Achillea ageratum, 296. — melegueta, 105.
-— coronopifolia, 295. — Walang, 196.
— millefolium, 295. Amorpha fruticosa, oil of, 485.
— moschata, 296. Amorphene, 486.
— nobilis, 296. Amygdalin, 406.
— oils of, 295. Amygdalus commuis, 405.
Acorus calamus, 89. Amyl-methyl ketone, 335.
— spurius, 91. Amyl tiglate, 286.
Acrimyl isothiocyanate, 500. Amyris balsamifeva, 190, 459.
— thiocarbimide, 499. Amyrol, 190, 459.
African copaiba, 236, 237. Amyrolin, 459.
Afromomum angustifolium, 106. Anacardiacese, 462.
Agathis robusta, turpentine from, 31. Andropogon caesius, 63.
Ageratum conyzoides, 302. — citratus, 62.
Agonis flexuosa, oil of, 390. — coloratus, 62.
Ajowan seed, oil of, 318. — confertiflorus, 62.
Alantic acid, 303. — flexuosus, 62.
Alantol, 303. — gryllus, 87.
Alantolactone, 303. — Ischsemum, 87.
Alectoria, 1. — muricatus, 63, 75.
Aleppo pine, 29. — nardus, 62.
Alicula'ria scalaris, 2. — polyneuros, 63.
Allium cepa, 92. — Schoenanthus, 60.
— sativum, 92. Anethol, 505.
Allolemonal, 74. Anethum graveolens, 308.
Allspice, wild, 153. — sowa, 308, 309.
Allyl cyanide, 496. Androl, 325.
— disulphide, 321. Angelica archangelica, 318.
— isothiocyanate, 495. — anomala, 319.
— methoxy-methylene-dioxybenzene, 176. — officinalis, 318.
— oxide, 92. oils of, 318.
— propyl-disulphide, 92. refracta, 319.
— sulphide, 92, 321. Angophora Bakeri, 376.
— tetramethoxybenzene, 317. — cordifolia, 376.
— thiocarbimide, 495. — intermedia, 376.
— trimethoxybenzene, 469. lanceolata, 376.
Almonds, oil of, 405. — rnelanoxylon, 376.
Aloysia citriodora, 270. — oils of, 376.
(537)
Angophora subvelutina, 376. BACKHOUSIA citriodora, oil of, 389.
Angostura bark, oil of, 459. Balsam of Peru, oil of, 484.
Anise bark oil, 152. Tolu, oil of, 485.
— ketone, 508. Barosma betulina, 456, 457, 459.
— leaf oil, 507. crenulata, 456.
Aniseed oil, 304, 501, 505. — pulchella, 457.
star, 501. — scoparia, 459.
Anisic aldehyde, 310, 484. — serratifolia, 456, 457, 459.
Anonaceae, 512. — venusta, 457, 459.
Anthemene, 286. Basil oil, 259.
Anthemis nobilis, 285. Bay, oil of, 382.
Anthemol, 286. Californian, 170.
Apiol, 114, 308, 317. Bay berry, oil of, 119
Apium graveolens, 314. Bdellium, 464.
Aplotaxis auriculata, 297. Benzaldehyde, 406.
— Lappa, 297. — determination of, 409.
Apocynacese, 284. Benzoin odoriferum, 153.
Apocynum androsaemifolium, 284. Benzyl acetate, 277.
Apopinol, 169. — thiocarbimide, 494.
Apricot kernel oil, 405. Bergamot oil, 440.
Araucaria Cunninghamii, 42. Bergamottella, 442.
Arborvitae, 36. Bergaptene, 450, 453.
Argentine mint oil, 268. Betel, oil of, 114.
Aristolochiaceae, 191. — phenol, 115.
Aristolochia serpentaria, 192. Betula lenta, 278, 279, 282.
Arnica montana, 296. Betulol, 282.
— oils of, 296. Birch, sweet, oil of, 278, 279.
Aroideae, 89. Bisabol myrrh, 464, 465, 466.
Aromadendral, 341, 343, 346, 352, 353, Bisabolene, 105, 161, 418.
357, 358, 363, 364, 366, 368, 369, 372, Blumea balsamifera, 301.
374, 375. Bog myrtle, oil of, 119.
Aromadendrene, 344, 345, 346, 350, 351, Bois de citron de Mexique, 470.
352, 355, 356, 359, 361, 362, 364, 365, Bois d'Inde anise, 387.
367, 368, 374, 375. Bois de rose, oil of, 146, 272.
Artanthe elongata, 113. Boldo, oil of, 178.
Artemisia absinthium, 287. Borneo camphor oil, 529.
— annua, 290. Boronia, oil of, 454.
— arborescens, 292. — polygalifolia, 454.
— Barrelieri, 290. Boswellia Carterii, 466.
— campestris, 290. Brassica alba, 499.
— caudata, 292. — juncea, 495.
— Dracunculus, 292. — nigra, 495.
— frigida, 292. — rapa, 495.
— glacialis, 290. — species, 496.
— glutinosa, 293. Brisbane white sassafras, 142.
— herba alba, 290. Bruyere d'Annam, 179.
— lavandulaefolia, 293. — du Tonkin, 179.
' — leudoviciana, 292. Buchu, oil of, 456.
— maritima, 289. Bulnesia sarmientii, 461.
— oils of, 287. Bupleurol, 325.
— vahliana, 289. Bupleurum fruticosum, 324.
— vulgar is, 292. Bursera aloexylon, 470.
Artemisia-ketone, 290. — Delpechiana, 470.
Asafoatida, oil of, 321. — fagaroides, 470.
Asarone, 191. — glabrifolia, 470.
Asarum canadense, 191. Burseraceae, 273, 464.
— europaeum, 191. Butneria occidentalis, 412.
Asarylic aldehyde, 90. Butyl isothiocyanate, 500.
Ascaridol, 121, 534. Bystropogon Mollis, oil of, 268.
Ashanti pepper, oil of, 115.
Atherosperma moschatum, oil of, 177. CADE, oil of, 8.
Athrotaxis leaf oil, 40. Cadinol, 323.
— selagenoides, 40. Caerulein, 254.
Atlas cedar, 4. Cajuput oil, 378.
Aucklandia costus, 297. Calabash nutmeg, oil of, 523.
Azulene, 286, 289. Calamintha nepeta, oil of, 258.
INDEX 539
Calamene, 90. Cardamom, wild, oil of, 104.
Calamenene, 91. Carlina acaulis, 297.
Calameone, 90. — oil of, 297.
Calamus aromaticus, oil of, 89. — oxide, 297.
— camphor, 90. Carlinene, 297.
California Bay, oil of, 170. Carrot, oil of, 319.
Callitris arenosa, 45, 47. Carum ajowan, 318.
— calcarata, 48. — carui, 304.
— Drummondii, 49. — gracile, 313.
— glauca, 46. — nigrum, 313.
— gracilis, 45, 48. Carvacrol, 244, 248, 258, 263, 269, 463.
— intratropica, 45, 47. Carvene, 306, 308.
— MacJeayana, 45, 50. Carvone, 305.
— Muelleri, 50. — estimation of, 305.
— oils, 45. Caryophyllene, 117, 120, 140, 335, 481,,
— oblonga, 50. 483.
— propinqua, 46. Caryophyllenic alcohol, 481.
— robusta, 45. Caryophyllin, 335.
— rhomboidea, 48. Caryophyllus aromaticus, 330.
— Tasmanica, 45, 49. Cascarilla, oil of, 178.
— verrucosa, 46. Cascarillic acid, 178.
Callitrol, 45. Cassia oil, 122.
Calycanthaceae, 412. lead in, 131.
Calycanthus floridus, 413. Cassie oil, 483.
— oils of, 412. Cathelus, fasciculata, oil of, 178.
— occidentalis, 412. Cedar camphor, 2, 5.
Camphor oil, 155. — leaf oil, 39.
Borneo, 529. — wood oil, 2, 494.
— heavy, 159. Cedrela brasiliensis, 494.
— Indian, 163. odorata, 494.
— leaf oil, Japan, 164. velloziana, 494.
— light, 160. Cedrene, 3.
— Malay States, 162. Cedrenol, 3.
— Mauritius, 162, 163. Cedrol, 2.
— tree, false, 164. Cedrus Atlantica, 4.
— tree, Ibean, 155. — deodara, 5.
Nepal, 143. — Libani, 4.
Camphora omcinalis, 155. Celery, oil of, 314.
Camphorene, 161. — top pine, 52.
Camphorogenol, 160. — wild, oil of, 316.
Cananga odorata, 512. Cetraria islandica, 1.
— oils of, 512. Chamaecyparis Lawsoniana, 7, 8-
java> 518. — obtusata, 7.
Canarium colophania, 469. — sphaeroidea, 39.
— euptoron, 469. Chamomile oil, 285.
— luzonicum, 467. Roman, 285.
— microcarpium, 469. German, 285.
— Schweinfurthii, 469. Chamomillol, 286.
— species, 467. Champaca flowers, oil of, 508.
— villorum, 469. — wood, oil of, 508.
Canella alba, oil of, 528. Champacol, 462.
— trista, 133. Champa-ka-utter, 510.
Canellaceae, 528. Chavica betle, 114.
Canelo tree, 153. Chavicol, 99, 115, 387.
Cannabinaceae, 115. Cheiranthin, 501.
Cannabinol, 118. Cheiranthus cheiri, 500.
Cannabis indica, 118. Chian turpentine, 462.
— sativa, 117. Chrysanthemum cinariaefoHum, 303,
Cannibene, 118. — Japonica, 303.
Capparapene, 153. — marginatum, 303.
Capparapi, oil of, 153. Chenopodium oils, 121, 534.
Capparapiol, 153. Cinnamic aldehyde, 129, 130, 131, 381.
Caraway oil, 304. Cinnamomum camphora, 155, 164.
— chaff oil, 306. — cassia, 122.
Cardamom, oil of, 101. — Ceciodaphne, 143.
— root, oil of, 105. — culilawan, 142.
Cinnamomum glanduliferum, 141. Copaiba, Surinam, 475, 476.
— Kiamis, 142. Copaifera species, 475.
— Litrea, 151. Copal limon, 470.
— Loureirii, 141. Coriander oil, 306.
— oil, 132. Coriandrol, 307.
— Oliver!, 142. Coriandrum sativum, 307.
— Parthenoxylum, 143. Costene, 298.
— peditinervium, 142. Costic acid, 298.
— pedunculatum, 143. Costol, 298.
— zeylanicum, 132. Costus lactone, 297.
Cistinese, 526. — root oil, 297.
Cistus creticus, 526. Coumarin, 202.
— ladaniferus, 526. Creosol, 522.
— monospeliensis, 527. Crithmum maritimum, 325.
— salvifolius, 527. — siculum, 325.
— species, 526. Croton cascarilla, 178.
Citral, 74, 417, 420. — Eluteria, 178.
— determination of, 420. Crotonyl iso-sulphocyanate, 499.
Citraptene, 418, 453. Cruciferae, 495.
Citron, oil of, 451. Cryptomerene, 6, 7.
Citronella grass, 62. Cryptomeria oil, 5.
— oil, Burmese, 71. — leaf oil, 6.
— Ceylon, 64. Cryptomeriol, 6.
— Formosan, 71. Cubebs, oil of, 109.
— French Guiana, 71. — false oil of, 110, 115.
— German New Guinea, 71. Cuitapatti, 285.
— Jamaican, 71. Culilavan oil, 142.
— Java, 67, 68. Cumic aldehyde, 140, 178, 268, 312, 341,
'— Seychelles, 71. 363, 366, 451, 465, 484.
Citronellal, 67. Cumin oil, 311.
Citrus aurantium, 425. Cuminum cyminum, 311.
(Bergamia), 440. Cupressinae, 2.
— bigaradia, 425. Cupressus lusitanica, 35.
— decumana, 450. — sempervirens, 35.
— limetta, 439. Curcuma longa, 106.
— limonum, 413. — Zedoaria, 107.
— madurensis, 427. Cusparia trifoliata, 459.
— medica, 413, 439, 451. Cymbopogon caesius, 63.
— nobilis, 427. — coloratus, 62, 86.
— triptera, 435. — confertiflorus, 62, 64.
— vulgaris, 425. — citratus, 62, 71, 72.
Clary, oil of, 257. — flexuosus, 62, 72.
Clausena anisum-olens, 461. — Iwarancusa, 60.
Cloves, oil of, 330. — javanensis, 87.
— leaf, oil of, 335. — Martini, 63.
Cnidium officinale, 329. — nardus, 62, 64, 68, 71.
Cochin grass, 62. — polyneuros, 63, 86.
Cochlearia officinalis, 500. — Schoenanthus, 60.
Cocos nucifera, 88. — Sennaarensis, 74.
Coleus amboinicus, 269. — Winteranus, 64.
Colorado Douglas fir, 57, 58. Cypral, 7.
Commiphora oils, 464, 466. Cypress camphor, 36.
Compositse, 285. — leaf oil, 36.
Coniferse, 2. Cypressene, 7.
Conium maculatum, oil of, 328.
Convolvulus floridus, 272. DACRYDENE, 50.
— scoparius, 272. Dacrydium Franklini, 50.
Copaene, 482. Dacroydes hexandra, 469.
Copaiba, African, 236, 237, 480, 481, 482 Damascenine, 533.
— Angostura, 475, 476. Damiana, oil of, 528.
— Bahia, 475, 476. Daniella thurifera, 486.
— Cartagena, 475, 476, 477. Daon Sisirihan, 115.
— Maracaibo, 475, 476, 477. Darwinia fascicularis, 360, 377.
— Maranham, 475, 476, 477. -»~ grandiflora, 378.
— Maturin, 475, 476. — taxifolia, 378.
— Para, 475, 476, 477. Daucus carota, 319.
INDEX 541
Decyl aldehyde, 38, 98, 99, 435, 453, 484. Eucalyptus, Bseuerleni, 350.
Dementholised peppermint oil, 226. — Baileyana, 350.
Dhelum Wangi, 251. — Behriana, 351.
Diallyl disulphide, 92. — Bicolor, 351.
Dicitronelloxide, 70. — Bosistoana, 351.
Digger pine, 58. — botryoides, 351.
Dihydro-costus-lactone, 298. — Bridgesiana, 351.
Dihydrocuminic acetate, 238. — Calophylla, 351.
— alcohol, 38, 238, 242. Cambagei, 352.
— aldehyde, 164, 264. — Gampanulata, 352.
Dihydroxy-thymoquinone, 242. — camphora, 352.
Dilem oil, 251. — capitellata, 352.
Dill apiol, 114, 308, 326. — carnea, 352.
— oil of, 308. cinerea, 353.
Dimethoxy-coumarin, 418. — citriodora, 353.
Dimethyl sulphide, 251, 496. — cneorifolia, 353, 363.
Diosma succulentum, 457. — coccifera, 353.
Diosphenol, 456. — conica, 354.
Dipterocarpaceae, 529. — cordata, 354.
Dipterocarpus, oil of, 530. — coriaceae, 354.
— tuberculatus, 531. — corymbosa, 354.
— turbinatus, 531. — cosmophylla, 354.
Dorema ammoniacum, 320. — crebra, 355.
Doremol, 321. — Dawsonii, 355.
Doremone, 321. — dealbata, 355.
Doremyl acetate, 321. — delegatensis, 355.
Douglas fir, 56, 57. — dextropinea, 355.
Drimys Winteri, 511. — diversicolor, 355.
Dryobalanops aromatica, 529. — dives, 345, 346, 356.
— dumosa, 340, 356.
ELÊIS guineensis, 88. — eugenoides, 356.
Elecampane, oil of, 303. — eximia, 356.
Elemi, oil of, 467. — fasciculosa, 357.
Elemicin, 143, 144, 468. — fastigata, 356.
Elemol, 469. — Fletcheri, 357.
Elionurus thymiodorus, 87. — fraxinoides, 357.
— tripsacoides, 87, 88. — globulus, 340, 341, 357.
Elletaria cardamomum, 103. — gomphocephala, 358.
Elsholtzia cristata, 265. — goniocalyx, 358.
Ericaceae, 278. — gracilis, 358.
Erigeron canadensis, 302. — gunnii, 358.
Erithamia Caroliniana, oil of, 293. — hsemastoma, 344, 358.
Eryngium Fcetidum, oil of, 328. — hemilampra, 359.
Erythroxylon coca, 282. — hemiphloia, 359.
Esters, artificial (vide Bergamot and — intertexta, 359.
Lavender oils). — lactea, 359.
Estragol, 260, 261, 293. laevopinea, 359.
Ethyl-amyl-carbinol, 224. — largiflorens, 360.
Ethyl-amyl-ketone, 202. — linearis, 345.
Ethyl citrate, 442. — longifolia, 360.
— oxalate, 444. — loxophleba, 360.
— succinate, 444. — Luehmanniana, 360.
— tartrate, 444. — Macarthuri, 360.
Eucalyptol determination of, 336. — macrorhyncha, 361.
Eucalyptus, oils of, 336. — maculata, 353, 361.
tables of, 342, 343, 344. — maculosa, 361.
— acacieeformis, 345. — marginata, 361.
— acervula, 345. — megacarpa, 361.
— acmenoides, 346. — microcorys, 861.
— aggregata, 346. — microtheca, 362.
— albens, 346. — Morrisii, 362. .
— amygdalina, 340, 346, 348. — Muelleri, 362.
— Andrewsi, 348. — nigra, 362.
— angophoroides, 348. — Nova Angelica, 362.
— apiculata, 348. — obliqua, 363.
— Australiana, 340, 348. — occidentalis, 363.
Eucalyptus, odorata, 363. Eupatorium, oils of, 298.
— oleosa, 340, 363. — triplinerve, 298.
— oreades, 364. Euphorbiacese, 178.
— ovafolia, 364. Evernia furfuracea, 1.
— paludosa, 364. — prunastri, 1.
— paniculata, 364. Evodene, 460, 461.
— patentinervis, 364. Evodia rutsecarpa, oil of, 460.
— pendula, 364. — simplex oil of, 453.
— perriniana, 365.
— phlebophylla, 365. FAGABA Xanthoxyloides, 453.
— pilularis, 365. Farnesol, 405, 484, 485, 532.
— piperita, 341, 365. Fenchone, 203, 310.
— Planchoniana, 365. Fenchyl alcohol, 16, 203.
— Platypus, 365. Fennel, oil of, 302.
— polyanthema, 366. — sea, oil of, 325.
— polybractea, 340, 366. Italian, 326.
— populifolia, 366. Sardinian, 326.
— propinqua, 366. Fenchyl alcohol, 16, 203.
— pulverulenta, 366. Ferula Narthex, 321.
— punctata, 366. — Scorodosma, 321.
— quadrangulata, 367. — Sumbul, 327.
— radiata, 367. Ferulene, 321.
— redunca, 367. Feverfew, oil of, 287.
— regnans, 367. Firpene, 17.
— resinifera, 367. Flacourtiacese, 533.
— risdoni, 367. Fleabane, oil of, 302.
— rosii, 368. Florida cedar, 2.
— rostrata, 341, 368. Fceniculum dulce, 309.
— rubida, 368. — piperitum, 310.
— rudderi, 368. — vulgare, 309.
— saligna, 368. Formylation process, 491.
— salmonophloia, 368. Frankincense, oil of, 466.
— salubris, 369. Fusanus spicatus, 189.
— santalifolia, 369. Fustic, oil of, 463.
— siderophloia, 369.
— sideroxylon, 369. GALANGAL, oil of, 99.
— Smithii, 340, 369. Galbanum, oil of, 323.
— squamosa, 372. Galipea cusparia, 459.
— staigeriana, 372. Galipene, 460.
— stellulata, 373. Galipol, 460.
— stricta, 373. Gardenia florida, 273.
— Stuartiana, 373. — grandiflora, 273.
— Tseniola, 373. — oil of, 273.
— tereticornis, 373. Garlic, oil of, 92.
— tessellaris, 374. Gaultheria, oil of, 278, 279.
— trachyphloria, 374. — procumbens, 278.
— umbra, 374. —• punctata, 283.
— unialata, 374. Genepides alpes, 290.
— urnigera, 374. Geraniaceae, 486.
— vernicosa, 375. Geranium oil, 486.
— viminalis, 375. Algerian, 490.
— virgata, 375. Bourbon, 490.
— viridis, 375. Corsican, 490.
— vitrea, 375. French, 490.
— Wilkinsoniana, 375. Indian, 490, 491.
— Woollsiana, 375. Sicilian, 490.
Eudesmic acid, 346, 348. Spanish, 490.
Eudesmol, 341, 352, 354, 357, 358, 361, Ginger, oil of, 98.
364, 365, 367, 370, 373. Gingergrass alcohol, 3.
Eugenia pimenta, 388. Gingrass oil, 79, 85.
— caryophyllata, 330. Globulol, 341, 358.
— Smithii, oil of, 335. Glyceryl acetate, determination of, 445.
Eugenol, 335, 387. Golden rod oil, 300.
— determination of, 333. Gouft, oil of, 290.
Eupatorium capillifolium, 298. Graminese, 60.
—•foenieulaceum, 298. Grape fruit oil, 450.
INDEX 543
•Grass oils, 60. Irone, 96.
Griffes de girofle, 393. Isoalantolactone, 303.
Guaicum officinale, 461. Isoamyl angelate, 286.
— wood oil, 893, 461. Isobutyl angelate, 286.
Guaiol, 45, 462, 527. Isocedrol, 3.
Gurjan oil, 531. Isocostene, 298.
Gurjun balsam oil, 530. Isocryptomeriol, 6.
detection of, 531. Isomenthol, 225.
— ketone, 482, 530. Isomenthone, 225, 243.
Gurjunene, 530. Isoneomenthol, 225.
Isononylic acid, 117.
HAMAMELIDACEÊ, 525. Isovaleric aldehyde, 185, 220, 230, 242.
Hamamelis virginiana, oil of, 525. lu-chhiu, 168.
Hardwickia Mannii, 482. Ivaol, 296.
— pinnata, 483.
Hedeoma pulegoides, 243. JABOBANDI leaf oil, 460.
Hedeomol, 243. Japanese pepper oil, 452.
Heeria paniculosa, oil of, 464. Jasmal, 277.
Helenine, 303. Jasmine, oil of, 274, 277.
Helichrysum angustifolium, 302. — pomade, 277.
Heliotropine, 486. Jasminum azonicum, 276.
Hemp, oil of, 117. — gnndiflorum, 274.
— Indian, 118. — hirsutum, 276.
Heptane, 24, 525. — odoratissimum, 276.
Heptine, 17. — officinale, 274.
Heptyl-methyl ketone, 335. — paniculatum, 277.
Herabol myrrh, 464. — revolutum, 277.
Heracleum giganteum, 324. — sambac, 274.
— oils of, 323. Juglandaceae, 118.
— sphondyleium, 32*3. Juglans regia, 118.
Hernandia peltata, 164. Jungermanniacese, 1.
Hexenol acetic ester, 226. Juniper, oil of, 33.
Hexyl angelate, 286. Juuiperus communis, 33.
— tiglate, 286. — oxycedrus, 8, 35.
Hibiscus abelmoschus, 532. — phcenicea, 34, 35, 38.
Himeshiho. — procera, 4.
Hops, oil of, 116. — sabina, 37.
Humulene, 117. — thurifera, 37.
Humulus lupulus, 116.
Huon pine, 50. KEMPFERIA ethelse, 108.
Hyacinth, oil of, 93. — galanga, 107.
Hydrocinnamic aldehyde, 139. — rotunda, 107.
Hydrocyanic acid, determination of, 411. Kesso oil, 285.
Hydrokinone methyl ether, 508. Kessyl acetate, 285.
Hydrothymoquinone, 7. — alcohol, 285.
Hydroxypaeonol, 94. Kobushi tree, oil of, 508.
Hypopitys multiflora, 282. Kuromoji oil, 151.
Hyssop oil, 264.
Hyptis suaveolens, 254, 263. LABIATJE, 192.
Ladanum, oil of, 526.
IBEAN camphor tree, 155. Lagam balsam, 469.
Illicium anisatum, 502. Lana batu grass, 62.
— Griffithii, 502. Lantana camara, oil of, 271.
— parviflorum, 508. — odorata, oil of, 272.
— religiosum, 146. Larix decidua, 32.
— verum, 501. Lauracese, 122.
Imperatoria ostruthium, 326. Laurel leaves, oil of, 171.
Incense cedar, 8. Laurus benzoin, 153.
Indian hemp oil, 118. — camphora, 155.
Indol, 273, 276, 278, 435, 486, 501. — nobilis, 171.
Inula helenium, 303. — sassafras, 154.
lonone, 98. Lavande femelle, 193.
Iridese, 96. — moyenne, 193.
Iris florentina, 96.' — petite, 193.
— germanica, 96. Lavender, bastard, 193.
— pallida, 96. — oil of, 192, 197.
Lavender, oil of English, 200, 201. Marjolaine douce, 247.
spike, 193, 204. — sauvage, 247.
Lavendula Burmanni, 203. Marjoram oil, 247, 248.
— Delphinensis, 193. Cyprus, 248, 249.
— dentata, 202. Marsh tea, oil of, 283.
— fragans, 193. Massoia aromatica, 150.
— hybrida, 193. Massoi bark oil, 150.
— latifolia, 193. Masterwort, oil of, 326.
— officinalis, 193. Mastic, oil of, 462.
— pedunculata, 203. Mastigobryum trilobatum, 1.
— spica, 193, 204. Matico camphor, 113.
— stoechas, 203. — oil of, 113.
— vera, 192. Matricaria chamomilla, 285.
Lebanon cedar, 4. — parthenium, 287.
Ledene, 283. Meadow sweet, oil of, 412.
Ledum camphor, 283. Melaleuca bracteata, 381.
— palustre, 283. — cajuputi, 379.
Leguminosee, 475. — genistifolia, 381.
Leioscyphus Taylori, 1. — gibbosa, 381.
Lemon oil, 413. — leucadendron, 378.
Spanish, 419. — linarifolia, 380.
terpeneless, 424. — Maideni, 380.
Lemoncillo, 386. — minor, 378, 379.
Lemongrass, 63, 270. — niaouli, 382.
— oil, 71, 72, 73. — nodosa, 381.
Lenabatu grass, 62. — oils of, 378.
Leptosperum flavescens, 377. — pauciflora, 382.
— liversedgei, 377. — Smithii, 380.
Levisticum officinale, 314. — thymifolia, 380.
Libanone, 4. — trichostachya, 381.
Librocedrus decurrens, oil of, 8. uncinata, 380.
Licari kanali, 148. viridiflora, 382.
— guianesis, 148. Melaleucol, 380.
Lichenol, 1. Meliacese, 494.
Liliacese, 92. Melissa officinalis, oil of, 255.
Limes, oil of, 439. Mentha aquatica, 239.
Limettin, 418. arvensis, 212.
Limoncello di Spagna, 439. — canadensis, 212.
Linaloe oil, 272. — longifolia, 237.
Cayenne, 146. — micrantha, 242, 243.
Mexican, 469. — piperita, 212.
seed oil, 475. — pulegium, 242.
Linalol monoxide, 472. — silvestris, 340.
Linalyl isobutyrate, 140. — spicata, 237.
Lindera benzoin, 282. — verticellata, 237.
— sericea, 151. — viridis, 237.
Lippia citriodora, 270. Menthene, 230.
Liquidambar Formosana, 525. Menthenone, 224.
— orientale, 525. Menthol, 225.
Litsea odorifera, 155. — determination of, 235.
Liverworts, oils of, 1. Menthone, 225, 231, 243.
Lodgepole pine, 58. Menthyl-iso-valerianate, 220.
Longifolene, 30. Meriandra benghalensis, oil of, 268.
Lophanthus anisatus, 267. dianthera, oil of, 268.
— rugosus, 267. Mespilodaphne pretiosa, 154, 389.
Lovage, oil of, 314. Methoxy-chavicol, 115, 152.
Methoxy-diphenyl ether, 94.
Methoxy-oxyphenyl-methyl-ketone, £ 32.
MACE, oil of, 172, 176. Methoxy-resorcylic acid, 273.
Madotheca levigata, 1. Methoxy-salicytic acid, 273.
Magnoliacese, 508. Methyl-amino-methoxybenzoic ester, 533.
Magnolia Kobus, 508. Methyl-amyl-carbinol, 335.
Maha pengiri grass, 62. Methyl-anthranilate, 273, 276, 278, 418,
Malabar grass, 62. 426, 435, 437, 486, 501, 511, 522.
Malvaceae, 532. Methyl-butenyl-dimethoxy-methylene-di-
Mandarin orange oil, 427. oxybenzene,114.
INDEX 545,
Methyl-chavicol, 260, 261, 262, 267, 293, Myrtol, 329.
310, 387, 458, 461, 508. Myrtus communis, 329.
Methyl-cyclo-hexanone, 243.
Methyl-heptenol, 472. NARDOSTACHYS Jatamansi, 285.
Methyl-heptenone, 418, 471. Nasturtium, oil of, 494.
Methyl-heptyl-carbinol, 88, 335. tfectandia caparrapi, 153.
Methyl-heptyl-ketone, 88, 455. — Puchury, 152.
Methyl-methyl-anthranilate, 108, 455. elitris species, 274.
Methyl-nonyl-carbinol, 88,155, 172. Neomenthol, 225.
Methyl-nonyl-ketone, 88, 89, 452, 453, 455, Nepal sassafris, 141.
456, 460. — camphor tree, 143.
Methyl-salicylate, 282. Nepeta cataria, oil of, 267.
Methyl-tetrahydroacetophenone, 5. — Nepetella, oil of, 268.
Methyl-undecyl-ketone, 88. Nero de Bergamotte. 442.
Meum athamanthicum, 329. Neroli, 149, 202, 405, 435.
Michelia aurantiaca. 510. — oil of, 425, 428.
— champaca, 510. --- Algerian, 435.
— longifolia, 510, 511. --- Chinese, 435.
— Rheedii, 510. --- Sicilian, 434.
— runner vis, 510. --- Spanish, 434.
Micromeria Chamissonis, oil of, 269. --- Syrian, 435.
Mignonette, oil of, 527. Nerolidol, 380, 435, 436, 484.
Mint, water, oil of, 239. Niaouli oil, 332.
Monarda citriodora, 241. Nigella damascena, oil of, 532.
— didyma, 241. — sativa, oil of, 533.
— fistulosa, 242. Nonyl aldehyde, 98, 99, 139, 405, 418.
— myristica, 241. N"onylene-methyl ketone, 155, 172.
— oils of, 240. Nopinene, 525.
Monimacese, 177. Norisoborneol, 185.
Monodora grandiflora, 524. Nortricycloeksantalal, 186.
— myristica, 523. Norfcricycloeksantalene, 185.
— oils of, 523. Nuanua leaves, oil of, 274.
Monotropha hypopitys, 282. Nutmegs, Bombay, 175.
Moreton Bay pine, 42. — New Guinea, 175.
Mosla grosserata, 263. — oil of 172, 176.
— japonica, 262.
— oils of, 262.
Motia grass, 63, 79, 82. OCTYL aldehyde, 418.
Mountain balm oil, 259. Olibanol, 467.
Mousse de Ch£ne, 1. Opoponax Chironium, 466.
Musk root, oil of, 327. — oil of, 466.
Mustard oil, 495. Orange, flower oil, 425, 428.
determination of, 497, 499. oil of, 425.
white, 499. --- bitter, 426.
Myrcene, 117, 162, 387. --- Manila, 426.
Myrcenol, 117. --- Mandarin, 427.
Myriaceae, 119. -- -- (Japanese), 427-
Myrica asplenifolia, 120. --- Spanish, 426.
— cerifera, 119. --- Tangerine, 427.
— gale, 119. ---- (Spanish), 427.
Myristica argentea, 175. -- . _ West Indian, 426.
— fragrans, 172.
— Malabarica, 175. Moutan, 532.
Myristic aldehyde, 155. Paeonol, 94, 532.
Myristiceae, 172. Palmarosa oil, 79, 84.
Myristicin, 143, 144, 176, 263. Palo Balsamo, 461.
Myroxylon Balsamum, 484, 485 — Santo, 462.
Myrrh, bisabol, 465, 466. Paracotene, 177.
— herabol, 464. Paracoto bark, oil of, 177.
— oils of, 464. Paracotol, 177.
Myrtaceae, 329. Parmelia, 1.
Myrtenal, 164. Parmeliaceae, 1.
Myrtenol, 3. Parsley, oil of, 317.
Myrtle, bog, oil of, 119. Parsnip, oil of, 327.
— oil of, 329. Parthenium argentatum, 302..
— wax, 119. Pastinaca sativa, 327.
VOL. I. 35
.546 THE CHEMISTEY OF ESSENTIAL OILS
Patchouli camphor, 254. Pilocarpus jaborandi, 460.
— oil of, 250. Pimenta acris, 382.
Java, 251, 252, 253. — officinalis, 388.
Singapore, 250, 252, 253. — oil of, 388.
Paracresol, 501. Pimpenella anisum, 304, 501.
— methyl ether, 522. Pine-needle oils, 53, 61.
Peach kernel oil, 405. Pinocarveol, 358.
Pelargonium species, 486. Pinus abies, 27.
Pelea Madagascarica, 461. — australis, 17.
Pennyroyal oil, 242. — cembra, 27.
American, 243. — contorta, 24, 58.
Pentane, 17. — echinata, 17.
Pentene, 17. — edulis, 25.
Pepper, Japanese, oil of, 452. — halepensis, 29, 32.
— oil of, 115. — heterophylla, 17, 19.
Peppermint oil, 211. — insularis, 32.
American, 213. — Jeffreyi, 26.
British E. African, 235. — Khasya, 32.
Chinese, 228. — Lambertiana, 25, 59, 344.
Dalmatian, 234. — laricio, 30.
dementholised, 226. — Ledebourii, 26.
English, 230. — longifolia, 12, 30, 55.
French, 228. — Merkusii, 32.
German, 233. — monophylla, 26.
(Colonial), 227. — palustris, 15, 17, 19.
Hungarian, 234. — picea, 29.
Italian, 231. — pinaster, 29, 32.
Japanese, 213, 222. — ponderosa, 23, 26, 59.
Javan, 235. (scopulorum), 23.
Mitcham, 227, 231. — pumilio, 55.
Russian, 232. — Sabiniana, 24, 58.
Perilla arguta, 264. — Sylvestris, 26, 27, 53.
— citriodora, 2€4. — Taurica, 27.
— oils of, 264. — Thumbergii, 32.
Perillic alcohol, 85. Piper acutifolium, 113.
— aldehyde, 85, 164, 264. — Aduncum, 115.
Persea gratissima, 152. — angustifolium, 113.
— peruviol, 484. — asperifoiium, 113.
— pubescens, 152. — betle, 114.
Petitgrain, oil of, 426, 436. — camphoricum, 113.
citronnier, 437. — guineense, 115.
lemon, 437. lineatum, 115.
lime. 437, 438. — longum, 115.
Mandarin, 437. — Lowong, Ho.
Petroselinum sativum, 317. — mollicomum, 113.
Peucedanum oils, 308, 323, 328. — nigrum, 115.
Phellandrium aquaticum, 310. — officinarum, 115.
Phenyl-acetic acid, 435. Piperaceae, 109.
Phenyl-aceto-nitrile, 436. Piperitone, 343, 345, 348, 354, 355, 356
Phenyl-ethyl-alcohol, 405, 435, 493. 360, 364, 367, 373, 375.
Phenyl-ethylene, 525. Piperonal, 242.
Phenyl-ethyl-thiocarbimide, 528. Pistacia lentiscus, 462.
Phenyl-glycol-methylene-acetal, 277. — terebinthus, 462.
Phenyl-propyl esters, 525. Pittosporaceee, 524.
Pherosphaera Fitzgeraldi, 52. Pittosporum resiniferum, 525.
Phloroglucintrimethyl ether, 301. — undulatum, 525.
Phlorol dimethyl ether, 296. Plectranthus graveolens, 250.
— isobutyric ether, 296. Pluchea fcetida, 301.
Phoberos cochinchinensis, 533. Pneumus Boldo, 178.
Phthalylisopropylidene, 315. Pogostemon Heyneamus, 251.
Phyllanthus cochin-chinensis, 178. — patchouli, 250, 251.
Phyllocladene, 53. Polianthes tuberosa, 94.
Phyllocladus Bhomboidalis, 52. Polygala species, 282.
Picea excelsa, 32. Poplar buds, oil of, 120.
Pichurim, oil of, 152. Popowia capea, 522.
Pilea, oil of, 120. Populus nigra, 120.
INDEX 547
Potassium myronate, 495. Rue, oil of, Algerian, 454.
Primulacese, 272. French, 454.
Primula officinalis, 272. Spanish, 454.
Primulaverin, 273. Syrian, 455.
Prisprioca, 389. Rusa grass, 63.
Prostanthera cineolifera, 268. Ruta bracteosa, 454, 455.
Protaceee, 172. •! — graveolens, 454.
Prunus laurocerasus, 412. — montana, 454, 455.
— virginiana, 412. Rutaceae, 413.
Pseudo-cedrol, 3.
Pseudo-ionone, 98. SABAI, serrulata, 88.
Pseudotsuga Douglasii, 32, 57. Sabinene, 38, 121, 298, 311.
— glauca, 57. Sabinol, 38.
— taxifolia, 56, 57. Safrene, 145.
Ptychotis Ajowan, 318. Safrol, 145.
Pulegium micranthum, 242, 243. Sage, oil of, 255.
Pulegone, 240, 243, 259, 269. black, 257.
Purpulut, 254. Salicinae, 120.
Pycnanthemum lanceolatum, 269. Salicylic aldehyde, 412.
Pyrethrum parthenium, 287. Salvene, 256.
Salvia cypria, 256.
RAMALINA calicaris, 1. — lavendufolia, 206.
Ramona stachyoides, 257. — mellifera, 257.
Ranunculacese, 532. — officinalis, 255.
Ravensara aromatica, oil of, 390. — sclarea, 257.
Resedacese, 627. — trilobata, 256.
Reseda odorata, 527. Sandalwood oil, 179.
Rhodinol, 405. East African, 191.
Rhodium, oil of, 272. Indian, 179.
Rhododendron, oil of, 284. Fiji, 188. r
Rhus cotinus, oil of, 463. Guiana, 169.
Robinia pseudacacia, oil of, 486. New Caledonian, 188.
Rosa alba, 391. Hebrides, 188. ;
— Brunner, 395, 397. South Australian, 189.
— centifolia, 394. Tahiti, 188.
— damascena, 391, 394. West Australian, 189.
— d'Hay, 395, 396, 397. Indian, 189, 459, 482,
— Druski, 395. Santalacese, 179.
— Paul Nabonnand, 395, 397. Santalal, 188.
— Safranos, 395. Santalene, 3, 186.
— Van Houtte, 395, 397. Santalic acid, 188.
Rosaceae, 390. Santalol, 3, 186.
Rose, oil of, Anatolian, 393. Santalone, 186.
Bulgarian, 391, 395. Santalum album, 179.
French, 394, 396. — austro-caledonicum, 188.
German, 399. — cygnorum, 189.
r Hungarian, 399. — Freycinetianum, 188.
Persian, 401. — Preissianum, 189.
Russian, 399. — Yasi, 188.
Spanish, 399. Santene, 54, 185.
Spartan, 400. Santenone, 185.
Rosemary, oil of, 205. — alcohol, 185.
Corsican, 208. Santolina chamsecyparissus, 304.
Dalmatian, 207. Santolinenone, 304.
English, 208. Sassafras officinale, 144.
French, 207. — oil, 144.
Greek, 208. artificial, 146.
Sardinian, 208. Brisbane white, 142.
Spanish, 207. Nepal, 141.
Tunisian, 208. Satureja, oils of, 257.
wild, 283. — Calamintha, oil of, 258, 259,
Roses des Jardins, 397. — cuneifolia, oil of, 258. .
Rosewood, oil of, 146, 272. — hortensis, oil of, 258, 259.
Rosmarinus officinalis, 205. — montana, oil of, 257.
Rubiaceae, 273. — thymbra, oil of, 258.
Rue, oil of, 454. Saussurea lappa, 297.
Savin oil, 37. Tansy, oil of, 294.
:Savory oil, 257. Tasmanol, 345.
Saw Palmetto, oil of, 88. Taxodium distichum, oil of, 7.
Scheih, oil of, 290. Tea, oil of, 532.
Schimmel's test, 67. Teresantalic acid, 188.
:Schimmelia oleifera. 190. Teresantalol, 186.
Schinus molle, oil of, 463. Terpinyl acetate, detection of, 444.
Scurvy grass, oil of, 500. Tetranthera polyantha, 153.
.Sea fennel, oil of, 325. Theaceae, 532.
Sedanolic acid, 314. Thea chinensis, 282, 532.
-Sedanolide, 314. Thuja leaf oil, 36.
Sedanonic acid, 314. — occidentalis, 36, 39.
:Selinene, 316. — plicata, 37.
Sequoia gigantea, oil of, 39. Thujaketonic acid, 256.
Seseli Bocconi, 325. Thujone, 36, 203, 288, 289, 294.
— Harveyanum, 508. Thujyl alcohol, 288.
Sesquicamphene, 161. Thyme oil, 244.
•Sesquicamphenol, 161. Algerian, 244.
Sesquicitronellene, 70. — British E. African, 244.
Shaddock, oil of, 450. French, 244.
Shikimi-no-Ki, 508. red, 244.
:Shikimol, 146. Spanish, 244.
Shiu, oil of, 168, 474. white, 244.
Shiu-Sho tree, 168. Thymohydroquinone, 241, 263.
Sho-Gyu oil, 164, 167. — dimethyl ether, 296.
Sium cicutsefolium, oil of, 328. Thymol, 244, 263.
Snake root oil. 191, 192. — determination of, 245.
— wood oil, 191. Thymoquinone, 242, 263.
Sofia grass, 63, 79, 82. Thymus algeriensis, 244.
Solidago, oils of, 300. — capitatus, 246.
— canadensis, oil of, 300. — hirtus, 266.
— caroliniana, 301. — hyemalis, 266.
— nemoralis, 300. — Mastichina, 246, 266.
— odora, 300. — serpyllum, 245, 246, 266.
— nyosa, 300. — sparsifolius, 266.
-Southern cypress, 7. — Zygis, 244.
Spanish Verbena oil, 266, 271. Tilam outan, 251.
Spearmint, oil of, 237. — wangi, 251.
American, 237, 239. Toddalia aculeata, oil of, 461.
Austrian, 238. — asiatica, oil of, 461.
— English, 237. Trawas tree, 155, 172.
Russian, 238. Trichamomillol, 286.
Spigoure, 193, 194. Trifolium incamatum, oil of, 485.
Spike lavender oil, 204. — pratense, oil of, 485.
Spikenard, oil of, 285. Trihydroxyacetophenone, 94.
Spiraea ulmaria, 282, 412. Trimethyl-hexanone, 527.
Spoonwort, oil of, 500. Tropseolacese, 494.
;Star aniseed oil, 501. Tropaeolum majus, oil of, 494.
Japanese, 508. Tuberone, 94.
Storax, oil of, 525. Tuberose, oil of, 94.
Styrol, 525. Turmeric, oil of, 106.
>Styrolene, 278. Turmerol, 107.
— alcohol, 278. Turnera aphrodisiaca, 528.
Styrolyl acetate, 273, 278. — diffusa, 528.
Suginene, 6. Turneracese, 528.
Sumbul, oil of, 327. Turpentine, oil of, 9.
Sweet basil oil, 259. Algerian, 32.
American, 9, 17.
TAGETES patulu, oil of, 296. Austrian, 30.
'Tanacetoketonic acid, 256. Burmese, 32.
Tanacetone, 294. Canada Balsam, 32.
Tanacetum balsamita, 294. Ghian, 462.
— boreale, 294. Finnish, 28.
— vulgare, 294. French, 11, 29.
Tanacetylhydrine, 294. Greek, 29.
Tangerine oil, 427. Indian, 12.
INDEX 549
Turpentine, oil of, Italian, 28. WALANG Dcerr, 328.
Wallflower, oil of, 500.
Mexican, 32. Walnut leaf oil, 118.
Oregon balsam, 32. Warburgia Stuhlmanni, oil of, 529.
Philippine, 32. Wartara seed, oil of, 452.
Russian, 26. Water mint oil, 239.
Spanish, 32. Wellingtonia gigantea, 39.
Strasburg, 32. Winter's bark, oil of, 511.
Venetian, 32. — grass, 62.
Wood, 15, 18. Wintergreen oil, 278.
Turpentines, from various Pinus species, Wood turpentine, 15, 26.
vide under Pinus. Wormseed oil, 121, 289, 534.
Wormwood oil, 287.
UMBELLIFERÊ, 304. XANTHOEBHCEA australis, 93.
Umbellol, 170. — hastilis, 93.
Umbellularia Californica, 170. — preissii, 94.
N
Umbellulone, 171. Xanthotoxin, 453.
Uncineol, 381. Xanthoxylum acanthopodium, 452.
Undecenol, 155, 172. — ailanthoides, 452.
Urena lobata, 254. — alatum, 452.
Urticacese, 120. — aubertia, 461.
Usnea, 1. — piperitum, 451.
— senegalense, 453.
VALERIANA Celtica, 285.
— Mexicana, 285. YABUNIKKEI, 143.
— officinalis, 284. Yamakorho, oil of, 452.
Valerianaceae, 284. Yama-nikkei, 143.
Valeric aldehyde, 202, 335. Yerba-Buena, 269.
Vanillin, 335, 484, 525. Ylang-ylang oils, 512, 521.
Verbena oil, 270. Yu-boku, 168.
Spanish, 266. Yu-bun-boku, 168.
— triphylla, 270. Yu-Ju oil, 164, 168.
Verbenacese, 270.
Vetivene, 78. ZEDOARY oil, 107.
Vetivenol, 78. Zingiber omcinale, 98.
Vetiver grass, 63. Zingiberacese, 98.
— oil, 75, 77. Zingiberene, 99.
Vetiveria zizanoides, 63, 75. Zingiberol, 99.
Virginia cedar, 2. Zygophyllacese, 461.
ABERDEEN : THE UNIVERSITY PRESS

VOLUME II.
THE CHEMISTRY OF
ESSENTIAL OILS
AND
ARTIFICIAL PERFUMES
BY
ERNEST J. PARRY, B.Sc. (LOND.), F.I.C., F.C.S.

OF GRAY'S INN, BARRISTER-AT-LAW
AUTHOR OF "FOOD AND DRUGS," "THE CHEMISTRY OF PIGMENTS," ETC.
FOURTH EDITION, REVISED AND ENLARGED
VOLUME II.
(i) THE ESSENTIAL OIL AND ITS ODOUR
(2) CONSTITUENTS OF ESSENTIAL OILS, SYNTHETIC
PERFUMES AND ISOLATED AROMATICS
(3) THE ANALYSIS OF ESSENTIAL OILS
LONDON
SCOTT, GREENWOOD AND SON
8 BROADWAY, LUDGATE, E.G. 4
1922
[All rights reserved]
NEW YORK
D. VAN NOSTRAND COMPANY
EIGHT WARREN STREET
NOTE
First Edition (Demy 8vo) 1899
Second Edition, Revised and Enlarged (Demy 8vo) 1908
Third Edition, Revised and Enlarged'to Two Volumes (Royal
8vo), of which this is Volume IT.1 June, 1919
Fourth Edition (Vol. II.), Revised and Enlarged . . . February/, 1922
PREFACE TO THE FOURTH EDITION.
IN bringing the second volume of this work up to date, I have

to express my thanks to Mr. T. H. Durrans, M.Sc., F.I.C., of
Messrs. Boake, Eoberts & Co.'s Research Laboratories for con-
tributing the chapter on the Relationship of Odour to Chemical
Constitution, a subject to which Mr. Durrans has devoted con-
siderable attention. I have also to thank Mr. Maurice Salamon,
B.Sc., and Mr. C. T. Bennett, B.Sc., F.I.C., for reading and
revising the chapter on the Analysis of Essential Oils.
ERNEST J. PARRY.
56x GREAT DOVER STREET,
LONDON, S.E. 1, January, 1922.
CONTENTS OF VOLUME II.
CHAPTER I.
THE ESSENTIAL OIL IN THE PLANT.
PAGES
Cultivation and Structure of the Plant—Experiments on Plants—Secretion of
Essential Oil—Glucose—The Linalol, Geraniol, Thujol and Menthol
groups and their Composition—Esterification 1-24
CHAPTER II.
THE RELATIONSHIP BETWEEN ODOUR AND CHEMICAL COMPOSITION.
Strength of Odour—Theory of Odour—Alcohols—Sesquiterpenes—Esters—
Ketones—Phenols and Phenolic Compounds—Aldehydes—Chemical Re-
actions that produce Odours 25-37
CHAPTER III.
THE CONSTITUENTS OF ESSENTIAL OILS.
Hydrocarbons; Heptane—1?erpenes—Pinene and its Compounds—Campene—
Fenchene — Thujene — Dipentene — Phellandrene—Terpinene—-Cantha-
rene. Sesquiterpenes: Bisabolene—Cadinene. Alcohols: Methyl Alcohol
Ethyl Alcohol—Higher Aliphatic Alcohols—-Geraniol—Closed Chain
Alcohols. Terpene Alcohols : Terpineol—Pinenol. Esters : Benzyl Esters.
Aldehydes : Aliphatic Aldehydes—Benzaldehyde—Vanillin—Heliotropin.
Ketones : A cetone—lonone — Santenone — Carvone—Camphor. Phenols
and Phenolic Compounds: Cresol Compounds—Thymol. Oxides and
Lactones : Coumarin—Eucalyptol. Nitrogen Compounds : Nitrobenzene
—Artificial Musk. Sulphur Compounds : Butyl Isothiocyanate—Vinyl
Sulphide. Acids : Formic Acid—Acetic Acid—Butyric Acid—Benzoic
Acid 38-298
CHAPTER IV.
THE ANALYSIS OF ESSENTIAL OILS.
Specific Gravity. Optical Methods : Refraction—Polarimetry. Melting and
Solidifying Points—Boiling Point and Distillation—Determination of
Esters—Tables for the Calculation of Esters and Alcohols—Determination
of Alcohols—Tables—Separate Determination of Citronellol in Presence
of Geraniol—Determination of Aldehydes and Ketones—Miscellaneous
Processes—Determination of Phenols—Detection of Chlorine—Deter-
mination of Hydrocarbons—Hydrogen—Number of Essential Oils—
Detection o f some Common Adulterants . . . . . . . 299-357
359-365
vii
CHAPTEE I.
THE ESSENTIAL OIL IN THE PLANT.
AN absolutely scientific definition of the term essential cr volatile oils is
hardly possible, but for all practical purposes they may be defined as
odoriferous bodies of an oily nature obtained almost exclusively from
vegetable sources, generally liquid (sometimes semi-solid or solid) at
ordinary temperatures, and volatile without decomposition. This defini-
tion must be accepted within the ordinary limitations which are laid
down by the common acceptation of the words, which will make them-
selves apparent in the sequel, and show that no more restricted definition
is either advantageous or possible. Many essential oils, for example,
are partially decomposed when distilled by themselves, and some even
when steam distilled.
The volatile oils occur in the most varied parts of the plant anatomy,
in some cases being found throughout the various organs, in others
being restricted to one special portion of the plant. Thus in the conifers,
of which the pine is a type, much volatile oil is found in most parts of
the tree; whereas in the rose, the oil is confined to the flower ; in the
cinnamon, to the hark and the leaves, with a little in the root; in the
orange family, chiefly to the flowers and the peel of the fruit; and in the
nutmeg, to the fruit. The functions of these bodies in the plant economy
are by no means well understood. Whilst it is easy to understand that
a fragrant odour in the unfertilised flower may be of great value in
attracting the insects with the fecundating pollen, this can have no
bearing on the occurrence of odorous bodies in, say, the bark or internal
tissues, except in so far as the presence of essential oil in one part of the
plant is incidental to, and necessary for, its development, and .transference
to the spot at which it can exercise its real functions. There may also
be a certain protective value in the essential oils, especially against the
attacks of insects. At present one is compelled to class the majority of
the essential oils as, in general, belonging to the by-products of the
metabolic processes of cell life, such as are many of the alkaloids,,
colouring matters, and tannins; with, possibly, in certain cases, ex-
cretionary functions. Some are undoubtedly the results of, pathological
processes. The structures of the plant which carry the secreted oils-
occur in the fibro-vascular as well as in the fundamental tissues. De-
pendent on their mode of origin, the receptacles may be either closed
cells containing nothing other than the matter secreted, or they may be
vascular structures which have their origin in the gradual absorption of
adjacent cell walls, and the consequent fusion of numerous cells into
one vessel; or, again, they may be intercellular spaces, large cavities
formed in two distinct ways, (1) by the decomposition of a number of
adjacent cells, leaving a cavity in their place, whose origin is thus lysigen-
ous, (2) by the separation of adjacent cell walls without injury to the
VOL. II. 1
cells themselves, thus leaving a space for the secretion, whose origin is
schizogenous. Sometimes the oils contain a non-volatile resin in solution,
forming an oleoresin. For example, isolated cells containing an oleoresin
are found in some of the Laurinese, Zingiberacese, and Coniferae, and
intercellular spaces (the so-called glands) in some of the Umbelliferae
and Coniferae.
There are, of course, numerous other functions which the essential oils
possess, but in regard to which any views must necessarily be of a highly
speculative nature. For example, Tyndall has suggested that, especially
where secretion (or excretion) takes place near the surface of an organ,
B
D
FIG. 1.
In the above diagram A represents an oil cavity below the upper surface of the leaf
of Diclamnus Fraxinella ( x 820). B represents the same in an early stage, and
shows the mother cells of the cavity before their absorption (lysigenousj. C is
an early and D a later stage of the formation of a resin passage in the young
stem of the Ivy (Hedera Helix) ( x 800). In both cases g shows the separating
cell (schizogenous).
the essential oil has a function which regulates the rate of transpiration.
Moisture which is saturated With essential oil has a different heat con-
ductivity from that of moisture alone, so that a plant which gives off
much perfume may be protected, during the day, from too great trans-
piration, and, during the night, from too great reduction of temperature.
The high rate of consumption of essential oil during fecundation points,
too, to a distinct nutritive value, possibly due to easy assimilation owing
to its chemical constitution, of the essential oil.
The study of the essential oils in situ have hitherto been compara-
tively restricted, and although much work has been done on a few oils,
the results obtained, valuable as they are, must be regarded as of a pre-
THE ESSENTIAL OIL IN THE PLANT 3
liminary nature, indicating possibilities of great interest as research
develops.
From a purely practical point of view, the principal problem which
requires solution—and which is gradually becoming more understood—
is the determination of the external conditions which will enable the
grower and distiller to produce the best results, both qualitatively and
quantitatively, in regard to any given essential oil.
This problem involves consideration as to the effect of external con-
ditions such as light, heat, moisture, altitude, manuring and other
cultural matters, and as is obvious, such considerations may, and do, vary
greatly with different plants. Such considerations are to some extent
within the scope of the knowledge and skill of the well-trained farmer
and the careful distiller. But there are other considerations of a much
more abstruse character to be taken into account, and here only the
chemist can undertake the necessary investigations. The questions which
present themselves for solution are, broadly, some such as the following:—
Where and in what form does the essential oil have its origin ?
What alterations does it undergo during the life history of the plant ?
How does it find its way from one part of the plant to another ? How
can external conditions be controlled so as to vary the character of the
essential oil at the will of the cultivator ?
These, and similar questions are all-important, if the production of
essential oils is to be placed on a really scientific basis.
The questions raised in the foregoing paragraphs will be examined
briefly, and in principle only, as the detailed 'account of many of the
researches which apply to one plant only, would be outside the scope of
this work.
At the outset, attention may be drawn to the fact that the greater
part of our knowledge of the development of the essential oil in the plant
tissue is due to the painstaking researches of Charabot and his pupils.
And a very considerable amount of the information included in this
chapter is acknowledged to this source.
From the practical point of view, the principal variation of environ-
ment which is definitely under the control of the cultivator, is, of course,
the alteration in the composition of the soil, which is brought about
by scientific manuring. The analysis of fruits and vegetables will give
the ordinary agriculturist much information as to the necessary mineral
ingredients to be added to the soil; but in the case of essential oils,
the conditions are entirely different. The various parts of the plant
tissue are affected in different ways by the same mineral salts, and suc-
cessful development of the fruit or any other given part of the plant may
have little or no relationship with the quantity or quality of essential oil
produced. So that it is only by actual distillations of the plant, or
portion of the plant, coupled with an exhaustive examination of the
essential oil, that informative results can be obtained.
The principles underlying this question are, mutatis mutandis, identical
for all cases, so that as a typical illustration the case of the peppermint
plant may be selected, as this has been worked on by several independent
investigators very exhaustively.
Charabot and Hubert 1 carried out an elaborate series of experiments
on a field containing 29 rows of peppermint plants, each about 5 yards
in length. The normal soil of-the field had the following composition :—
1
Boure-Bertrand Fils, Bulletin, April, 1902, 5.
Pebbles 250 per mille.
Fine soil, dry 750 „
Nitrogen (parts per 1000 in the dry fine soil) . . 1-44 ,,
Lime (expressed as GaO per 1000 in the dry fine soil) 309-45 ,,
Phosphoric acid (expressed as P2O5 per 1000 in the
dry fine soil) 2-82
Potash (expressed as K2O per 1000 in the dry fine
soil) 1-74
A number of the plants were watered with a solution of 500 grams
of sodium chloride in 20 litres of water, and a number with a similar
quantity of sodium nitrate. These salts were administered on 23 May,
and the following observations were made on the dates specified, on the
essential oils obtained under the usual conditions, from the plants
normally cultivated, and then treated with the salts above mentioned:—
Plants Cut on 24 July.
Normal. Sodium Chloride. Sodium Nitrate.
Optical rotation . . . . - 3° 38' 0° - 0° 10'

Menthyl esters . . . . 12'0 per cent. 12*8 per cent. 12*3 per cent.
Total menthol . . . . 38-2 38-2 36-7
Menthone . . . . . 8*2 ,, 4*0 „ 6-0
Plants Cut on 20 August (Green Parts only).
Menthyl esters . . . . j 33'3 per cent. I 39-6 per cent. 39 2 per cent.
Plants Cut on 16 September (after Fall of Petals).
Optical rotation . . . . - 5° 30' - 12° 18' - 2° 30'
Menthyl esters . . . . 2 7 * 0 per cent. 30-1 per cent. 28-9 per cent.
Total menthol . . . . 47 '0 „ 48-1 45-8
Menthone . . . . . 2'5 ,, I'l 2'5
The oil distilled from plants normally cultivated, which were cut on
18 July, that is six days before the earliest of the above experiments,
Menthyl esters . . . . . . . . 8*8 p e r cent.
Total menthol 41-1 „ ,,
Menthone 4*0 ,, ,,
The facts established by these experiments are that both sodium
chloride and sodium nitrate favour esterification but impede the forma-
tion of menthone.
These facts, however, cannot be correctly studied without taking
into account a considerable amount of collateral matter. For example,
whilst the actual percentage of esters in the essential oils is increased
by the use of sodium chloride, this salt has an inhibiting action on the
vegetation generally, so that the actual weight of methyl esters per
acre is less than when no sodium chloride is used, whilst the reverse is
true when sodium nitrate is used.
A very elaborate investigation on the subject has recently been
carried out by Gustav Hosier.1
J
Pharm. Post, 1912, i. 2.
THE ESSENTIAL OIL IN THE PLANT
Eight different cultivations were carried out under the following
conditions :—
1. Without any manure.
2. With farmyard manure.
3. With sodium nitrate.
4. With sodium nitrate and farmyard manure.
5. With sodium nitrate and calcium superphosphate.
6. With sodium nitrate, calcium superphosphate, and farmyard
manure.
7. With sodium nitrate, calcium superphosphate, and potash salts.
8. With sodium nitrate, calcium superphosphate, potash salts, and
farmyard manure.
The following are the details of yield of plants and essential oil, with
the market values of the product, all being calculated on the same basis :—
Per Hectare.
Dried Plants in Weig

Kilos. Per Cent., Oil. KU™ °U " Value.
1 1300 0-77 10-01 500

2 2000 0-88 16-40 820
3 1860 0 74 18-76 938
4 2820 0-81 1 22-84 1142
5 1940 0-73 14-16 708
6 2320 0*84 ' 19-94 974
7 2200 0-72 15-84 792
8 3140 0-95 j 29-83 1491
The essential oils, distilled from the plants cut in September had the
1. 2. 3. 4. 5. 6. 7. 8.
Per cent, on dry

herb 0-87 0-93 0-83 0-91 0-83 0-95 0-83 1-08 I
Specific gravity 0-9088 0-9092 0-9105 0-9090 0-9100 0-9087 0-9111 0-9099
Optical rotation -29-67° - 29-22° -60-25° - 30-44° -31-78° - 30-41° -32-05° - 30-25°
Acid number . 0-77 0-51 0-78 0-46 6-58 0-50 0-52 0-37
Ester „ 37-47 33-49 41-13 43-32 44-14 32-28 45-52 36-75
Menthyl esters . 10-73 9-33 11-74 12-07 12-30 9-27 12-58 10-24
Ester number of
acetylated oil 196-05 187-75 197-04 195-24 189-36 194-07 192-70 197-65
Free menthol . 50-13 48-59 48-82 47-76 45-89 30-93 46-08 50-97
Total 60-86 57-92 60-56 59-83 57-69 60-20 58-66 61-21
Menthone . 3-52 6-11 0-89 2-94 4-01 1-37 3-75 2-14
It will be noted that the experiments with sodium nitrate confir m the
results of Charabot and Hebert, both as regards the increase in menthyl
esters and the decrease in menthone in the essential oil.
The influence of sunlight on vegetable growth, and the results of
etiolation are, of course, well known to botanical students. There is no
room for doubt that the production and evolution of the odour-bearing
constituents of a plant are in direct relationship with the chlorophyll
and its functions, and that therefore the iquestion of sunlight has a very
great effect on the character of the essential oil.
In the case of sweet basil, Ocimum basilicum, Charabot and Heêrt 1
have examined the essential oils distilled from plants which had been
cultivated in full light and from those kept shaded from the light. Jn
the former case the oil contained 57*3 per cent, of estragol and 42*7 per
cent, of terpene compounds, whilst in the case of the shaded plants the
estragol had. risen to»74'2 per cent, and the terpene compounds fell to
25*8 per cent.
A more elaborate investigation on the influence of light was carried
out in the case of peppermint plants.2 The plants were put out at the
commencement of May, 1903, and on 10 May a certain art a of the field was
completely protected from the sun's rays. Many of the plants so shaded
died, and in no case did flowering take place. The essential oils were
distilled on 6 August, the control plants being deprived of their flowers,
so as to make them strictly comparable with the shaded plants. The
yield of essential qil was 0*629 per cent, on the dried normal plants but
only 0*32 per cent, on the shaded plants. The essential oil of the normal
plants contained 18*1 per cent, of menthyl esters a<* against 17*3 per
cent, in the oil from the shaded plants. The flowers of the normal plants
were distilled separately and yielded 1*815 per cent, on the dried material.
It is therefore clear that the restriction of light considerably reduces the
proportion of essential oil contained in the plant. This point will become
more obvious when the importance of the leaf and its contained chloro-
phyll is examined.
The effect of altitude on the composition of essential oils has, per-
haps, been somewhat exaggerated, since in reality the factors concerned
are in the main the sum of the effects of moisture and light, with some
slight influence of temperature and rarification of the atmosphere.
Gastin Bonnier, in his published works, has shown that the effect of
moisture and drought has an equally important effect on plants with that
of sunlight and shade. Little experimental work has been carried out in
regard to the effect of moisture during cultivation on the essential oils,
but there seems no reason to doubt that it is very considerable. As an
example one may quote the case of the essential oil distilled from the
plants of Lavandula vera. When this plant is grown at comparatively
high altitudes in the South-East of France and on the Italian frontier it
yields an essential oil which contains from 25 to 55 per cent, of linalyl
acetate and no cineol. If the same plants grown in England are
distilled, the essential oil contains from 6 to 11 per cent, of linalyl acetate,
and an appreciable amount of cineol. There are,r no doubt, many causes
which contribute to this great difference betw een the essential oils
distilled from lavender plants grown in different districts, but there
appears to be little doubt that the comparative moisture of the soil
in England, and the dryness of the mountainous, regions of France tin
which the lavender plant flourishes, are the dominating factor. Indeed,
Charabot has examined an oil distilled from French plants cultivated
near Paris and found it to contain only 10*2 per cent, of esters, thus
approximating in character to English lavender oil.
The above considerations indicate the great importance of experi-
mental studies on the influence of externally controlled conditions, in
1
2
Charabot and Hebert, 2,1905, xxxiii. 584.
Roure-Bertrand Fils, Bulletin, April, 1904, 9.
regard to individual plants, with a view to obtaining from them the
greatest amount of essential oil which shall have the characters which
are particularly required. It is probable that there is a good deal of
unpublished work in this direction, which has been undertaken, but
which has been kept secret from commercial motives.
There are many cases in which the action of parasites produces
great changes in the anatomical structure of the plant, which changes
are usually reflected in the character of the essential oils. Molliard has
made a careful examination of the effect of the parasite Eriophyes
mentha on the peppermint plant. The presence of this parasite causes
a practically complete suppression of flowers, the branches which,
normally terminated by inflorescences, become luxurious in growth with
innumerable branching, but without flowers. Distinct changes in the
nervation are also observable, and various other structural changes aie
to be noticed, all of which profoundly modify the general character
of the plant. The essential oil from these sterile peppermint plants is
more abundant than in the case of normal plants, but it contains only
traces of menthone, and much more of the menthol is in the combined
form, as esters. Further, the mixture of esterifying acids is richer in
the case of the normal oil, in valerianic acid, than in the case of the oil
from the sterile plants.
The essential oil may be secreted in numerous organs, such as cells,
hairs, vessels, etc., and may rest stored in the place of secretion; or
may be secreted from the cells in which it is produced into organs ex-
ternal to the cells. As pointed out previously, the canals or vessels in
which essential oils are formed to a considerable extent are usually
termed schizogenous or lysigenous, according to their mode of origin.
Many such vessels are schizogenous in the inception, but are enlarged
by a later absorption of cell walls. They are then known as schizolysi-
genous. The mechanism of the actual secretion is b» no means well
understood, and most views on the subject must be regarded as within
the realms of undemonstrated theories. An ingenious explanation ot the
process of secretion has been advanced by Tschirch.1 He considers that
the external portions of the membranes of the cells which border on the
vessel become mucilaginous, and form the first products of the trans-
formation of the cell substance into the essential oil, which then appears
in the vessel in the form of tiny drops of oil. This conversion into
mucilaginous matter proceeds rapidly until the fully developed vessel is
completely surrounded by the secreting cells, whose membranes, on the
side bordering on the vessel, is jellified in tis external portion forming a
mucilaginous layer—the outer layer of which Tschirch terms the resino-
genous layer (Resinogeneschicht).. This resinogenous layer is separated
from the cavity of the vessel by a cuticle common to all the cells form-
ing the walls.
The essential oil is formed throughout the rednogenous layer,
whence it passes into the vessel, the minute particles uniting to form
small oil drops. According to Tschirch, the essential oil is first produced
in the inner portions of the resinogenous layer, and has not diffused
through the actual cell membrane as essential oil, but in ths form of an
intermediate product, the actual genesis of the oil as such being in the
resinogenous layer.
1
Published works, pa&sim.
There is, however, a considerable weight of opinion that the essential
oil passes through membrane of the cell iri which it is secreted. There
is, so far as the author can see, no substantial evidence of the existence
of Tschirch's resinogenous layer, and there is no doubt that the theo-
retical need for its existence as assumed by Tschirch is based on a mis-
conception. Tschirch claims that it is not probable that resins and
essential oils can diffuse through membranes saturated with water. But
he leaves out of consideration the fact that all essential oils are slightly
soluble in water, and that diffusion in very dilute aqueous solution is
obviously possible and even very probable. On the whole, there does
not appear to be much theoretical reason for, nor experimental evidence
of, the existence of the resinogenous layer.
An interesting contribution to this question has recently been made
by O. Tunmami l entitled " Contribution to the knowledge of the cuticu-
lar glands," some volatile oils owing their existence to these glands.
The author discusses the formation of secretions, and concludes that
there is a correspondence between the formation of secretions in the
vegetable kingdom and the same process in the glandular tissues of the
human skin, that is to say, the sebaceous glands and gland surfaces.
The secreted matter is only found outside the glandular cells, as it is
divided from the plasma of the cells by a wall of cellulose which is
always visible. The first investigator who suggested the resin-secreting
layer was Tschirch, who gave, as above stated, to this part of the mem-
brane the name of "resinogenous layer". The determination of this
layer in the glands of the skin is easier when the material worked upon
has been soaked for one or two months in concentrated aqueous solution
of acetate of copper, which hardens it. If fresh material is employed,
the modus operandi, according to Tunmann, should be as follows:
Delicate horizontal cuts should be made, so that the glands may be in-
spected from above, or in diagonal section. Next add an aqueous solu-
tion of chloral hydrate (10, 20, 30, or 40 per cent.). If the layer should
not yet be visible the strength of the solution should be increased by
degrees until the major part of the resin has been dissolved. Now
exert with the finger a gentle pressure upon the side of the covering
glass. This will burst the cuticle and push it aside, while the resin-
ogenous layer will be placed either upon the top of the cells, or, separ-
ated from the latter, at the side of the gland-head. It is not necessary
that all the resin should be dissolved. Staining with diluted tincture of
alkanet will show the residual resin, leaving the resinogenous layer un-
coloured.
By the aid of the processes described Tunmann claims to have
discovered the resinogenous layer in all the plants examined by him.
In the course of his investigations he was able to determine various
typical forms of the layer. These he divides into three principal types :
the rod-type (Viola Fraxinus, Alnus}, the vacuola-type (Salvia.Hyssopus),
and the mesh or grille-type (Rhododendron, Azalea).
The cuticle of the glands of the skin is partly enlarged by stretching,
partly by subsequent development. Its principal purpose is unquestion-
ably to prevent a too rapid exudation or loss of the secretions. In the
case of all the persistent glands of the Labiatce, Pelargonic&, Composite,
etc., all of which possess a strong cuticle, a continuous volatilisation of
1
Berichte dentsch. pharm. Ges., 18 (1908), 491: from SchimmePs Report.
essential oil takes place throughout the whole life of the plant. In the
course of this process the chemical composition of the essential oil must
of course undergo some modification, but it does not reach a demon-
strable process of resinification, because new volatile portions are con-
tinuously being formed. Only in autumn, when the period of growth is
reaching its end, this formation of volatile constituents ceases, and the
remainder of the oil resinifies. Thus it is that autumnal leaves are
found to contain in lieu of the usual, almost colourless, highly refractory
essential oil, a dark yellow, partly crystalline, partly amorphous, some-
what sparingly soluble lump of resin.
Generally speaking, the view has been accepted that vegetable
secretions are decomposition products formed in the course of the
metabolism, but Tschirch considers that these secretions are built up to
serve quite definite and various biological objects, and in this view he is
supported by Tunmann.
In some cases, the formation of essential oil in the plant begins
at a very early stage, in fact, before the gland has attained its full
development.
In opposition to Charabot, Tunmann considers that the constant
change in the chemical composition of vegetable essential oils during the
progress of the development of the plant, is chiefly due to the continuous
evaporation of the more volatile parts. He agrees with Charabot in
deducing, from pharmaco-physiological considerations, that plants in
flower cannot yield so valuable an oil as can the young spring leaves.
The solubility of essential oils in water, or in aqueous solutions of
other substances is obviously a question of considerable importance in
reference to the transference of the oil from one portion of the plant to
another, as will be seen in the sequel. From a laboratory point of
view, the question has been thoroughly investigated in a number of
cases by Umney and Bunker.1 The following table indicates the results
obtained by these observers, the methods adopted by them being (1) the
determination of the difference between the refractive index of the dry
oil and that of the oil saturated with water, and (2) the determination of
the difference between the specific gravity of the dry oil and that of the
oil saturated with water :—
J
P. and E.O.B. 1912, 101.
I. 11. III. IV. V. VI. VII. VIII. IX. X.
S. G. S. G. Ref. Ind. Ref. Ind. Per Cent. Per Cent.

Essential Watered Watered Dif- Per Cent.
Dried Oil Oil Difference. Dried Oil Oil ference. Water from Water from Water Actually
Oil. at 15° C. at 25° C. S. G. Ref. Ind. Added.
at 15° C. at 25° C.
TYP I.
Nutmeg \. •9018 •9018 nil 1-4795 1-4795 nil nil nil nil w
tei
Juniper •8734 •8734 nil 1-4785 1-4785 nil nil nil nil
Lemon •8576 •8576 nil 1-4729 1-4729 nil nil nil nil o
Orange
TYPE II.
. •8539 •8539 nil 1-4715 1-4715 nil nil nil nil
i
Santal •9756 •9760 •0004 1-5038 1-5035 •0003 1-7 per cent. 0-17 per cent. 0*44 per cent.
Savin . . . . •9139 •9140 •0001 1-4735 1-4732 •0003 0-12 0-23 0-23
Citronella . •9034 •9034 nil 1-4770 1-4769 •0001 nil 0-07 0-31 „
Geranium (Turkish) . •8886 •8898 •0012 1-4723 1-4715 •ooos ' 1-22 per cent. 0-64 0-82 Hi
O
TYPE III.
Lemon-grass . . •8820 •8823 -0003 1-4824 1-4823 •0001 0-28 per cent. 0*07 per cent. 0'21 per cent.
Cassia 1-0702 1-0694 - -0003 1-6003 1-5999 •0004 1-07 0-14 0-54
Citronella (Java) •8935 •8937 •0002 1-4660 1-4659 •0001 0-21 0-08 0-36 02
QQ
TYPE IV.
Cinnamon leaf . 1-0533 1-0531 - -0002 1-5315 1-5814 •0001 0-35 per cent. 0'05 L er cent. 0-28 per cent.
Clove . . . . 10509 1-0508 - -0001 1-5300 1-5295 •0005 0-18 0-24 0-41
Thyme •9144 •9150 •0006 1-4913 1-4810 •0003 0-78 0-22 0-40
TYPE V.
Bergamot . •8831 •8835 •0001 1-4634 1-4631 •0003 0*09 per cent. 0-26 per cent. 0-24 per cent.
Geranium (Bourbon) . •9132 •9133 •0001 1-4639 1-4638 •0001 0-12 0-03 0-55
TYPE VI.
Eucalyptus (Glob.) •9204 •9209 •0005 1-4602 1-4600 •0002 0-68 per cent. 0-17 per cent. 0*20 per cent.
TYPE VII.
Caraway •9135 •9135 nil 1-4847 1-4847 nil nil nil 0*13 per cent.
A second series of experiments was carried out to determine the
amount of wafer which the same oils were capable of dissolving. These
results are embodied in the following table :—
Eef. It.d. Ref. Tnd.

Essential Oil. at 25° C. at 25° C. of Difference. PerCent. 1 part in
of Water
of " Steamed" Water.
Dried Oil. (approximately).
Oil.
TYPE I.
Nutmeg . 1-4795 1-4795 nil —
—
Juniper . 1-4800 1-4800 nil — —
Lemon . 1-4729 1-4729 nil —
Orange . —
1-4715 1-4715 nil — —
TYPE II.
Santal . 1-5040 1-5037 •0003 0-17 °/0 590
Savin 1-4737 1-4733 •0004 0-30 „ 330
Citronella 1-4800 1-4794 •0006 0-44 „ 230
Geranium (Turkish) 1-4726 1-4712 •0014 1-13 „ 90
TYPE III.
Lemon-grass . 1-4830 1-4824 •0006 0-45 °/0 220
Cassia 1-6017 1-6005 •0012 0-41 „ 220
Citronella (Java) 1-4666 1-4657 •0009 0-75 „ 130
TYPE IV.
Cinnamon leaf 1-5325 1-5316 •0009 0-42 % 220
Clove 1-5305 1-5295 •0010 0-47 „ 210
Thyme . 1-4917 1-4911 •0006 0-41 „ 220
TYPE V.
Bergamot 1-4635 1-4631 •0004 0-34 °/0 300
Geranium (Bourbon) 1-4654 1-4648 •0006 0-49 „ 200
TYPE VI.
Eucalyptus (Glob.) . 1-4604 1-4602 •0002 0-16 °/0 620
TYPE VII.
Caraway . 1-4847 1-4847 nil — "
The oils consisting mainly of terpenes do not appear to dissolve

water, nor to be soluble in water, or at all events, to any appreciable
extent.
It must, however, be remembered that we are here dealing with pure
water only, whereas in the plant economy we are dealing with solutions
of organic substances, in which essential oils would almost certainly be
dissolved more easily than in pure water.
As has been mentioned above, essential oils occur in the most varied
parts of the plant anatomy, and in many cases in almost every part of
a given plant, whilst in many others the essential oil is restricted to one
or two parts of the plant only.
Charabot and Laloue have especially studied the evolution and
transference of the essential oil throughout the whole of the plant, and
their results form the basis of our knowledge on the subject.
A plant which yielded particularly instructive results on the general
question is Ocimum basilicum. The investigations were carried out at
a number of stages ,of the plant's growth, the four principal of which
1. 4 July, before flowering. There was a considerable preponderance
of leaves which were found to be distinctly richer in odorous consti-
tuents than the stems, the essential oil being present as such in the
young leaves.
2. 21 July, at the commencement of flowering. The stems now
preponderated, and the green parts of the plant showed a smaller per-
centage of essential oil, whilst the young flowers already contained a
larger proportion of essential oil.
3. 26 August, with flowering well advanced. The leaves and flowers
were both considerably more numerous than in the preceding stage, and
it was found that the percentage of essential oil diminished very sensibly
in the green parts of the plants, whilst the flower was fulfilling its
functions. The percentage of oil diminished during fecundation in the
flowers, but not so considerably as in the green parts of the plant. It
is therefore during the period immediately preceding fecundation that
the essential oil accumulates most, and during fecundation that it is
used up.
4. 15 September, the seed having matured. An increase in the
percentage of essential oil in the green plants since the last stage was
noted and a diminution in the inflorescences.
The essential oil is therefore formed at an early period of the plant's
life, and accumulates most actively towards the commencement of repro-
duction. Before flowering, the accumulation reaches its maximum and
the diminution sets in as reproductive processes proceed, and the transfer
of the oil from the green plant to the inflorescences slows down, and
when fecundation is accomplished the essential oil, less on the whole,
again increases in the green parts and diminishes in the inflorescences.
It appears obvious, therefore, that the essential oil, manufactured in the
green parts of the plant, is transferred together with the soluble carbo-
hydrates to the flower, probably not as nutriment, and, fecundation ac-
complished, it returns, at all events in part, to the green parts of the
plant. The mechanism of this return may possibly be explained by the
desiccation of the inflorescence after fecundation, with a consequent
increase of osmotic pressure, so that some of the dissolved matter is driven
out. Throughout all the stages dealt with no essential oil was detected
in the roots.
As another example of the experiments, Artemisia absinthium may
be selected. The four stages of special interest were as follows :—
1. 26 September, 1904, long before flowering time. The roots did
not contain any essential oil. The leaves contained considerably more
than the stems—about eleven times as much.
2. 10 July, 1905, commencement of flowering. The roots were now
found to be richer in essential oil than the stefns. In all the organs the
proportion had increased, and in the leaves it had doubled.
3. 4 August, 1905, flowering advanced. The accumulation of es-
sential oil in the roots was still more marked. (This fact does not
appear to hold good for any annual plants : Artemisia is a perennial,
The proportion of essential oil sensibly diminishes in the stems, in the
leaves, and especially in the inflorescences, and in the whole plant. The
most active formation of essential oil is, therefore, in the early part of
the plant's life up to the commencement of flowering.
4. 2 September, 1905, the flowering completed. The percentage of
essential oil in the roots has increased still further; a slight increase has
taken place in the stems; no alteration is noticed in the leaves, and a
diminution has taken place in the inflorescence.
The general conclusions drawn by Charabot and Laloue as the
result of these and a number of similar experiments are as follows:—l
" The odorous compound first appears in the green organs of the plant
whilst still young. It continues to be formed and to accumulate up
till the commencement of flowering, but the process becomes slower
as flowering advances. The essential oil passes from the leaves to the
stems and thence to the inflorescence, obeying the ordinary laws of
diffusion. Part of it, entering into solution, passes into the stem by
osmosis. Arriving here, and finding the medium already saturated with
similar products, precipitation takes place, the remaining soluble portion
continuing to diffuse, entering the organs where it is consumed, especially
the inflorescence. Whilst fecundation is taking place a certain amount
of the essential oil is consumed in the inflorescence. It is possible, and
even probable, that at the same time the green organs are producing
further quantities of essential oil, but all that can be said with certainty
is that a net loss in essential oil occurs when the flower accomplishes its
sexual function. This leads to the practical conclusion that such perfume-
yielding plants should be gathered for distillation just before the fecunda-
tion takes place. This act accomplished, the odorous principles appear
to redescend into the stem and other organs of the flower, a movement
probably brought about by the desiccation of the flower which follows
fecundation, with a resulting increase in the osmotic pressure.''
If these assumptions of Charabot and Laloue be correct—and they
are borne out by much experimental evidence, after laborious research—
the theory of Tschirch and his pupils, which depends on quite opposite
assumptions, is clearly unacceptable. According to Charabot and Laloue,
the essential oil circulates in the plant in aqueous solution and can
traverse the plant from organ to organ in this form, and wherever
meeting already saturated media, is precipitated, and the points at
which such precipitation occurs are known as secreting organs. This
being true, the assumption of a resinogenous layer, based on the hy-
pothesis of the non-solubility of essential oils in water—and in solutions
of organic matter—becomes unnecessary and improbable.
Most essential oils appear to be evolved directly in the form of
terpenic or non-terpenic compounds separable from the plant tissues in
the same form as they exist therein. A considerable number, however,
are evolved in the form of complex compounds known as glucosides, in
which the essential oil complex is present, but wherein the essential oil
itself does not exist in the free state.
The glucosides are compounds, which, under the influence of hydrolytic
agents are decomposed into glucose or an allied aldose or ketose, and one
or more other bodies, which, in the cases under consideration, form con-
stituents of essential oils. The hydrolytic agents which bring about these
changes are soluble ferments, such as diastases, enzymes and similar
1
Le Par/tint Chez la Plante, 233.
bodies, or, where the hydrolysis is produced artifically, dilute acids or
alkalis.
The ferments able to decompose particular glucosides are usually
found in the plants containing the glucosides, separated from the latter
by being enclosed in special cells which do not contain the glucoside,
so that the two substances must be brought into contact, in the presence
of water, by mechanical means, such as crushing, etc.
Two principal cases of such decomposition are known.
Firstly, there are those cases where the hydrolysis takes place within
the plant itself during the life of the plant, so that the essential oil is
actually a product, in the free state, of the metabolic processes of the
living plant; and secondly, there are those cases where the glucoside is
not decomposed except by artificial processes, independent of the life of
the plant.
The former case is of particular interest and importance as bearing
on the proper method for the extraction of the perfume. Typical
instances are those of jasmin and tuberose, which have been carefully
investigated by Hesse. This chemist showed that the essential oil of
jasmin, which resides in the flower alone, does not, when extracted with
a volatile solvent, contain either methyl anthranilate or indole, whereas
when the flowers are allowed to macerate in fat by the enfleurage pro-
cess, and the pomade so obtained extracted, the essential oil does contain
both methyl anthranilate and indole; and further, the yield of essential
oil obtained by the latter process is at least five times as great as that
obtained by extracting the flowers with a volatile solvent. The following
considerations arise here. If the detached flowers are treated with a
volatile solvent, the living tissues are at once killed, and the actual
amount of oil present in the flowers is obtained in the condition in which
it exists when they were picked immediately before extraction. But if
the detached flowers are macerated in cold fat, the living tissues are not
destroyed and the flower continues to live for a certain time. Since a
reat increase in the quantity of the oil is obtained if, for example, the
f owers are exposed to the fat for twenty-four hours, and since new com-
pounds, namely, methyl anthranilate and indole now appear in the oil, it is
obvious that much oil and the new compounds are elaborated in the flower
during its life after being detached from the plant, quite independently of
the chlorophyll-containing organs. There is little reason to doubt that
this is the result of a glucosidal decomposition in the flower, the glucoside
existing therein at the time of gathering, and steadily decomposing into
the essential oil and a sugar so long as the flower is alive, but not when
it is killed, as, for example, by the action of a volatile solvent. Hesse
has established the same principle in the case of the tuberose, the flowers
of which yield about twelve times as much essential oil when exposed to
enfleurage as they do when extracted with a volatile solvent. Further,
the oil obtained by enfleurage contains far more methyl anthranilate than
the oil obtained by extraction with a volatile solvent, and also contains
methyl salicylate.
In the case of most plants where the essential oil is due to a glucosidal
decomposition, the products are of a non-terpenic character, but this is
not invariably the case.
In many plants the glucoside is decomposed durmg the life of the
plant in a manner different from that just described. The conditions are
not understood, but in the case of such flowers as the jasmin and tuberose
it appears that only a partial decomposition of the glucoside takes place,
until the removal of the decomposition products (e.g. by enfleurage) when
more glucoside is decomposed. In most plants, however, the decomposi-
tion is complete, all the essential oil possible is formed, and can be
obtained by any of the usual processes without being further increased
by more glucosidal decomposition.
One case in which the essential oil does not exist at any stage of the
plant's life in the free condition, until the ferment and the glucoside have
been brought into contact by artificial means, will suffice to illustrate this
type of production of essential oils in the plant. The essential oil of
bitter almonds does not exist as such in the kernels, which have no odour
such as we ascribe to bitter almonds. The glucoside which gives rise to
the essential oil is a body known as amygdalin, of the formula C20H27NOn.
This body crystallises in orthorhombic prisms with three molecules of
water of crystallisation, which are driven off at 110° to 120°. Under the
action of the ferment, emulsin (which is rarely, if ever, in contact with
the amygdalin in the plant tissues) in 'the presence of water, amygda-
lin splits up into glucose, hydrocyanic acid, and benzaldehyde, the char-
acteristic odour-bearer of essential oil of bitter almonds. The reaction
(which probably occurs in two stages which need not be discussed here)
is as follows :—
C20H27NOn + 2H2O = 2C6H12O6 + C6H . CHO + HNC. •
Amygdalin. Glucose. Benzaldehyde.
The above illustration is typical of the method of formation of a large
number of essential oils, which need not be discussed here in detail.
The actual genesis of the odoriferous compounds in the living plant
has been studied, as indicated above, principally by Charabot and his
colleagues, Laloue and Hebert, but interesting work in the same direc-
tion has been carried out by Blondel and by Mesnard.
There are three conditions to consider in regard to the physiological
activity of the living cell: (1) where the product—the essential oil in the
present case—pre-exists in the tissues generally and the function of the
phytoblast of the cell is limited to isolating the product at the desired
moment. This may be regarded as an excretion; (2) where the product
has its origin in the cell itself by means of combination and reaction of
other bodies transported from other parts of the plant tissue, and (3)
where the product is completely built up in the cell, without it being
supplied with the materials for the synthesis by transport from other
parts of the tissues. These may be regarded as cases of secretion.
Numerous theories have been advanced to explain the origin of es-
sential oils in the plant, but the evidence in favour of most of them is in
no case at all conclusive, and the question must still be regarded as un-
settled.
Fliickiger and Tschirch originally suggested that the essential oil was
elaborated at the expense of the starch, or possibly even of the cellulose,
the intermediate products of which were transported through the tissues
to the locality of elimination, undergoing gradual alteration until the
final product of transformation was the essential oil. Mesnard regarded
the chlorophyll as the parent substance of the essential oils, and Tschirch
more recently suggested the tannin as the more probable substance to
give rise to essential oils and resins.
One thing is certain, and that is that the chlorophyll-containing
parenchyma is, generally speaking, the seat of formation of the essential
oils. The physiological activity of the phytoblast of the cell can be
demonstrated experimentally, and Blondel has illustrated it in the case
of the rose. He took the red rose General Jaqueminot, as one having
a well-marked odour, and placed two blooms from the same branch, of
equal size and development, in vases of water under two bell jars. Into
one of the jars a few drops of chloroform on a sponge were introduced.
At the end of half an hour the bell jar was lifted, and the weak odour of
the rose was found to have given place to an intense odour of the flower.
The odour of the rose kept without chloroform was feeble, exactly as at the
commencement of the experiment. A similar experiment was carried
out with the tea rose Gloire de Dijon. In this case the odour of the
flower treated with chloroform entirely altered, and was quite disagree-
able, with no resemblance to that of the rose itself. In the former case
the action of a minute amount of chloroform acts as an irritant, and the
stimulus causes a greatly increased secretion of essential oil, whilst in
the latter case the functions of the secreting cells were actually changed
and a different odorous substance was evolved. With a larger dose of
chloroform the contents of the cells are killed and no further exhalation
of perfume is noted.
The actual course of the evolution of the essential oil has been par-
ticularly studied by Charabot and Laloue in plants, the principal con-
stituents of whose oils belong to four different groups, namely :—
1. Compounds of the linalol group.
2. „ ,, geraniol ,,
3. ,, „ thujol
4. ,, „ menthol ,,
Linalol is a tertiary alcohol of the formula C10H18O, which, with its
acetic ester (and traces of other esters) forms the basis of the perfumeôf
bergamot and lavender oils. By dehydration linalol is converted into
terpenes of which the principal are limonene and dipentene, and by
esterification into its acetic ester. The examination of the essential oil
at different periods of the development of the bergamot fruit has led
Charabot and Laloue to the following conclusions.1 As the fruit matures
the essential oil undergoes the following modifications :—
1. The amount of free acids decreases.
2. The richness in linalyl acetate increases.
3. The proportion of fiee linalol and even of total linalol decreases to
a very sensible extent.
4. The quantity of the terpenes increases, without the ratio between
the amounts of the two hydrocarbons limonene and dipentene being
altered.
The fact that the amount of total linalol decreases whilst the rich-
ness in linalyl acetate increases, proves that linalol appears in the plant
at an earlier period than its acetic ester. Further, the free acetic acid
acting on the linalol esterifies a portion of it, whilst another portion of
this terpene alcohol is dehydrated, with the production of limonene and
dipentene, which are the usual resultants of linalol in presence of certain
dehydrating agents. This view is corroborated by the fact that the
quantity of the mixed terpenes increases during the esterification,
without the slightest variation being observed in the ratio between the
1
Roure-Berbrand Fils, Bulletin, March, 1900, 12.
amounts of the two terpenes, which shows that their formation is simul-
taneous and is the result of one and the same reaction.
The practical conclusion to be drawn from this is as follows: Oil of
bergamot having a value which increases according to the richness in
ester, it will be profitable to gather the harvest at the period at which the
fruit is fully ripe.
The same compound, linalol, is the parent substance of oil of lavender.
The study of the progressive development of this oil in the plant tissues
was carried out on three samples wrhich were distill c d at intervals of a
fortnight, the first from flowers in the budding stage, the second from the
fully flowering plants, and the third from the plants with the flowers
faded. The essential oils thus obtained had the following characters :—-
Oil from the Plants with —
Buds. Flowers. Faded Flowers.
Specific gravity at 15° C. . 0-8849 0-8854 0-8821

Optical rotation . . . . - 6° 32' - 6° 48' - 6° 50'
Acidity, as acetic acid per litre
of water collected during distil-
lation 0-5241 gm. 0-4716 gm. 0-3846 gm.
Ester per cent 36-6 40-4 39-75
Free linalol per cent. . 21-0 16-7 18-9
Total „ „ 49-8 48-4 50-3
Hence, the acidity decreases in the course of vegetation; the pro-

portion of free linalol and the proportion of total linalol also decrease in
the essence up to the time when the flowers are fully opened, whilst the
proportion of ester increases; then, when the flower fades, the essential
oil becomes richer in linalol, whilst, on the other hand, its ester-content
decreases.
Thus as in the case of oil of bergamot, esterification is accompanied
by a decrease in. the total proportion of linalol and in the proportion of
free acid. These facts prove that, here also, the esters originate by the
direct action of the acids on the alcohols. Under these conditions,
as the plant develops, part of the linalol is esterified whilst another
portion is dehydrated. So that not only does the proportion of free
alcohol, but also that of the total alcohol decrease. But as the esterifica-
tion process is completed, which happens when the flower commences to<
fade, the total alcohols increase at a fairly rapid rate.
The progressive development of the geraniol compounds in essential
oils has been principally studied in the case of oil of geranium.
The typical plant which was selected for investigation in the case
of the geraniol compounds was the ordinary geranium. The principal
alcohol present in this oil is geraniol, C10H18O, and this is accompanied
by a smaller amount of citronellol, C10H20O. A ketone, menthone, is also
present. •
An oil was distilled from the green plants on 18 July, and a second
sample from the still green plants on 21 August. These two samples had
VOL. II.
Product Collected-
Oil 18 July. On 21 August.
Density at 15° C. . 0-897 0-899

Rotatory power in 100 mm. tube . - 10° - 10° 16'
Coefficient of saturation of the acids 43-8 41*0
Esters (calculated as geranyl liglate) 5-8 10-0
Free alcohol (calculated as C10H]8O) 64-0 02-1
Total alcohol 67'8 08-G
It will be seen that (1) the acidity decreases during the maturing
of the plant; (2) as in all the cases previously considered, oil of geranium
becomes richer in esters during vegetation; (3) the proportion of total
alcohol increases slightly and the quantity of free alcohol decreases, but
not to an extent corresponding with the increase of esters, so that in the
course of esterification, which takes place in this case without dehydration,
a small quantity of alcohol is produced.
Practically no menthone was found in either oil, but in the oil ob-
tained from the plant after flowering and complete maturation, an appre-
ciable quantity of menthone was found. It is thus clear that the
menthone is formed, as would be expected, principally during the period
of the greatest respiratory activity.
The thujol group, in reference to these studies, is represented by the
absinthe herb (Artemisia absynthium], which contains a secondary
alcohol thujol, C10H18O, and its esters, and its corresponding ketone,
thujone, C10H10O. The conclusions drawn in this case are as follows:—
From the early stages of vegetation, before the influence of flowering
is seen, an essential oil is present in the chlorophyll-containing organs,
which is already rich in thujol, but which contains very little thujone.
Esterification steadily increases up to the time of flowering, and then
diminishes, and afterwards increases again as new green organs develope.
The amount of thujol diminishes during the evolution of the plant, but
increases again when new green organs are developed. The thujone
gradually increases up till the time of flowering, and then steadily de-
creases owing to consumption in the flowers themselves.
It is therefore probable that the alcohol is formed in the first instance,
which is afterwards esterified to thujyl esters and oxidised to thujone.
The last of these investigations to which reference will be made is
that of the peppermint, as representing the menthol group of compounds.
Four samples of essential oil were examined :—
1. That distilled from young plants not exceeding 50 cm. in height,
the inflorescence having formed, but the buds not having made their ap-
pearance.
2. That distilled from the plant when the buds were commencing to
.appear, but from which the inflorescences were removed.
3. That distilled from the inflorescences so removed.
4. That distilled from the normal plant in full flower.
The oils in question had the following characters:—
i 1. Oil Extracted Oil Extracted after the Formation 4. Oil Extracted

of the Buds.
before the from the
Formation of Flowering
the Buds. Plants.
2. Leaves. 3. Inflorescences.
Specific gravity
at 18° C. . . 0-9025 0-9016 0-9081 0-9200
Optical rotation
at 18° C. in 100
mm. tube - 24° 10' - 26° - 20° 15' - 2° 37'
Ester (calculated)
• as m e n t h y l
acetate) . 3 '7 per cent. 10-3 percent. 7-5 per cent. 10*7 per cent.
Combined men-
thol . 2-9 8-1 „ ! 5-9 „ 8-4
Free menthol 44-3 ,, 422 i 29-9 32-1
Total „ 47-2 5')-3 „ I 35-8 40-5
Menthone . 5-2 4'2 ,, 16'7 10-2
After allowing for the relative weights of the leaves and inflorescences,
the composition of the average oil which would have been yielded by (2)
and (3) if distilled together would have been as follows :—
Combined menthol 7-6
Free menthol 39-0
Total „ 46-6
Menthone 7-5
It is thus apparent that at the commencement of vegetation of the
peppermint the oil is rich in menthol, but only a small amount is present
in the esterified condition. Menthone only exists in small quantity. As
the green parts of the plant develope, the proportion of esterified menthol
increases, as has been found to be the case with other alcohols. This
esterification, however, only takes place in the leaves, and when the
essential oil extends towards the flowering tops, it becomes poorer in
esters.
The net result is an increase in esters in the total essential oil distilled
from the whole of the plant, owing to the development of the green parts.
The menthone increases during the development of the inflorescences,
whilst the menthol decreases correspondingly. So that the oil obtained
from plants systematically deprived of their inflorescences only contains
a small amount of menthone, but is very rich in free menthol and in
esters. The oil, however, distilled from the flower shoots, even at an
early stage of their development, contains a considerable quantity of
menthone and comparatively small quantities of free menthol and esters.
It is therefore seen that the formation of the esters of menthol takes
place in the green parts of the plant, whilst the menthone originates
more especially in the flowers. This latter point is further corroborated
by the fact that if the peppermint becomes modified by the puncture of
an insect so as to suffer mutilation, the greater part of the menthone
disappears, as well as the flowers.
These observations throw light on the mechanism which governs the
transformation in the plant of the compounds belonging to the menthol
group. This alcohol being produced simultaneously with the green parts
of the plant, is partially esterified in the leaves; the esterification here
again is manifested as a consequence of the disappearance of the chloro-
phyll. Then, when the heads bearing the buds and later the flowers
are formed, a certain quantity of oil accumulates and the menthol, both in
the free and combined state, is there converted into menthone by oxida-
tion.
Investigations of the character detailed above lead to the following
conclusions. The esters are principally formed in the green parts of the
plant by the action of free acids on the alcohols. The latter easily losing
water are, at the same time partially dehydrated without combining with
acids and so give rise to terpenes. Isomerisation is also going on, so
that starting from the compound linalol, we see the following compounds
formed : linalyl acetate by esterification, terpenes by dehydration, and
the isomeric alcohols geraniol and nerol by isomerisation. All three
reactions can be effected artificially in the laboratory, as they are natur-
ally in the plant tissues. The alcohols and their esters are easily con-
verted into aldehydes and ketones, especially when the inflorescence
appears, since it is in these organs that oxygen is fixed to a maximum
extent.
Whatever may be the complex functions of the chlorophyll in the
plant, so far as the essential oils is concerned, there can be no doubt that
it favours the process of dehydration. Gaston Bonnier has shown that
under the influence of a mountain climate the green parts of a plant
undergo considerable modification. The leaves are thicker and of a more
rich green colour, and the assimilatory tissues of the stem are better
suited for the exercise of the chlorophyll functions. The green palissade
tissue is more strongly developed, either by the cells being longer, or be-
cause the number of layers of palissade cells is greater, so that the
chlorophyll bearers are larger and more numerous. Under similar
conditions, plants grown at low altitudes have a lower chlorophyll func-
tion than the same plants grown at high altitudes. Charabot's observa-
tions are supplementary to these, and prove that the more intense the
chlorophyll function, the greater the power of dehydration of the alcohols,
and therefore the greater the ester value of the oil. This has been de-
monstrated clearly in the case of lavender oil, when it is generally true
that the higher the altitude at which the plants are grown, the higher
the ester content. Grown in the neighbourhood of Paris, as before
mentioned, the plants yield an essential oil with so low an ester value
that it approximates to English lavender oil in composition. The in-
fluence of the altitude appears to be due to (1) greater light; (2) drier at-
mosphere, and (3) lower temperature. The first two of these influences
tend to assist esterification, whilst the third acts in a contrary sense, and
may even neutralise the others.
In the esterificatidn of an alcohol, water is always formed, according
to the equation—
EOH + AH = EA + H2O
Alcohol. Acid. Ester. Water.
This action is reversible, so that to maintain the ester value it is ob-
vious that the removal of water is advantageous. As a matter of fact, if
transpiration is increased, or the absorption of moisture by the roots is
diminished, the esterification is more rapid.
In regard to the distribution of the essential oil from one organ of the
plant to another, it has been established that there is a circulation of the
odorous compounds from the green portions of the plant into the flowers,
which may be regarded as the consuming organs, and that the constitu-
ents which travel through the tissues are, as would be expected, the most
soluble present in the oil. He*nce as Charabot, Hebert, and Laloue have
shown,1 it results that this phenomenon of circulation and that which
governs the chemical transformations which modify the composition of
the essential oils, combine their effects when the aldehydes or ketones in
question are relatively soluble constituents. In such a case the essential
oil of the inflorescences will be appreciably richer in aldehydic prin-
ciples than the essential oil of the leaves. This is what was found in
the case of verbena in which the citral is one of the most soluble con-
stituents of the oil, as clearly indicated from the fact that the portion
extracted from the waters of distillation is richer in citral than the por-
tion which is decanted. Thfe essential oil of the inflorescences contains
an appreciably higher proportion of citral than the essential oil extracted
from the green parts of the plants.
If, on the other hand, the aldehydic or ketonic portion of the essential
oil is sparingly soluble, the effects of the phenomenon of circulation on
the composition of the essential oils from the various organs will be the
reverse of those produced by the chemical changes which take place in
the inflorescence, since the principles which are displaced are principally
those which are most soluble. The relative insolubility of such ketones
and aldehydes will tend to make the oil of the leaves richer in these
compounds on account of their restricted power of circulation, and on the
other hand, to make the oil of the inflorescences richer in alcoholic prin-
ciples, whilst the actual formation of these compounds in the inflor-
escence will have the effect of increasing the proportion of aldehydes
or ketones in the inflorescence. The net result depends on which of the
two features predominates.
It has been shown while studying the formation and circulation of
the odorous products in the wormwood, that the ketone thujone is,
contrary to the usual rule for ketones, one of the most insoluble con-
stituents of the oil, and this is why, in spite of the tendency which thujol
possesses to become converted into thujone in the inflorescence by oxi-
dation, the essential oil from the leaves is richer in thujone than the
flower oil. This is due not only to the fact that the insoluble thujone
passes very slowly from the leaves to the flowers, but also to the fact
that the thujone which does so circulate, and also the thujone actually
formed in the flowers, being already a partially oxidised product on the
way to degradation, is the one which is principally consumed by the
flower in the exercise of its life function, namely, the fecundation process.
In the case of peppermint, the nature of the actual chemical transforma-
tions which occur in the green organs has a predominant influence on
the distribution of the odoriferous constituents. This was demonstrated
by distilling 200 kilos of the plant and collecting 200 litres of distilla-
tion water. This water was exhausted by shaking three successive times
with petrolium ether, which on evaporation yielded 35 grams of essential
oil which had been originally dissolved in the water. The oil obtained
by decantation, and that by extraction from the distillation waters gave the
following results on analysis :—
1
Roure-Bertrand Fils, Bulletin, May, 1908, 4.
Essential Oil
Separated by Extracted from

Decantation. the Waters.
Specific gravity at 15° C. 0-9194 0-9140

Soluble in 1 vol., Soluble in 1 vol. ;
becoming opales- separation of
cent on the crystals on the
further addition further addition
of alcohol of alcohol
Rotatory power . . . . . . - 11° 28' - 17° 36'
,, ,, of the acetylated oil - 20° 12' - 35° 28'
Colour . . . . . . . Pale green Reddish -brown
Acid number . . . . . . 0-2 12-8
Saponincation number . . . . 43-9 39-1
Ester number . . . . . . 43-7 26-3
Menthyl acetate . 15 5 per cent. 9'3 per cent.
Combined menthol . . . . . 12-2 7-3
Saponification number of acetylated oil 161-7 198-3
Esters i n acetylated o i l . . . . 57*2 per cent. 70'1 per cent.
Free menthol i n original o i l ... 37-4 56-3
Total „ „ „ . 49-6 63-6
Saponification number of the reduced and
acetylated o i l . . . . . . 188-1 215-9
Saponification number corresponding to the
menthone . . . . . . . 26-4 17-6
Menthone i n original o i l . . . . 7-4 per cent. 4-9 per cent.
Comparing the undissolved essential oil with that which was dis-
solved in the waters, it is seen that the former is richer in esters,
poorer in free menthol and total menthol, and richer in menthone than
the second. In other wrords the relatively sparingly soluble constituents
are esters and menthone, whilst menthol is particularly soluble.
The earlier researches of Charabot have shown that the essential oil of
the flowers is richer in menthone than the essential oil of the leaves. And
it is in spite of a circulation of menthol, a soluble principle, from the
leaf to the inflorescence, that this latter organ contains an essential oil
particularly rich in menthone. It must therefore be that the menthol is
there converted into menthone by oxidation.
The differences in composition between the two essential oils ex-
amined show well, if they be compared with those wrhich exist between
the essential oils of the leaves and the inflorescences, that the distribution
of the odorous principles between the leaf, the organ of production, and
the flower, the organ of consumption, tends to take place according to
their relative solubilities. But this tendency may be inhibited, or on the
other hand, it may be favoured by the chemical metamorphoses which
the substances undergo at any particular point of their passage or at any
particular centre of accumulation. Thus, in the-present case, some of the
least soluble principles, the esters of menthol, are most abundant in the
oil of the leaves, whilst another, menthone, is richest in the oil of an organ
to which there go, by circulation, nevertheless, the most soluble por-
tions. This is because this organ (the flower) constitutes the medium
in which the formation of this insoluble principle is particularly active.
Some highly interesting conclusions as to the relationship of essential
oils to the botanical characters of the plant have been drawn by Baker
THK ESSENTIAL OIL IN THE PLANT
j?ic,. 2.—Types of eucalyptus leaf venations, which indicate the presence of certain
chemical constituents in the oil. (Baker and Smitli.} For explanation see next
page.
1
and Smith, as a result of their exhaustive researches on the eucalypts of
Australasia. These investigators have shown that there is a marked
agreement between the chemical constituents of the essential oils of these
trees, and ths venation of the lanceolate leaves of the several species; so
marked, indeed, that in the majority of cases it is possible to state what
the general character of the essential oils is by a careful examination of
the leaf venation. There are three principal types of venation, which
are shown in the accompanying illustration (see previous page).
The first type is representative of those eucalyptus trees whose oils
contain the terpene pinene in marked quantity, cineol either not at all or
only in small amount, and from which phellandrene is absent.
The second type is characteristic of trees yielding oils which contain
pinene3 but are more or less rich in cineol and free from phellandrene.
The third type represents trees in which phellandrene is an impor-
tant constituent.
There appears reason to suppose that with the eucalypts a gradual
deviation from a type has taken place, and that the formation* of
characteristic constituents in these oils has been contemporaneous with
the characteristic alteration or deviation of the venation of their leaves.
That the constituents have been fixed and constant in the oils of the
several eucalypts for a very long period of time is demonstrated by the
fact that whenever a species occurs over a large area of country the
constituents of the oil are practically identical also, only differing in
about the same amount as is to be expected with the oils from trees of
the same species growing together in close proximity to each other.
The venation of the leaves of individual species is comparatively similar
throughout their geographical distribution, and their botanical characters
show also a marked constancy. All this comparative constancy is
probably accounted for by the long period of time" that must have
elapsed before a particular species could have established itself as such
over so extensive a range over which they are found to-day.
EXPLANATION OF PLATE.
1. Leaf of Eucalyptus corymbosa, Sm.—This venation is indicative of the pre-
sence of pinene in the oil. Note the close parallel lateral veins, the thick mid-rib,
ancf the position of the marginal vein close to the edge of the leaf. The yield of oil
from leaves showing this venation is small, there not being room between the lateral
veins for the formation of many oil glands.
2. Leaf of Eucalyptus Smithii, K. T. B.—This venation is characteristic of
species whose oil consists principally of eucalyptol and pinene. Note the more acute
lateral veins which are wiier apart, thus giving more room for the formation of oil
glands; the yield of oil is thus larger in these species. The marginal vein is further
removed from the edge and is slightly bending to meet the lateral veins.
3. Leaf of Eucalyptus radiata, Sieb.—This venation is characteristic of those
species whose oil consists largely of phellandrene and the peppermint ketone. Note
the still more acute and fewer lateral veins. The marginal vein has also become
so far removed from the e Ige that a second one occurs, and the slight bending, as seen
in 2, has culminated in this group in a series of loops. The spaces for the forma-
tion of oil glands are also practically unrestricted and a large yield of oil is thus
obtainable.
l
Jour. and Proc. Boy. Soc., N.S.W., xxxv. 116, and lieport to British Association,
Section B., Manchester, 1915-
CHAPTEK II.
THE RELATIONSHIP BETWEEN ODOUR AND CHEMICAL CONSTITUTION.

THE connections between chemical constitution, on the one hand, and
-colour or physiological action on the other have been continually studied
for many years, but the allied property of odour has only engaged occa-
sional attention within quite recent times.
The reason for this apparent neglect is not far to seek and lies largely
in the fact that no adequate means have yet been devised for measuring
and classifying odours.
The most noteworthy attempts to remedy this defect are those of
Zwaardemaker, C. van Dam,1 and Fournie,2 but for details of the
•" olfactometers " devised by them the original papers should be consulted.
These instruments are of distinct value for the matching of perfumes but
they all suffer from a fundamental defect inasmuch as they make no
allowance for the relative vapour pressures of the substances under ex-
amination.
The strength of an odour, up to a certain point, will depend upon the
amount of substance which reaches the nostrils; it is therefore necessary
that this factor should be taken into account when comparing odours.
In the ordinary manner of smelling we have to deal with a mixture of
the vapour of the substance and air. The maximum amount of sub-
stance which can thus be conveyed depends on the vapour pressure of
the substance and this in turn depends on the temperature, being greater
when hot and lesser when cold. In order therefore to make any com-
parisons of a fundamental nature the vapour pressure factor must be
allowed for.
It is the almost universal practice to record the nature and strength
of an odour at the particular temperature which may obtain at the time
of examination. Substances at their temperatures of boiling have a
common vapour pressure equal to that of the atmosphere, but it is clearly
impossible to smell a substance in such a condition, whereas, if we could
go to the other extreme, the absolute zero, it is probable that no vapour
would exist as such and for this reason alone, apart from any physio-
logical one, no odour would be discernible.
To operate at a fixed definite vapour pressure is also an obvious
impossibility, since this would involve a large range of temperature suffi-
cient to caus3 physiological complications.
H. Erdmann 3 considers that the volatility of a perfume does not
depend on its vapour tension alone but also on its specific solubility in
the air. This he deduced from the fact that certain bodies lose, more or
less completely, their odours in liquid air, but that on shaking the
mixtures the odours become strongly apparent. He argues therefore that
1 2
Jour. Chem. Soc., A. 3i. 1917, 606. P. and E.O.R., 1917, viii. 278.
Jour. Prakt. Chem., 1900, 225.
(25)
the perfumes dissolved in the liquid air evaporate with it in spite of the
fact that the temperature is in the region of — 190° C.
This is a doubtful conclusion since if temperature-vapour tension
curves for volatile substances be examined it will be seen that at low
temperatures the rate of diminution of the vapour tension falls off
rapidly and hence the-vapour tension at — 190° C. is often not vastly
different from what it is at normal temperature, and hence is not by any
means negligible when we take into account the very small quantity of
substance that needs to be inspired in order for its odour to be percep-
tible.
It has been satisfactorily demonstrated by Henning that the vapours
of odoriferous substances obey the general gas laws, and there is conse-
quently no need to assume any additional factor of the nature of specific
solubility.
A. Durand 1 attributes the sense of smell to " odourant ions". He
found that bodies such as musk and camphor greatly increase the condens-
ing power of dust free air for aqueous vapour and that the more strongly
odorous the air is, the greater becomes that effect, the amount of con-
densation being proportional to the number and the size of the ions in
the air. He considers that it is upon these "odourant ions" that the
sense of smell depends, and that this accounts for the fact that hygro-
metric conditions influence the sense. When air containing the perfume
is inspired, the odourant ions are retained in the olfactory region and
give rise to the sensation of smell.
The fact that the hygrometric state of the air influences the sense of
smell is probably more validly explained by the fact that moist air is
capable of carrying a larger proportion of the vapour of a volatile sub-
stance than is dry air.
It is interesting in this connection to note that Zwaardemaker 2 has
found that dilute aqueous solutions of odorous substances when sprayed
from an earthed sprayer yield a cloud having a positive charge of elec-
tricity. He found that on diluting these solutions to such an extent that
the electrical phenomenon is only just appreciable, the odour is also just
appreciable, but he found that the phenomenon is exhibited by other
substances which are3 inodorous but physiologically active. In a similar
manner Backmann compared the smallest quantities of benzene,
toluene, xylene, cumene, and durene that can be detected by the
olfactory organ. He found that the quantity diminishes as the number
of substituent methyl groups increases, also that the electrical charge
produced by spraying equimolecular aqueous solutions increases from
benzene to xylene and then diminishes.
In spite of the coincidences shown above it is doubtful if there is any
connection between odour and electrical charge. Heller 4 discards the
view that odour is of an electrical nature and criticises very severely an
electronic theory put forward by Tudat.5
Teudt considers that the nasal sensory nerves have electron vibrations
which are increased by resonance when odoriferous substances having cor-
responding intramolecular electron vibrations are inspired with air, and he
concludes that a chemical element can the more readily induce odour in
1
2
Comptes Rendus., 1918, 166, 129.
Jour. Chem. 6'oc., 1917, A. ii. 63 ; 41918, A. ii. 351 ; 1920, A. ii. 74.
*Ibid., 1917, A. i. 498. P. and E.O.R., 1920, 38.
*Ibid.9 1920, 12 ; and Jour. Chem. Soc., 1919, A. i. 607.
ODOUK AND CHEMICAL CONSTITUTION 27
its compounds in proportion as its electrons are more firmly united to
the atomic nucleus.
While there is little reason seriously to consider Teudt's first con-
ception, yet there is some justification for his second one, because the
osmophoric elements are all grouped together in the periodic table and
are therefore likely to have a fundamental common characteristic.
Of historical interest is Tyndall's observation,1 made so long ago as
1865, that gases with an odour possess the power of absorbing radiant
heat to a marked degree. Grijns 2 in 1919 was not able to detect any
relation between the intensity of the odour and its power of absorbing
radiant heat, and he therefore concluded that the stimulation of the
olfactory apparatus is not effected by the liberation of energy absorbed
from radiant heat.
The actual mechanism or process involved in the operation of smell-
ing is not exactly known. The most important investigation in this
direction is that of Backmann.3 He observed that in order that a sub-
stance may be odorous it must be sufficiently soluble in both water and
in the lipoid fats of the nose cells. The odours of the saturated aliphatic
alcohols first increase as the molecular weight increases and then de-
crease. The lower alcohols are comparatively odourless because of their
low degree of solubility in the lipoid fats, while on the other hand the
highest, members are odourless because of their insolubility in water.
The intermediate alcohols which are soluble in both fats and water have
powerful odours. Backmann used olive oil in his experiments as a sub-
stitute for the lipoid fats.
This explanation is probably applicable to the results recorded by
Passy,4 who found that with the homologous aliphatic acids the strength
of the odour—as measured by the reciprocal of the smallest quantity that
could be perceived—of formic acid is comparatively small, a maximum
is reached with butyric acid and after diminution to the weak oenanthic
acid, another maximum is reached with pelargonic acid, thereafter the
odour diminishes very rapidly.
Backmann's conclusions are of the highest importance and give a
reasonable explanation of many facts concerning the odours of substances,
such as the almost invariable rule that substances of high molecular
weight are odourless; the increase in the strength of the odours of
members of a homologous series to a maximum and subsequent diminu-
tion ; the lack of odour with the sugars and so on. Possibly also the
consistent lack of odour of polyhydroxy alcohols generally and of poly-
carboxylic acids may be satisfactorily explained in a similar manner.
In this connection it is interesting to recall Kremer's experiments.5
By means of a spectroscopic method, Kremer demonstrated that when air
saturated with an odoriferous substance such as pyridine or camphor is
bubbled through a liquid containing a lipoid—such as a suspension of
lecithin of a fatty animal tissue in Ringer's solution—more of the
odoriferous substance is adsorbed than when the saturated air passes
through water only.
It appears from this that some sort of reaction, physical or chemical,
takes place between odoriferous bodies and the lipoid fats of the
l
Heat as a Mode of Motion, London, 1865, 366.
2
Jour. Chem. Soc., A. i. 1919, 423.
:l
J. Physiol. Path, general, 1917, 17, 1; Jour. Chem. Soc., A. i. 1918, 88.
5
*Zeit. Angew. Chem., 1900, 103. Jour. Chem. Soc., A. i. 1917, 607.
olfactory organ. Buzicka x goes so far as to define an odoriferous body
as one which is soluble in the air (i.e. volatile) and which reacts chemically
with substances in the mucous membrane of the nose stimulating the
nose nerves. Haller 2 also considers that the action is undoubtedly of
a chemical nature and that the odoriferous molecule undergoes a change
of some kind.
That odoriferous bodies must undergo a change in the nose follows
from the simple fact that the sensation only lasts for a short while after
the removal of the source of odour. The substances in the mucus
membrane by means of which the odoriferous body is " fixed " are termed
" osmoceptors " by Euzicka.
The well-known phenomenon of smell-fatigue is explained by the
theory that actual chemical reaction takes place between the odoriferous
body and some reacting material in the nose ; thus it can easily be con-
ceived that some sort of addition reaction takes place and that directly
the osmoceptor in the nose becomes saturated no further reaction is
possible and no further odour can be appreciated until fresh osmoceptor
has been formed. Buzicka has suggested that two such osmoceptors
are involved since substances inspired in a concentrated state have
odours different to those perceived in a dilute condition. He suggests
that one osmoceptor reacts more readily than the other and in conse-
quence is the more readily saturated or consumed, this osmoceptor is
responsible for the sensation produced when dilute odours are inspired.
If the odour be concentrated, the first osmoceptor is saturated almost
instantaneously and then the sensation produced is the result of the
reaction between the odoriferous substance and the second osmoceptor.
These conceptions fit in very well with the facts and are probably
not far from the truth.
It seems likely that the sequence of events in the process of smelling
is, after the odoriferous substance has reached the nostrils, first for the
substance to dissolve in the aqueous outer layer, thence passing to the
lipoid fats, wherein an addition reaction takes place, causing a change
of energy which produces a sensation perceptible to the nervous centre.
It will be realised that the strength of an odour may suffer successive
diminutions in the process of smelling. It will be governed firstly, by the
vapour pressure .of the odoriferous body, secondly, by the degree of
solubility of the substance in water, thirdly, to its relative solubility in
the lipoid fats with respect to that in water, and, lastly, to the speed of
the chemical reaction. To a less extent the type of odour is similarly
governed and this may account for the many " shades " of odour that exist.
It is obvious that too much importance must not be placed on the
chemical aspect of the problem, especially as regards the strength of an
odour.
The first publication of importance regarding the relationship3 between
odour and chemical constitution per se, is that of Klimont, who at-
tempted an explanation on the lines of Witt's colour theory.4 Klimont
introduced the term " aromataphore " to designate groups which carry a
pleasant odour with them.
Bupe and Majewski5 renamed such groups "osmophores " and de-
3 2
P. and E.O.R., 1920, 37. Ibid., 39.
'"Die Synthetische und Isolierten Aromatea, Leipzig, 1899-
J 5
-Berichte, 1876, 522 and 1888, 325. Ibid., 1897, 2444, and 1900, 3401.
fined them as groups which confer a characteristic odour; such groups
are:—
—OH ; —0— ; —CHO ; —CO . CH 3 ; —OCH 3 ; —NO 2 ; —CN ; — N3.
They stated that the influence of these groups is not easily definable
with exactness and that the presence of other groups may modify pro-
foundly their effect, even so far as entirely to suppress the odour.
Kupe and Majewski attempted to determine by experiment the influence
of the relative positions of osmophores on each other in the same molecule.
In the case of the three methyl tri-azo-benzoates no great difference in
the type of odour exists, only a difference in the strengths, the para com-
pound being the strongest and the ortho the weakest. Of the three
methoxy-acetophenones, as another example, the meta isomer is almost
odourless in comparison with the ortho and para.
Rupe also found that one osmophore can be replaced by another
without greatly altering the type of the odour, thus vanilline, p-mtro-
guaiacol, and _p-cyanoguaiacol all have similar odours but varying in
strength.
Cohn l instanced a similar phenomenon in the similarity of the
odours of, benzaldehyde, nitro-benzene, benzonitrile, azimidobenzene, and
phenyldi-imide. He developed the " osmophore " theory and introduced
the terms " kakosmophore " and " enosmophore " to indicate those groups
which impart an upleasant and a pleasant odour respectively. The
kakosmophore groups are :—
—SH ; —S— ; —NC ; —As—but —CN is enosmophoric.
Cohn also drew attention to the fact that the molecular weight must
not be excessive if the substance is to have an odour, and that it frequently
happens that the addition of more osmophores to an odoriferous molecule
results in odourlessness due to an excessive molecular weight.
Itishould be noticed that the similarity between the osmophore theory
and Witt's chromophore colour theory does not extend much beyond the
initial conception and there seems to be no connection between the odour
and the colour of a body, it is indeed quite the exception for a body to
have both a strong odour and a strong colour. Two prolific sources of
colour, viz. the diazo group and a large molecule have no counterpart as
regards odour, and it is probably only by chance that quinone and
chroman both have pronounced odours and are the sources of colour.
The lack of connection between the two phenomena is, of course, to
be expected since colour is an objective phenomenon whereas odour is
subjective, or, as Kuzicka puts it, colour has a physical and odour a
chemical influence on the human senses.
Cohn points out that position isomerism is of the greatest importance
as regards the odours of isomerides, this is strikingly instanced in the
case of the tri-nitro tertiary butyl xylenes since the only one possessing
the powerful musk odour is that in which the nitro groups are situated
each in the meta position to the two others ; again the ortho-amido-
benzaldehyde has a strong odour but the meta and para isomerides are
odourless.
Cohn concludes that with benzenoid bodies " side chains " only im-
part odour when they occupy the ortho or para positions relatively to
one another, and he further states that the 1 . 3 . 4 positions are the most
1
Die Riechstoffe, 1904-
favourable for the production of odour. Many instances can be quoted in
refutation of these statements. It is, however, an undoubted fact that
the para isomers tend to possess stronger and more pleasant odours than
either the ortho or the meta.
One of the most important publications on this subject, considered
from the chemical side, is that of Gertrude Woker.1 This investigator
drew attention to the importance of multiple bonding. The double bond
is often accompanied by a pleasant, but the triple or acetylenic linkage
generally produces a disagreeable smell ; a multiplicity of double bond
can produce an effect equivalent to a triple bond.
Inasmuch as the terms pleasant and disagreeable are merely relative,
these statements are not capable of being accurately examined, but with-
out doubt there is a strong tendency for multiple bonding to produce a
strengthening of the odours.
Woker attributes this fact to an internal tension or strain caused by
the multiple bonding and the consequent increase in the volatility of the
body. Thus by loading one and the same carbon atom in a molecule
with the same or similar groups each having the same " polarity," — as in
the case of tertiary compounds —great intramolecular repelling forces are
set up, and this results in the well-known camphor type of odour which
almost invariably accompanies compounds with tertiary carbon atoms.
A group of opposite " sign " operates against the other three and has a
great influence, thus — COOH will greatly weaken the effect of three
methyl groups.
Woker attempts to apply this strain theory to ring compounds, and
considers that the five carbon atom ring produces less strongly odoured
substances than any other and points out that, according to Baeyer's
strain theory, the five carbon ring has the least internal tension. It is
very doubtful if this contention is correct, since the penta-methylenes do
not seem to be less strongly odoured than other polymethylene ring
compounds.2
Woker points out that the closing of a chain compound to form a ring
compound does not affect the odour much, thus the aliphatic terpineol
of W. H. Perkin, Jr.,3 2*3 di-methyl 5 hexenol 2 has a very similar
odour to a-terpineol, their respective formulae being : —
CH, C . CH3
V /\
CH CH, CH
CH8 CH,
r i
CH, CH,
\ / \/
CH CH
I I
C . OH C . OH
2*3 di-methyl 5 hexenol 2. a-Terpineol.

If the closing of the chain involves the disappearance of double bonds
l
2
Jour. Phys. Chem., 1906,
x. 455
:;
Cf. P. and E.O.R., May,
1919, 115, 123.
ODOUE AND CHEMICAL CONSTITUTION - - 31
the odour also diminishes, thus formaldehyde polymerises to the odour-
less trioxymethylene.
O
CH CH9
3CH2=0 -, I
CH,
Woker has apparently overlooked the classic example of the icon-
version of pseudo-ionone to ionone.
CMe
/ \
CH2 CH—CH=CH— CO.CH 3 -*
CH., CMe2 Pseudo-ionone.
\ S
CH
CMe,
/ \
CH, CH—CH= CH— CO . CH3
CH2
r CMe
i a-Ionone.
\ /
CH
'This transformation involves both the closing of the ring and the
disappearance of a double bond, and the result is an enormous strength-
ening of the odour. ^
Woker considers the cases of elements other than carbon, hydrogen
and oxygen, and shows that if the last be replaced by sulphur the odour
becomes more marked and less pleasant ; also that nitrogen when function-
ing as a trivalent element, frequently imparts a characteristic ammoni-
acal odour ; if it be bound to another atom by two bonds the odour is
intensified and deteriorates in quality. Phosphorous likewise frequently
imparts a disgusting odour to its compounds, and the odour of hydrogen
phosphide becomes progressively more penetrating when its hydrogen
utoms are successively replaced by alkyl, phenyl, or tolyl radicles, the
tertiary phosphines causing positive pain when smelt, but this last fact
is probably due to the reaction which takes place between tertiary phos-
phines and water in the nose.
Arsenic, antimony, and bismuth all impart unpleasant odours to their
compounds, and Woker points out a highly important fact that it is only
when the total valency of these elements is not employed that these
odours are produced.
Woker points out the apparent anomaly presented by uric acid.
NH— CO
I I
CO C— NH X
II )CO
NH— C— NH/
Uric acid is odourless in spite of three carbonyl groups, four trivalent
nitrogen atoms and a double bond, and that it is similarly colourless in
spite of four chromophores. Measurements of its refractive and disper-
sive properties indicate that it is a saturated body which suggests that
molecular attraction exists between the various groups.
The explanation of the odourlessness of this acid probably rests on
physical grounds. It is extremely insoluble in water and in oils, and is
practically non-volatile.
In 1909 Mehrling and Welde1 investigated experimentally the cause
of the " violet" odour of the ionones.
They formulated the rule that:—
" The aldehydes of cyclogeraniolene (or A° 1 * 3 • 3 tri-methyl cyclo-
hexene) form with acetone, bodies having a violet odour, so long as the
aldehyde group is next to the methyl or to the di-methyl group or to both,,
and the intensity of the violet odour increases with the number of alde-
hyde groups in the neighbourhood of the methyl. The odour of the
acetone condensation product disappears when the aldehyde group is-
removed from the neighbourhood of the methyl."
Thus in the case of the four cyclocitrals:—
CMe2 CMe, CMe2 CMe2
/\ . /\ /\ / \
CH2 C.CHO CH, CH.CHO CH2 CH. CHO CH CH. CHO
CH 2 CMe CH2 CMe CH CHMe CH CHMe
/ \ -/ \ / \ /
H2 CH CH CH2
their acetone condensation products all have an odour of violets, being
respectively /3-ionone ; a-ionone ; a-irone; and /3-irone.
Mehrling and Welde first determined if hydro-aromatic ring alde-
hydes in general gave violet like odours when condensed with acetone, and
it was found that in the case of the four following aldehydes only the
first yields a body having a violet odour:—
CHMe CH2 CH.C 3 H 7 CH
CH2 CH . CHO CH, CH . CHO CH., CH CH., C . CHO
I I " I |* I I fCMe2li
CH CHMe CH CHMe CH2 C.CHO CH, CH
CH CH CHMe CMe
the other yielding bodies having odours of fenchone and camphor.
They concluded, therefore, that in order to obtain the violet odour
the side chain must be connected to a cyclogeraniolene ring, e.g.:—
CHMe CHMe
//\ / \
CH CH CH2 CH.CHO
| | or | | etc.
CH2 CMe2 CH CHMe
\ /
CH
1
Annalen, 366, 119.
In order to determine if any other condition is necessary they con-
densed acetone with the following isomers of the cyclocitrals : —
CMe2 CMe2 CMe2
X \CH / \
CH CH 2 GH 2 2 CHO . C CH 2
CHO . C CHMe CH CHMe CH CHMe

\ /
\/
CH CHO CH2
and so obtained isomers of the ionones and irones.
The first of these cyclocitrals yielded an almost odourless product, but
the two others gave violet odoured bodies, hence they concluded that the
violet odour is only obtained when the side chain — CH= CH . CO . CH3
is next to a methyl group in the cyclogeraniolene ring.
To the conditions enunciated by Mehrling and Welde might be added
that the side chain must be unsaturated since di-hydroionone only has a
faint odour, and also that the violet odour is occasiopally present with
bodies of quite different structure from the ionones, for instance A' 2 '2*4
tri-methyl-tetra-hydro-benzaldehyde.
They next determined if the property of forming this violet odour
rests in the grouping — CMe2 — C(CHO) — CMe — such as occurs in the
cyclocitral ring, but it was found that the simplest aldehyde with
this grouping, viz. iso-propyl butyl aldehyde, CHMe2 . CH(CHO)CH2Me
when condensed with acetone yields a body having only a floral and not
a violet odour.
Austerweil and Cochin l in 1910 published the results of an experi-
mental investigation into the chemical nature of bodies having a rose
odour. The citronellol molecule was modified by the introduction of
various groups, but it was found that no very profound change results
when one or two methyl groups are introduced by substituting the
hydrogens attached to the carbon atom adjacent to the hydroxyl group.
Thus, citronellol,2 CMe2=CH . CH2 . CH2 . CHMe . CH2 . CH2 . OH, has a
rose like odour ; 1 methyl citronellol,
CMe2-CH . CH2 . CH2 . CHMe . CH2 . CHMeOH,
has the same odour but more pronounced, and suggestive of tea roses.
2 Di-methyl-citronellol, CMe2=CH . CH2 . CH2 . CHMe . CH2CMe2OH,
has the rose odour but is also slightly camphoracious (as is to be expected
with a tertiary alcohol) ; 1 ethyl citronellol has a very fine odour of roses
and 2 di-ethyl-citronellol is like the di-methyl compound but the rose
odour is more pronounced ; 1 phenyl citronellol is very strong.
They concluded that the rose odour accompanies the alcoholic group
whether primary, secondary, or tertiary, that is to say is represented by
the group —CH2CRBOH, where R is either a hydrogen atom or am
alkyl or aryl group. Semmler 3 had previously noticed that the rose-
odour is only evinced with an eight carbon atom chain in combination
with the group — CH2 . CRR . OH, thus di-methyl-heptenol,
CMe2= CH— CH2—CH2 . CMe2 . OH,
1
Comptes Rendus, 150, 1693.
8
There is some doubt concerning the formulae quoted here, but the conclusions
we no* vitiated thereby.
3
Die Aetherischen Oele, Vol. I, 249 250.
VOL. II. 3
has a fruity but not a rose odour. It should be noted, however, that
saturated alcohols with eight and nine carbon atom chains such as octyl
and nonyl alcohols do not have a rose odour, and it seems as if the pre-
sence of a double bond is also necessary for a distinct rose odour to exist.
Similar results with geraniol were published in the following year.1
It was found that 1 methyl geraniol,
CMe2 =CH . CH 2 . CH 2 . CMe= CH . CHMeOH,
has a pronounced odour of geraniums, 1 ethyl and 2 di-ethyl-geraniol
are more like the original alcohol. Au^terweil and Cochin concluded
that the more the group —GEE . OH increases in importance the less
the influence of the neighbouring double bond since 1 phenyl geraniol has
a geranium odour strongly reminiscent of roses ; further that the odour
changes from the rose to the geranium type on the introduction of a
second double bond.
W. H. Perkin, Jr., and his collaborators during the course of an ex-
tended investigation into the synthesis of the terpenes recorded some
interesting facts. It was found that A 3 ' 8/9 ^j-menthadiene has an even
more pronounced lemon odour than A r8/1 '_?>menthadiene (dipentene)
CMe CMe
CJdL., OH, (_yjLl2 CH
CH2 CH CH2 CH,

\S \/
C CH
<! A
CH, CH,
A 3 ' 8 /' > p-menthaciiene. Dipentene.
and the conclusion was drawn that the lemon odour was independent of
the position of the double bond. On removing the double bond from
the ring there results A 8/9 j>-menthene and the lemon odour disappears,
;giving place to a faint parsley odour; similarly A* jo-menthene which
has one double bond in the ring and none in the side chain also only
Jhave a faint odour. It follows that both double bonds are necessary for
the lemon odour to be manifest.
The methyl group, para to the isopropyl, modifies, but is not essential
for, the production of the lemon odour since A 3%/89 nor-menthadiene is
very like lemons in odour.
CH2
X\
CH, CH,
r CHi "
CH2
C
C
CH, CH,
J
Cowiptes itettdws, 151, 440.
ODOUR AND CHEMICAL CONSTITUTION 35
It should also be noted that the lemon odour is not confined to the
para isomers, as it is even more pronounced in several of the ortho and
meta bodies, although generally modified.
Perkin pointed out that open chain compounds, which are analogous
in structure to a terpene, show a certain similarity in behaviour ; thus
the addition of an ethyl group to 2-methyl 1'5-hexadiene by converting it
into 2-methyl 3-ethyl 1'5-hexadiene changes the unpleasant acrid odour
into a pleasant one reminding of lemon and peppermint.
CH2 =CH— CH2 CH2 =CH— CH2
\ \
CH 2 .CMe=dL> -> CH— CMe-CH,
9
2-methyl 1'5-hexadiene. 2-methyl 3-ethyl l*5-hexadiene.
Turning again to the theoretical aspect. Electrical theories have been
advanced by Teudt,1 Aronsohn, Zwaardemaker, and others, but little
attention need be paid to these.
Durrans 2 in 1919 attempted to develop a theory based on the ex-
amination of the odours of substances considered class by class, and
expressed the opinion that, from a chemical point of view, odour is caused
primarily by the presence of unsatisfied or residual affinity, but that the
possession or otherwise of an odour by a body depends on physiological
and physical as well as chemical properties. This theory, which is
named the " Eesidual Affinity Theory of Odour," demands that if a sub-
stance has an odour, it must answer to the following requirements : —
1. It must possess free or residual affinity.
2. It must be sufficiently soluble in both the water and the lipoid fats
of the nose.
3. It must be volatile in order that it can reach the nostrils.
If a body be what we term odourless, its odourlessness may be due to
its failure to satisfy any one or more of these demands.
The second of the premises of the residual affinity theory has already
been dealt with here, the third is obvious, it remains therefore only to
consider the first.
The " Residual Affinity Odour Theory " can have both a qualitative
and a quantitative conception since the nature, distribution, and amount
of affinity may vary from substance to substance. It is well known that
bodies of similar type and construction frequently have similar odours.
This fact was drawn attention to by Parry 3 who instanced the various
types of odoriferous alcohols : —
1. The fruity odours of the higher fatty alcohols.
2. The soft rose-like and similar odours of the di-olefinic alcohols of
the geraniol type.
3. The soft heavier odours of the cyclo substituted aliphatic alcohols
such as benzyl and phenyl-ethyl alcohols.
4. The sharp (camphoraceous ?) alcohols of the terpene alcohols of
the borneol type.
5. The heavy '" oriental " odours of the sesquiterpene alcohols.
6. The phenolic odours.
!P. and E.O.R., Jan. 1920, 12; Feb. 1920, 38.
2 Ibid., 21 May, 1919, and Dec. 1920, 391.
*Ibid.t May, 1916, 129.
As other instances of typical " class " odours might be quoted :—

Para substituted phenol ethers . Aniseed
Ring substituted dihydroxy benzenes Quinone
Cyclohexane alcohols Menthol
Menthenols . Terpineol
Menthadienes Lemons
Ketenes Piercing
Aldehydrates . Intense lemon
Acetals . Soft ethereal
1-2-di-ketones Quinone.
Very many other examples might be quoted, but these suffice to show
that each of the classes of substances quoted has some common inherent
characteristic quite apart from questions of volatility, solubility, or
physiological action.
Durrans attributes this concurrence to the unsatisfied or residual
affinity of the molecules, the residual affinity of each molecule being com-
parable with that of other molecules of the same type, any variation of
odour between the substances of cne type or between the types being due to
variations in the residual affinity either in kind, quantity, or distribution.
This theory takes account of the view that the sensation of odour is
the result of a chemical reaction in the nose, since in order for a body to
be able to enter into chemical reaction the possession of residual affinity
is probably a sine qua raw, but it should be noted that the converse does
not hold.
It is easy to conceive that a class of similar bodies possessing similar
residual affinities would react with the osmoceptors of the nose in similar
manners and in consequence produce similar odours.
It is not easy exactly to determine the amount or distribution of the
residual affinity of a molecule, but certain examples afford satisfactory
ground for surmise.
Consider the benzene molecule. When not overpowered by other
osmophores, it generally imparts a typical " aromatic " odour, but directly
the nature of the ring—with all the possibilities of its six "fourth affini-
ties "—is upset by the introduction of two or more hydrogen atoms which
are themselves non-osmophoric, an entirely different but still character-
istic class odour results. A large change in the residual affinity of the
molecule has been accompanied by a large change of odour.
Mere substitution of hydrogen, by a weak osmophore methyl, for in-
stance, does not produce any striking change of odour; this corresponds
with the fact that the affinities of the benzene ling are only slightly in-
terfered with in this case. It should also be noted that the hydrobenzenes
no longer possess the chemical properties of benzene, being more like
aliphatic bodies. This fact is again in accordance with the idea that
odour is the result of a chemical reaction in the nose.
Another interesting example to examine is that of the ketenes. These
bodies of extremely piercing odour have the general formula KK'C=CO,
and they give ample evidence of unsatisfied affinity, polymerising with
exceptional rapidity, combining easily with water and alcohols and con-
densing with other substances in many ways. If the double bond of the
ketenes be hydrogenated there result the corresponding ketones, which
are much milder in odour, much less reactive, and which show much
less evidence of unsatisfied affinity.
Unsaturated bodies, generally, have stronger odours than the corre-
sponding saturated compounds and are known to possess more residual
ODOUR AND CHEMICAL CONSTITUTION 37
affinity than the latter, and to be more reactive chemically. Thus for
example the very pungent dipropargyl or l*5-hexadiine, which is very
reactive chemically, corresponds to the stable and nearly odourless
saturated hexane; other pairs which might similarly be enlarged upon
are allyl and w-propyl alcohols ; carbon suboxide and propylene glycol;
crotonic aldehyde and n-butylaldehyde, and so on.
The effect of a particular element on the odour of its compound seems
also to lend support to the "residual affinity" theory, for it is only the
elements which possess residual affinity in certain of their compounds,
which function as osmophores. Oxygen, nitrogen, sulphur, phosphorous,
halogens, arsenic, antimony, bismuth, etc., whose valencies vary under
certain conditions are powerfully osmophoric whereas carbon, hydrogen,
and many others which have a constant valency are practically non-
osmophoric, and it is very instructive to note that the element is osmo-
phoric when it is not employing its full number of valencies and therefore
has free affinity.
By far the larger number of elements are non-osmophoric because
they or their compounds fail to satisfy one or more of the three essential
conditions of the residual affinity theory. Thus the majority of salts
cannot have an appreciable odour because of two reasons—non-volatility
and non-solubility in the lipoid fats, also in many cases the chance of
the existence of free, residual affinity is remote. These defects are not
necessarily inherent in the atom itself but may be due to its manner of
combination ; thus arsenic, when functioning as a metal, does not yield
odoriferous compounds, for example, arsenious chloride, in spite of its
high volatility, is odourless. But when it is part of a radical, it fre-
quently gives rise to bodies of great pungency such as cacodyl As 2 Me 4 ;
the fact that cacodyl readily takes fire in air is good evidence that it
possesses unsatisfied affinity.
The osmophoric elements are all closely associated in the periodic
table and are therefore likely to have a fundamental common character-
istic and the property of varying valence is one of their common charac-
teristics, whereas it seldom occurs with the non-osmophoric elements.
If in an odoriferous body the atoms with which the possibility of free
affinity exists be replaced by others where such possibility does not exist
the odour is removed. Thus cacodyl would yield the odourless ethane ;
methyl iodide would give methane; ethyl hydro-selenide would yield
ethane, and so on.
It seems evident therefore that the unsatisfied affinity of an odori-
ferous body plays a fundamental part in the production of its odour by
reason of one or more chemical reactions taking place in the olfactory
organ; the reactions must necessarily be complicated and rapid. They
are at present entirely unknown and problematical, but no very great
progress in the knowledge of this subject* is likely to be made until the
chemical properties of the osmoceptors have been determined.
CHAPTER III.
THE following groups of compounds will be described in the present
chapter : —
1. Hydrocarbons.
2. Sesquiterpenes.
3. Alcohols.
4. Esters.
5. Aldehydes.
6. Ketones.
7. Phenols and phenolic compounds.
8. Oxides and lactones.
9. Nitrogen compounds.
10. Sulphur
11. Free acids.
1. HYDROCARBONS,
HEPTANE.
The aliphatic hydrocarbon heptane, C7H16, has recently been dis-
covered as a constituent of the oil obtained by the distillation of the
resinous exudation of Pinus Sabiniana, Pinus Jeffreyi, and a few other
essential oils. It is a highly volatile liquid of specific gravity 0-688 and
boils at 98° to 99°. It has, probably, the lowest specific gravity of all
liquids found naturally in essential oils.
STYROLENE.
Styrolene, C8H8, also known as styrol, is phenyl-ethylene, of the con-
stitution.
CH
HO- .CH
C . CH : CH2
It is a very aromatic oil, useful in some bouquets, and is found
naturally in storax and other balsamic substances. It is prepared by
various methods, amongst them being the heating of cinnamic acid with
lime to 200°. It is a colourless, highly refractive liquid having the
Specific gravity ....... 4 . . 0-9074
Refractive index ......... 1-5403
Boiling-point ......... 140° to 145°
(38)
THE CONSTITUENTS OF ESSENTIAL OILS 89
It yields two sets of halogen derivatives, the a-derivatives—for example,
bromostyrolene, C6H5CH: CHBr—and the /^-derivatives, such as
C6H6CBr: CH2. The ^-products are useless in perfumery, but the a-
products are highly odorous bodies, possessing a powerful odour of
hyacinths, a-chlorostyrolene is obtained by the action of caustic alkali
on dichlorethyl-benzene. a-bromostyrolene is obtained by boiling di-
brom-hydrocinnamic acid with water, o-chlorostyrolene boils at 199°,
and a-bromostyrolene melts at 7C and boils at 220°.
Styrolene yields a dibromide, C6H5 CHBr. CH9Br, melting at 74°
to 74-5°.
DIPHENYL-METHANE.
This hydrocarbon, C 6 H 5 . CH 2 . C6H5, is a synthetic body, with an odour
which is in the main that of geranium leaves, but which also has a sug-
gestion of oranges. It has lately come into considerable vogue, together
with the corresponding body, diphenyl-oxide, as the basis of artificial
geranium oil. It can be prepared by treating benzyl chloride and benzene
with zinc-dust; or from methylene chloride, benzene, and aluminium
chloride ; or by the reduction of benzophenone with zinc-dust. It is a
crystalline body melting at 26*5°, and boils at 261°.
TERPENES.
The terpenes proper are mostly volatile liquids—rarely solids—all
having the formula C10H16; they form the principal portion, from a
quantitative point of view, of an enormous number of essential oils, but
rarely have any great odour value. They are easily decomposable, es-
pecially under the influence of air, moisture, and light, and it is the
decomposition of the terpenes in an essential oil, due to age or faulty
storage, which is the most frequent cause of the oil spoiling. Since most
terpenes boil within a comparatively narrow range, it is somewhat
difficult to separate them in a state of purity. Even when converted
into crystalline compounds from which the terpene is regenerated, there is
a possibility of molecular rearrangement, so that the regenerated terpene
may be different from the original. Hence the fact that numerous
terpenes have been described from time to time, which are in reality im-
pure forms of a well-known terpene with traces of some other body.
This is especially true of pinene which has been described under
numerous other names. The ease with which molecular rearrangement
takes place in many terpenes, renders evidence of constitution based on
analytical reactions of these bodies of doubtful value, and it is only in the
case of those terpenes which have been synthesised that their constitution
can be regarded as definitely settled.
The type substance upon which the nomenclature of the terpenes is
based is hexahydro-p-cymene, which is termed j}-menthane, the carbon
atoms being numbered as shown in the following formula:—
/CH2—CH2x
/ 2 a \
4N
CH3—CH/ ^ >CH—CH
X « * o /
X3H.,—CH.,/
Following'the usual rules of chemical nomenclature, the examples below
are readily understood:—
X/V^-1-J. . V_^J.J.ij\. s\Jl
CH 3 . Of " >CH—CH/
\CB8. CH,/ XJI
containing one double linking, is A ^-menthene.
i
PTT . r^TT r TT
<
v^n o_ri9v s,\jrL. y
- \CH-Cf "
CH,.CH,/ \CH,
or limonene, containing two double Unkings, is A l 8(9)-^-menthadiene.
2
CH 3 .C/ ' \CH.C(OH)/
\CH 2 . CH,/ \CH,
or terpineol is A ^jj-menthenol (8), the (8) referring to the ol, or hydroxy
group.
The abbreviated nomenclature of the compounds of the ortho and meta-
series follows the same rules. For example :—
CHgv g
>C(OH) — CH — CH
CH/ /* » \
10
CH,.«
7 x
CH,—CH,
is A 3 -o-menthenol 8.
8 'CH,
CH = C — Cf
^CH3
s ^ 10
CH 3 . CH/ l
\6 5/
CH,—CH,
2 8
A - .(°)-w-menthadiene.
PlNENE.
There are four distinct terpenes known under this name, namely,
a-pinene, /3-pinene, 8-pinene, and isopinene. It must be emphasised, how-
ever, that they are all of different constitution, and the customary nomen-
clature is ill-chosen, as they should be known by entirely different names.
Pinene in one form or another has been described under numerous
names, such as terebenthene, australene, eucalyptene, laurene, olibene, and
massoyene, all of which are more or less impure forms of a-pinene or
/ft-pinene.
a-pinene is the most commonly occurring terpene found in nature,
and, according to most modern views, has the following formula :—
CH,
A
CH
«-pinene is an optically active terpene, which occurs both in the dextro-
rotatory and the laevo-rotatory forms, but is not found in the inactive
form, except as a mixture in unequal quantities of the two active forms,
with a varying specinc rotation.
It is obtained from American turpentine as dextro-a-pinene, or from
French turpentine as laevo-a-pinene. It is also obtained in a very pure
form as dextro-a-pinene from Greek oil of turpentine. Optically inactive
a-pinene can be obtained by regeneration from the nitrosochloride. The
purest specimens of a-pinene yet obtained have the following char-
acters :—
Dextro-a-Pinene. Laevo-a-Pinene.
Boiling-point . . . . 155° to 156° 155° to 156°
Specinc gravity at 15° 0*864 0-865
Specinc rotation + 48-4° - 48-6°
Optically inactive a-pinene can be obtained by heating a-pinene
nitrosochloride with aniline.1 It has the following characters:—
Wallach2 has also obtained laevo-a-pinene by heating nopinol-acetic
acid in a current of hydrogen.
a-pinene forms a number of well-defined crystalline compounds,
several of which serve for its identification. Of these one of the best
known is the nitrosochloride. This body was discovered by W. A.
Tilden, who prepared it in the following manner: the pinene is dis-
solved in two to three times its volume of petroleum ether, cooled to 0°,
and an 8 per cent, solution of nitrosyl chloride in equal volumes of
petroleum ether and chloroform added with constant stirring, care being
taken that the temperature is kept as near 0° as possible. When the
reaction is over alcohol is added, and the crystalline precipitate is
separated, washed with alcohol, and dried at 50°. The melting-point of
the compound is usually given as 103°, but by careful crystallisation from
a chloroform solution it can be raised to 115°. It is possible that the true
melting-point is about 109°, and that higher figures may be due to decom-
position into nitroso-pinene. Tilden stated that only very small yields of
the nitrosochloride, which is optically inactive, could be obtained from
1 2
Wallach, AnnaUn, 252, 132; 258, 343. Ibid., 368, 1.
a-pinene with a high optical rotation: the lower the optical rotation of
the pinene used, the higher is the yield of nitrosochloride obtained. The
formula for pinene-nitrosochloride has been assumed to be C10H16NOCly
but Baeyer showed it to be a bi-molecular compound of the formula
(C10H16NOC1)2, and always consists of equal quantities of the nitroso-
chlorides of the two optically active forms of a-pinene. Hence its optical
inactivity. Where the pinene, from which it is derived, is highly
optically active, that is, contains much excess of one of the optically
active forms, the nitrosochloride of that active form is the result of the
reaction. This body, however, is very unstable and tends to become
inverted to optical inactivity, but during the inversion so much heat is-
liberated that the bulk of the nitrosochloride is decomposed. This,
then, is the explanation of the fact that the yield of nitrosochloride is in
inverse ratio to the optical activity of the a-pinene.
In the preparation of the nitrosochloride, Wallach proposed to use
pinene in glacial acetic acid and amyl nitrite. Ehestadt has recently
proposed the following method, which is very simple and yields excellent
results : The pinene (or oil of turpentine) is diluted with its own volume
of ether, the solution cooled with ice, and the gas generated by dropping
a saturated solution of sodium nitrite into concentrated hydrochloric
acid passed through the solution. Fine crystals of pinene-nitrosochloride
soon commence to separate out. Schimmel & Co. obtained the following
yields of nitrosochloride by the methods quoted :—
Rotation of Per Cent. (Tilden). Per Cent. (Wallach). Per Cent. (Ehesttidt).
Pinene.
+ 11° 10' 10 per cent. 30-31-4 per cent. 37'5 per cent.
+ 40° 23' 4 4-6
- 33° 42' 9-11 10
+ 0° 20 22
Nitroso-pinene is obtained from pinene-nitrosochloride by the action of

alcoholic potash,
C10H16NOC1 + KOH = C10H15NO + KC1 + H2O.
Nitroso-pinene may be prepared for identification purposes as follows:
To a solution of 12 grams of sodium in 30 c.c. of 90 per cent, alcohol,
100 grams of pinene-nitrosochloride are added. The mixture is boiled
on a water-bath, under a reflux condenser, until the reaction is complete.
Water is added, the • clear solution filtered from insoluble impurities,
and the filtrate poured into excess of acetic acid. The nitroso-pinene
separates as an oil which solidifies to a yellowish mass in a few days.
This is broken up, washed with water, and dried on a porous plate. It
can be recrystallised from acetic ether, when it is obtained in the pure
condition, and then melts at 132°.
Pinene-nitrosochloride forms a series of compounds with various
bases, such as propylamine, amylamine, benzylamine, etc., known as
pinene-nitrolamines. If two molecules of benzylamine in alcoholic
solution be allowed to act on one molecule of pinene-nitrosochloride,
pinene nitrol-benzylamine separates on the addition of water, and on
recrystallisation from a mixture of ether and alcohol, forms beautiful
rhombic crystals melting at 122° to 123°. Dextro-a-pmene and laevo-a-
pinene yield the same optically inactive nitrolamines. The corresponding
nitrol-piperidine melts at 118° to 119°. Wallach considers the formula
for the nitrolamines to be—
/NO
°»H'<NHB
whilst Baeyer considers them to be bi-molecular and to have the
formula —
NHK EHN,
An important compound for the identification of pinene is the hydro-

chloride C10H16HC1, a body once known as artificial camphor, on account
of its odour being very similar to that of natural camphor. This body
is obtained by saturating well-cooled perfectly dry pinene with dry
hydrochloric acid gas. If the reagent is moist or the temperature be
allowed to rise, the terpene molecule suffers rearrangement and some
dipentene dihydrochloride is formed. Pinene hydrochloride is a volatile
substance, having a camphor-like odour, and melts at 127°. The optical
properties of pinene hydrochloride are peculiar. Wallach states that the
hydrochloride from laevo-pinene is laevo-rotatory, whilst that from dextro-
pinene is optically inactive. Long,1 however, has shown that this is
not correct, and in this has recently been fully confirmed by Tsakalotos
and Papaconstanfinou.2 The laevo-rotatory hydrochloride prepared by
Wallach had a specific rotation - 3O7°, and the last-named chemists
have prepared numerous samples from dextro-pmene, whose specific
rotation varied only between +33° and + 33*4°.
Pinene hydrobromide, C10H16HBr, is prepared in a manner similar
to that described for the hydrochloride. It melts at 80° and has a specific
rotation of about + 30° or - 30°, according to the rotation of the pinene
from which it is prepared.
Sometimes, on account of the difficulty in preparing the nitroso-
chloride from a highly active a-pinene, it is necessary to examine the
oxidation products before it is possible to come definitely to a conclusion
as to the presence or absence of the hydrocarbon. Pinene yields numer-
ous acids as the result of oxidising processes, so that the method of
preparing the product to be examined must be rigidly adhered to if
useful results are to be obtained. The terpene is transformed into
pinonic acid, Cj0Hlt5O3, in the following manner : A solution of 233
grams of potassium permanganate in 2000 c.c. of water is placed in a
flask, and an emulsion of 100 grams of the hydrocarbon in 600 c.c. of
water is gradually added in small portions. The mixture is kept cool
by means of a current of cold water, and shaken continuously. The
oxidation products are then treated as follows : The liquid is filtered
from manganese oxide, and evaporated to about 1000 c.c., saturated
with carbon dioxide, and the neutral and unaltered compounds removed
by extracti )n with ether in the usual manner. The crude pinonic acid
is separated from its potassium salt by sulphuric acid and is then ex-
tracted with ether. If /3-pinene be present, nopinic acid will be present
1
2
Jour.Amer. Cliem. Soc., 21, 637.
Jour, de Pharm. et de Chim., 1916, 97.
amongst the oxidation products. This forms a highly insoluble sodium
salt, and is removed in this form.
There appear-to be either several isomerides of pinonic acid, or such
closely related oxidation products as to render the purification of the
acid a matter of great difficulty. The characters of the dextro- and laevo-
rotatory forms of this acid have, however, been settled by the researches
of Barbier and Grignard * and Schimmel & Co.2
By oxidation of d- and Z-pinene of high rotatory power, Barbier and
Grignard obtained the optically active forms of pinonic acid. Z-pinene
from French turpentine oil (boiling-point 155° to 157°, a D - 37'2°; 157° to
160°, aD - 32'3°) was oxidised with permanganate. From the product
of oxidation, which (after elimination of the volatile acids and of nopinic
acid) boiled at 189° to 195° under 18 mm. pressure, Z-pinonic acid separ-
ated out in long crystalline needles, which, after recrystallisation from
a mixture of ether and petroleum ether, melted at 67° to 69°. The
acid was easily soluble in water and ether, fairly soluble in chloro-
form, and almost insoluble in petroleum ether. Its specific rotation is
[a]D - 9O5° in chloroform solution. Oximation produced two oximes ;
one, laevo-rotatory, melting-point 128°; and the other, dextro-rotatory,
melting-point 189° to 191°.
14°
rZ-pinene from myrtle oil (boiling-point 155° to 158°; d—^ 0-8635 ;
nD 1-46977; [a]D + 39'4°) yielded upon oxidation a mixture of racemic
and ^-pinonic acids. The latter melted at 67° to 68° and showed the
same properties as the acid described above, except as regards its specific
rotatory power, which was found to be [a]D -f- 89'0°. By mixing the two
active pinonic acids the inactive form, melting-point 104°, was obtained.
Oximation produced the two oximes corresponding to the above. A pre-
paration obtained by Tiemann from a-dihydroxy-dihydrocampholenic
acid by means of distillation, and described as Z-pinonic acid (melting-
point 98° to 99°; oxime melting-point 147°) possibly represents, accord-
ing to Barbier and Grignard, a stereo-isomeric acid.
Schimmel & Co. have published the following method, based on the
oxidation of a-pinene to pinonic acid, and /?-pinene to nopinic acid, for
the identification of pinene in mixtures, such as, for example, with
limonene in the case of lemon oil: Five c.c. of the oil or fraction of the
oil containing pinene is shaken with 12 grams of powdered potassium
permanganate, 2'5 c.c. of sodium hydroxide, and 700 c.c. of iced water for
about three hours. The mixture is then saturated with carbonic acid gas
and distilled with steam to remove any unoxidised products. After filtration
the liquid is evaporated in a current of carbon dioxide to about 200 c.c.
and repeatedly extracted with chloroform to remove impurities. Gradu-
ally, on further evaporation, a crystalline incrustation appears, which is
principally the highly insoluble sodium salt of nopinic acid, the oxidation
product of ^-pinene. This is separated by means of a suction filter and
treated with dilute sulphuric acid, when nopinic acid, C10H16O3, readily
separates out in crystals which melt at 125°. If nopinic acid be oxidised
by passing a current of steam through water in which the acid and lead
peroxide are suspended, the ketone, nopinone C9H14O, is produced. This
substance is a liquid ketone of unmistakable odour, forming a semicarba-
zone melting at 188'5°. The oxidation products of a-pinene remain in
1
Comptes rendus, 147 (1908), 597. -Report, April, 1909, 120.
the mother liquor after filtering off the sodium nopinate. At present,
however, no satisfactory method has been devised for separating this,
unless it be present in a comparatively large amount, when its semicarba-
zone can be prepared, which melts at 204°.
The hydration product of a-pinene is particularly interesting. If
pinene be allowed to remain in contact with dilute mineral acid for some
time, at ordinary temperature, terpin hydrate, C10H18(OH)2 + H2O, is
formed. The best method for the preparation of this body is as follows :
A mixture of 8 parts of pinene, 2 parts of alcohol, and 2 parts of nitric
acid, of specific gravity 1/250, is placed in a flat evaporating basin. After
standing for several days the liquid is poured off from the crystalline crust
which is formed, and neutralised with alkali, when a second crop of
crystals is obtained. The successful preparation of this compound depends
largely on the temperature of the atmosphere, and the best yield is
obtained during the cooler part of the year. Terpin hydrate, which also
results from the oxidation of limonene and dipentene, under suitable con-
ditions, crystallises from alcohol in transparent, well-defined monoclinic
prisms, soluble in 200 parts of cold water and in 22 parts of boiling water.
It melts at 116° to 117°. When distilled, or dried over sulphuric acid,
anhydrous terpin is formed. This body, C10H18(OH)2, ii.elts at 104C to
105°, and probably has the constitution indicated below, which suggests
that it is the hydrated compound of cineol or eucalyptol:—
PTT /^TT
U±la O±la
COH
COH
CH
J L
3 " 2^J VJ L L
- - 3
Terpin. Cineol.
It is convenient to here mention the hydrocarbon verbenene, C10H14,
on account of its relationship with pinene. It results from the action of
acetic anhydride on verbenol, thet alcohol corresponding with the ketone,
verbenone. So produced it is laevo-rotatory. The dextro-rotatory and
racemic varieties are also known.1 The sesquiterpenes have the following
characters when regenerated from their respective dibromides :—
^-Verbenene. rf-Verbenene.
Specific rotation - 100-61° + 100*71°
Refractive index — 1-1980
They yield beautifully crystalline dibromides melting at 70° to 72° and
having a specific rotation ± 298°. The racemic dibromide melts at
50° to 52°.
1
Berichte, 1921, 54, 887; Annalen, 1913, i., 495.
/-Verbenene is reduced by sodium and alcohol to dihydroverbenene,

which is so closely related to pinene that it has been named 8-pinene.
This body has the following characters :—
Boiling-point . . . . . . 158° t o 159° a t 7 6 2 m m .
Specific rotation + 36-52°
It yields ordinary pinene hydrochloride when treated in the usual
manner with hydrogen chloride. Verbenene and 8-pinene have the fol-
lowing constitutions:—
C . CH, CH . CH3
\
HC \ CH
S
C(CH,),
H,C H2C
\ CH
V
CH
8-Pinene.
/3-pinene, which is also known as nopinene, is found associated with
a-pinene in turpentine oil, and in numerous other terpene-containing
essential oils. The properties of yS-pinene, in as pure a state as it has
been obtained, are as follows :—
NATURAL /^-PINENE (FROM HYSSOP OIL).
Specinc gravity , 0-865
The artificially obtained terpin, prepared as described below, has the
(1) (2)
Boiling-point 162° to 163° 162° to 163°
Specific gravity 0-S66 0-8675
Refractive index ' 1-47^4 1-4749
Optical rotation - 22° 20' - 22 J 5'
/2-pinene has the following constitution :—
CH,
C
(CH<)
H9C CH,
CH
Wallachl has prepared this terpene artificially in the following manner:
The starting-point for the preparation of the hydrocarbon was the ketone
mopinone, which is the oxidation product of nopinic acid, which itself
results from the oxidation of /3-pinene or nopinene. By treating no-
pinone with bromacetic acid in the presence of zinc-dust, the ethyl ester
of nopinolacetic acid was obtained. This body, on dehydration by means
of acetic anhydride yields, together with other products, /2-pinene, which
has the characters given above,
/3-pinene does not yield a nitrosochloride. By treatment with dry
hydrochloric acid it yields a mixture of bornyl chloride and dipentene
dihydrochloride. The terpene is best identified by oxidation to nopinic
acid, as described under a-pinene, or, when existing in more than very
small quantity by the following method of procedure :—
Three parts of the oil or fraction containing much /2-pinene are well
shaken with a solution of 7 parts of potassium permanganate in 90 parts
of water, with 1-5 parts of caustic soda. When reaction is complete, the
product is steam distilled, and the residue, after removal of unaltered
products, filtered from the manganese oxide. The filtrate is reduced to
30 parts by evaporation, and the nopinate of sodium separated by cool-
ing the liquid. Excess of dilute sulphuric acid is added, and the nopinic
acid so released is extracted by benzene, from which it crystallises in
fine needles melting at 125° to 127°. The identification can be completed
by the further oxidatiorj of the nopinic acid to the ketone nopinone. Ten
grams of the nopinate of sodium are dissolved in 100 c.c. of boiling water,
and a solution of 3 grams of potassium permanganate in 75 c.c. of water
is added, and then 2 grams of sulphuric acid in 20 c.c. of water. The
ketone is obtained from the reaction mass by distillation with steam. It
yields a semicarbazone melting at 188° to 189°.
Varon 2 considers that a-pinene and /2-pinene exist in the following
approximate proportions in French, American, and German turpentine
oils:—
French Oil
Rotation [a]- Per Cent.
a-pinene - 39-5° <3
/3-pinene . . . - 19 8° 37
American Oil.
Rotation [a]j Per Cent.
a pinene . . . . . . . . . + 24° 73
j8-pinene - 19-8° 27
German Oil.
Rotation [a],- Per Cent.
a-pinene + 7-5° 7i
0-pinene - 18*3° ^8
Isopinene is a name which has been applied to at least two terpenes.
Of these the earliest so-named is that isolated by Aschan 3 by decompos-
ing the liquid chlorides obtained in the process of preparing pinene
hydrochloride, by the action of bases. He thus obtained a hydrocarbon
which he termed pinolene, C10H1(3, boiling at 145° to 146°. By converting
pinolene into its hydrochloride, and then removing the hydrochloric acid
by means of aniline, he prepared a terpene, which he termed isopinene,
1 2
Annalen, 245, 251. s
Comptes rendus, 149 (1909), 997.
Berichte, 40 (1907), 2250.
boiling at about 156°. Both terpenes yielded a hydrochloride melting
at 36° to 37°, which appear to be identical.
Further investigations showed that the two hydrochlorides are
identical in all respects. Moreover, pinolene is not a single body, but
a mixture of at least two hydrocarbons which the author has called a-and
/3-pinolenes. The separation of the two isomerides may be effected by
the action of potassium permanganate at 60° to 80° C.: a-pinolene is
completely destroyed, whilst the /3-isomeride persists.
fi-pinolene has the following characters :—
Boiling-point 14-2° to 144°
Its molecular refraction is 42*37, appearing to indicate a trrcyclic
compound, whilst the value calculated for a tricyclic body C10H16 is
41-83.
/3-pinolene, when saturated in ethereal solution with dry hydrogen
chloride, at 15° C., yields a very readily liquifiable hydrochloride, melting
at 25° to 26° C., which does not appear to be identical with the hydro-
chloride obtained from crude pinolene. Aniline converts it into pure
The isopinene used in subsequent researches was obtained by frac-
tionating the pinolene boiling at 144° to 145° C., a mixture of the a- and
/?-isomeride, then treating it with hydrogen chloride and removing this
acid by means of aniline. The hydrocarbon obtained was purified by
oxidation with permanganate in acetone solution. It possesses the follow-
ing constants:—
orv°
Specific gravity . . . . . . . 0-8677 at
When purified by conversion into its hydrochloride and regenerated
by means of aniline, its properties were practically unaltered, as follows :—
Boiling-point 154-5° to 155'5°
20°
Specific gravity 0- 658 at -V_
Optical rotation . . . . . . . . + 2-61°
According to Aschan the formula for isopinene is—
CH
C. CH.,
C(CH3)2
CH
CH
which is the formula proposed by Wallach for fenchene. The relationship
of this body to Wallach's fenchene is still a matter of uncertainty, and

requires further investigation (see vide under Fenchene, p. 55).
Zelinsky,1 apparently overlooking Aschan's isopinene, has improperly
appropriated the same name to a quite different terpene.
He prepared this in the following manner:—
U-pinene (boiling-point 155° to 155-5°; d ^ 0'8587; [a]D - 43-81°;
wD200 1*4652) in absolute ethereal solution was allowed to react with
palladium black. After a few hours hydrogen was passed into the liquid
at ordinary temperature, giving rise to a terpene possessing the following
20°
constants : boiling-point 158-5° to 159'5° d ~ 0-8573 ; [a]D - 38'09° ;
w020o 1*4641. It does not form a crystalline hydrochioride or nitroso-
chloride. Zelinsky assumes that a-pinene first absorbs hydrogen, with
the formation of hydropinene, and that wopinene results from the latter,
according to the following formulae : —
C.CH, CH . CH C . CH
EC/
CH9 CH9
X
CH CH
a-Pinene. Hydropinene. Isopinene.
The behaviour of a-pinene towards palladium black is very different
when it is exposed for a period of four weeks to the action of hydrogen
under very low pressure. In this case it yields hydropinene (boiling
on°
point 167-5° to 168°; d -^ 0-8567; [a]D - 19-84°; ?zD200 1-4605).
FlRPENE.
Firpene is a terpene, which may be a chemical individual, but which

may be an impure terpene not yet definitely characterised. It was
isolated from the turpentine of the " Western fir," by Frankforter and
Frary,2 who found it to have the following physical characters:—
Boiling-point . 152° to 153-5°
Specific gravity 0-8598 at 2Q°-
Specific rotation - 47-2°
It yields a crystalline hydrochioride melting at 130° to 131°. This com-
pound is much more easily volatilised than pinene hydrochioride. With
chlorine it yields a dichlor-firpene hydrochioride, whilst pinene yields no
similar compound. It also yields a crystalline hydrobromide melting at
102°. No crystalline nitrosochloride has been prepared. The melting
1 2
Berichte, 44 (19J1), 2782. Jour. Amer. Chem. Soc., 1906, xxviii. 1461.
VOL II. 4
points of the halogen compounds are barely sufficient to prove that they
are not mixtures of pinene and other hydrochlorides, and it is well
recognised that the nitrosochloride is extremely difficult to prepare when
the pinene is of high optical activity. Hence further evidence is neces-
sary before firpene can be regarded as a terpene of established individu-
ality.
CAMPHENE.
Camphene is the only well-recognised terpene which occurs in nature
in the solid condition. It occurs, like pinene, in both optically active
forms. The constitution of this terpene has been a matter of consider-
able difference of opinion, and the constitution assigned to it by Semmler
based on its similarity to bornylene was thought by many to be finally
accepted. Kecent researches, however, have clearly established that the
formula assigned to it by Wagner is the correct one.
Wagner's formula is as follows :—
CH,
C
/\
H
1
\
CH,
c \iCH
\
The synthetic evidence in favour of this formula is now quite indis-
putable.1
Camphene has the following characters :—
Melting-point . . 50° to 52°
Boiling-point . 159° „ 161°
Specific rotation 104° (sed quayre]
Specific gravity 0-8555 „ 40°
Camphene is extremely difficult to separate in the solid condition from
essential oils, and it may therefore be taken for granted that natural
camphene is rarely prepared in the pure condition. The figure given
above for the specific rotation is for a sample artificially prepared from
pinene hydrochloride.
Camphene is prepared artificially by the isomerisation of pinene with
sulphuric acid or by the withdrawal of HC1 from pinene monohydro-
chloride, or by the action of heat in the presence of acetic anhydride on
bornylamine, C10H17NH2, which causes the withdrawal of ammonia and
leaves camphene, as follows :—
C1(1H17NH2 :C10H10
1
Lipp, Berichte, 47 (1914), 891; Komppa, Berichte, ibid., 934; Haworth and
King, Journ. Chem. Soc., 1914,
It is best prepared, however, by converting the alcohol, borneol, into
hornyl chloride. The bornyl chloride is carefully dried and then gently
warmed with an equal weight of aniline. The mixture is then heated to
the boiling-point of aniline when the reaction, which is suddenly violent,
is quickly completed. The reaction mass is neutralised by hydrochloric
acid and distilled over in a current of steam. Camphene is rapidly
condensed and solidifies to a crystalline mass.
Camphene is not very stable at high temperatures, and when kept at
250° decomposes to a considerable extent, yielding other terpenes.
The identification of camphene is best carried out by its conversion
into isoborneol under the influence of acetic acid in the presence of
sulphuric acid. In order to effect this conversion, 100 grams of the
fraction containing the terpene in substantial quantity are mixed with
250 grams of glacial acetic acid and 10 grams of 50 per cent, sulphuric
acid. Tne mixture is heated for two to three hours on a water-bath to
a temperature of 50° to 60°. At first the liquid separates into two layers,
but soon becomes homogeneous and takes on a pale red colour. Excess
of water is added, and the oil which is precipitated, and which contains the
isoborneol in the form of its acetate, is well washed with water repeatedly.
It is then saponified by heating with alcoholic potash solution on a water-
bath. The liquid is then evaporated and extracted with water, and the
residue recrystallised from petroleum ether.
The isoborneol so formed melts at 212°, but the determination must
be carried out in a sealed tube, as the melting-point is very dose to the
temperature of sublimation. It is, however, very rarely that the
isoborneol so prepared is free from impurities, and the melting-point will
often be found to be as low as 203° to 205°. It is therefore necessary to
prepare derivatives of the isoborneol in order to identify it with certainty.
The compound with bromal melts at 71° to 72°. Other compounds will be
found mentioned under "isoborneol". By dehydration by means of
zinc chloride, isoborneol is easily converted into camphene, melting at
about 49° to 50°.
A number of characteristic derivatives of camphene have been pre-
pared of which the following are the most important.
Camphene hydrochloride, C10H16HC1, is prepared by passing dry
hydrochloric acid into an alcoholic solution of camphene. When re-
crystallised from an alcoholic solution containing excess of hydrochloric
acid, it melts at 155° (or possibly a few degrees lower). Melting-points
from 149° to 165° have been recorded for this compound, but the products
examined were probably not in a state of purity.
It is possible, however, that camphene hydrochloride is not a uniform
body, but that some of the terpene suffers some rearrangement in the
molecule by the action of hydrochloric acid, and that the hydrochloride
consists of a mixture of a-camphene hydrochloride and /3-camphene
hydrochloride; there is, however, no evidence to suggest that camphene
itself is a mixture of two terpenes, so that the two camphenes are not
known to exist. Aschan1 obtained an alcohol, camphene hydrate, by
acting on camphene hydrochloride with milk of lime, a reagent which
does not produce molecular rearrangement in the terpene nucleus.
In the same way bornyl and zsobornyl chlorides react with milk of
lime. But, whereas bornyl chloride gives an almost quantitative yield of
1
Annalen, 383 (1911), 1.
camphene hydrate, isobornyl chloride yields camphene with traces of
camphene hydrate. Camphene hydrochloride yields about equal quan-
tities of camphene and camphene hydrate so that Aschan assumes it to
be a mixture of two hydrochlorides, a- and /3-camphene hydrochloride,
of which the a-modification when treated with alkalis yields camphene
hydrate, while the /^-modification yields camphene. Assuming this view
to be correct, bornyl chloride would consist chiefly of a-, and isobornyl
chloride, chiefly of ^-camphene hydrochloride.
Aschan has not succeeded in separating a- and /2-camphene hydro-
chloride.
Camphene hydrobromide, C]0H16HBr, forms well-defined crystals
melting at 133°, and the hydriodide melts at about 50°.
Monobromcamphene, C10H15Br, is prepared by treating a solution of
camphene in four times its weight of alcohol and four times its weight of
ether, with the equivalent of two atoms of bromine. Monobromcam-
phene is also produced by treating camphene hydrochloride with bromine
and distilling the product with quinoline. It has, according to Jiinger
and Klages,1 the following characters :—
Refractive index 1-5260 ,, 15°
Molecular refraction 52*3u
Camphene dibromide, C10H16Br.,, is obtained by bromination, and
subsequent purification from the monobromcamphene formed. It
crystallises from alcohol in colourless prisms, melting at 90°. It is best
formed by slowly adding bromine to a solution of camphene in petroleum
ether, the mixture being cooled to - 10°.
Camphene forms a well-defined nitrite, and a nitroso-nitrite, when
treated in the following manner: A well-cooled solution of camphene in
petroleum ether is mixed with a saturated solution of sodium nitrite, and
dilute acetic acid is added. The mixture is well stirred, being kept cool
all the time. Camphene nitrosonitrite, C10H16N3O5, separates and on
recrystallisation forms crystals which decompose at about 149°. The
petroleum ether solution, which has been filtered off from this compound,
is shaken with a concentrated solution of potassium hydroxide, which
removes camphene nitrosite, C10H1(5N2O3, in the form of its potassium
salt. When this is decomposed with acids it yields the free nitrosite.
This compound is a greenish oil, with a pleasant odour, easily decompos-
ing when heated to 50°.
After having separated the nitrosonitrite and the nitrosite, the residual
solution in petroleum ether is evaporated. There then separates cam-
phene nitrite, C10H15NO2, in fine needles which melt at 66°, and boil at
147° at a pressure of 12 mm.
The oxidation products of camphene are of considerable interest,
but as they vary very considerably according to the exact method of
oxidation employed, they are not of very great use in the characterisa-
tion of the terpene.
When pinene hydrodide is heated with 40 per cent, alcoholic potash
at 170° for four hours, a mixture of camphene and a second hydrocarbon
is produced. This body, C10H16, melts at 97*5° to 98° and has been
termed bornylene by its discoverer, Wagner.2 It is closely related to
2
* Berichte, 29, 544, Ibid., 33, 2121.
camphene, and Wagner proposed to term camphene zsobornylene. It
is quite certain that the two bodies are different in constitution, since
bornylene on reduction by the method of Sabatier and Senderens yields
dihydrobornylene, identical with camphane, whilst camphene yields
dihydrocamphene which is not identical with camphane. Both cam-
phene and bornylene yield camphenanic and isocamphenanic acid on
oxidation, so that they are obviously closely related.
According to Buchner and Weigand,1 bornylene has the constitution—
FENCHENE.
This terpene is not found in nature, or if so, only to a very minute
extent, possibly being present in traces in turpentine and in oil of
Eucalyptus globulus. It may be prepared by reducing the ketone,
fenchone C10H160, to its alcohol, fenchyl alcohol, C10H17OH, from which
the elements of water can be separated by means of potassium bisulphate
at a high temperature, when fenchene, C10H16, results. It is, however,
certain that the terpene so obtained is a mixture of probably two chemical
and several stereo-chemical isomers. According to Wallach 2 fenchene
thus prepared is a liquid boiling at 155° to 156°, of specific gravity 0'867
and refractive index 1-4690 at 20°. According to Gardner and Cockburn
its boiling-point is 150° to 152°, its 3specific gravity 0*8667 at 18°, and its
optical rotation - 6*46°. Wallach found that when Z-fenchyl alcohol
prepared from ^-fenchone is treated with phosphorus pentachloride, it
yields two fenchyl chlorides, and these in turn yield two fenchenes, one
laevo- and the other dextro-icot>a>t>ory. They are both derived from dextro-
fenchene, and Wallach designated them D-deotfro-fenchene and ~D-laevo-
fenchene.
The corresponding hydrocarbons obtained from Z-fenchone were
termed by Wallach L-d-fenchene and L-Z-fenchene, the capital letter
being used to indicate the rotation of the parent fenchone, and the small
letter that of the terpene.
A terpene yielding isofenchyl alcohol on hydration, which Wallach
considers to be one of the fenchenes, was artificially prepared by convert-
ing nopinone into a hydroxy ester by means of bromoacetic ester and
zinc-dust. The hydroxy ester is dehydrated by potassium bisulphate,
and so yields an unsaturated ester, which on saponification yields an acid
from which the terpene results by distillation. This fenchene has the
iBerlchte, 46, 2103. * Annalen, (263), 149 ; (302), 376.
*Ibid. (302), 371; (315), 273.
Optical rotation -f 15-93°
Boiling-point 158°
By using d-fenchone a D-Z-fenchene was prepared, having an optical
rotation — 32°, and yielding a dibromide melting at 87° to 88°.
Up to this point no evidence was forthcoming that any one off the
fenchenes prepared was pure, as1 the optical rotation of nearly every speci-
men was different. Wallach has, however, more recently prepared
fenchene by treating fenchyl-amine with nitrous acid. The resulting
terpenes were separated by fractional distillation into two main portions,
one of which had the following characters:—
Refractive index '. 1-4724 „ 19°
This is the purest D-Z-fenchene prepared, and it yielded a dibromide
C10Hl6Br2, melting at 87° to 88°. Wallach considers that D-Z-fenchene
has the following constitution :—
CH
H .c/
.o^ \CH, \JJ—La
C(CH3)2
C : CH2
CH
2
Bertram and Helle some years ago prepared a fenchene, which they
termed isofenchene, by splitting off water from isofenchyl alcohol. L-fZ-
fenchene prepared from Z-fenchone in a similar manner was found to
have an optical rotation -f 29°.
By treating D-Z-fenchene with ozone, a portion of it is converted into
D-d-fenchene.
Komppa and Koschier3 now propose a revision of the nomenclature
of the fenchene terpenes, Wallach's D-fenchens being termed a-fenchene,
D-Z-fenchene becoming Z-a-fenchene, and D-d-fanchene becoming d-a-
fenchene. The fenchene obtained by Bertram and Helle's method, by
dehydrating fenchyl alcohol with potassium bisulphate, is now termed
/3-fenchene. This nomenclature is certainly preferable as it contains no
suggestion that the two bodies are identical in chemical constitution, nor
is there any particular evidence that D-Z-fenchene and L-Z-fenchene are
not the same actual terpene, and equally so in the case of D-d-fenchene
and L-d-fenchene.
Accepting the later nomenclature, /2-fenchene can be prepared almost
free from the a- variety by heating fenchyl alcohol with KHSO4. After
repeated fractionation over sodium, /3-fenchene has the following char-
acters :—
1
Annalen (362), 174.3 *Jour. prakt. Chem. 61 (1900), 303.
Chem. Zentr. (1917), i. 407.
„ rotation -f 10*7°
On oxidation it yields hydroxyfenchenic acid melting at 138° to 139°.
The derivatives of fenchene are not in most cases crystalline, but the
optically active a-fenchenes form a dibromide, C10H10Br9, which crystal-
lises well, and melts at 87° to 88°. The racemic form melts at 62°.
By hydration with acetic and sulphuric acids, isofenchyl alcohol is
formed, and this can be oxidised to isofenchone.
The following are the characters of various derivatives of the active
and the racemic forms :—
Melting points of
Active Compound. Racemic Compound.
Fenchene dibromide . . . 8 7 ° t o 8^° 62°
Urethane of isofenchyl alcohol . 100° „ 107° 94°
Isofenchone semicarbazone . . 221° „ 222° 223° to 224°
oxiine . . . 82° 133°
Monobrom-isofenchone . . . 56° to 57° 46° to 47°
Isofencho-camphoric acid . . 158° ,, 15J° 174° ,, 175°
Fenchene is more resistant to the action of nitric acid than other ter-
penes, and may be regarded as of particularly stable constitution.
On page 49 the possible relationships of isopinene and fenchene were
mentioned. Komppa and Boschier1 have prepared a fenchene from
a-fencho-camphorone, which they had previously prepared synthetically.
The complete synthesis of this fenchene has, therefore, been achieved,
a-fencho-camphorone is converted by magnesium methyl iodide into the
corresponding alcohol, which is dehydrated by distillation at atmospheric
pressure, yielding a-fenchene having the following characters:—
9QO
Specific gravity at ^ 0-866

Molecular refraction 43*93
It yields a hydrochloride melting at 35° to 37°, which when treated
with aniline regenerates the same hydrocarbon, which is identical in all
respects with isopinene. The admixture of this fenchene hydrochloride
with that prepared from isopinene causes no depression of the melting-
point, and Komppa regards the identity of inactive a-fenchene and iso-
pinene as established. He assigns the following constitution to a-fenchene
(isopinene):—
CH
H2
C(CH8)2
C . CH,
CH
1
Ann. Acad. Sci. Fennicae, 1916, [A], 10, iii. 3-15; Journ. Ctem. Soc., 1917
Abst., i. 466.
The latest contribution to the chemistry of this abstruse subject is
contained in papers by Komppa and Roschier,1 and by Boschier.2 They
have obtained a fenchene by treating methyl-/2-fenchocamphorol with
potassium bisulphate, which is the inactive form of /2-fenchene, mixed
with a small amount of a terpene they term y-fenchene. ^-fenchene
(identical with D-rf-fenchene of Wallach), and y-fenchene have the fol-
lowing constitutions :—
CH CH
CH9 CH.,
JC : CH., H9C . CH,
CH CH
j8-Fenchene. 7-Fenchene.
Several other synthetic fenchenes are also described.
SABINENE.
This terpene occurs principally in oil of savin, but has also been found
in marjoram, cardamom, sho-gyu and a few other essential oils. It is
obtained from the fraction of oil of savin which boils below 195°, which
amounts to about 30 per cent, of the oil. It has probably not been iso-
lated in a state of absolute purity, but its characters are approximately
as follows :—
By systematic fractionation of a large quantity of sabinene obtained
from oil of savin, Schimmel & Co. separated the crude terpene into the
following fractions :—
Per Cent. Boiling-point. Specific Gravity. Rotation
20 162° to 163° 0-8481 + 59° 30'

49 163° „ 164° 0-8480 + 63° 50'
31 164° '„ 165° 0-8482 + 68° 54'
By the action of hydrochloric acid gas on sabinene dissolved in acetic

acid, terpinene dihydrochloride is produced, melting at 52°. If no trace
of moisture is present the monohydrochloride alone is yielded.
By oxidising sabinene with ice-cold solution of potassium permanga-
nate, sabinene glycol, C10H16(OH)2, results. This body melts at 54°, and,
together with the above-described hydrochloride serves for the characteri-
l
Ann. Acad. Sci. Fennicae, 1917, [A], 15, x. 1-15.
2
Ibid:, 1919 [A], 10, i. 1.
sation of the terpene. During the oxidation there is also formed sabi-
nenic acid, C10H16O3, an oxyacid which crystallises from water and melts
at 57°. If this acid be oxidised with peroxide of lead, sabinene ketone,
C9H140, is formed, which is quite characteristic of the terpene. It has
Boiling-point . . . 213°
Specific rotation . . . . . . . . . - 18°
To prepare sabinenic acid for the identification of the terpene, Wallach1

operates as follows : 10 grams of the crude terpene are mixed with the
theoretical amount of potassium permanganate in water at ice tempera-
ture. The oxide of manganese is filtered off, the liquid rendered acid and
extracted with ether, and the ethereal solution shaken with caustic soda
solution. The sodium salt is very sparingly soluble, and is precipitated,
collected, and decomposed with dilute sulphuric acid and purified by a
further solution in ether. It must be well dried in a desiccator before
its melting-point is determined. Sabinene has the following constitu-
tion :—
C : CH.,
CH,
C : CH(CH3)2
Sabinene appears to be fairly closely related to thujene (tanacetene),
since both a-thujene and /5-thujene yield the same body, thujane C10H18,
as does oabinene when reduced by hydrogen in the presence of platinum
black.
Considerable difference of opinion exists as to the relationships of
sabinene to terpinene, and the conversion of sabinene into terpinene
hydrochloride is to be explained by a molecular rearrangement, and can-
not be said to be evidence of relationship/2
By treating sabinene with formic acid at reduced temperatures
Semmler has obtained an alcohol of the formula C10H18O which has the
Optical rotation . . . . . . . . . +14°
This alcohol is probably identical with the alcohol " origanol " dis-
covered by Wallach in marjoram oil and termed by him terpineol.
l
Annalen, 357(1907), 78.
d., 350 (1906), 162 ; Bcrichte, 39 (1906), 4416, and 40 (1907), 2959.
THUJENE.
Thujene has not been isolated from any essential oil, and the numer-
ous terpenes described under this name are in all probability non-uniform
bodies.
The body originally known under this name was prepared by the
dry distillation of thujylamine or isothujylamine hydrochloride, and is
identical with Semmler's tanacetene.1
Tschugaeff prepared thujene by distilling thujyl xanthogenate.2 This
body had the following characters :—
Specific gravity 0-8275 at AQ
4
Boiling-point . 151° to 152-5°
According to its discoverer, this body is the true .terpene of the
thujone series, and he prefers to call Semmler's thujene or tanacetene,
isothujene, as being the true terpene of the isothujone series.
By the dry distillation of trimethyl - thujylammonium hydroxide,
Tschugaeff obtained a thujene quite similar to the above, but of consider-
ably higher optical rotation. He therefore considers that two stereoisomers
may result from different methods of preparation from thujone.
A hydrocarbon was also prepared by Kondakoff, to which he gave the
name thujene, which may have been a crude mixture of the two stereo-
isomers. The characters of these bodies are summarised in the following
table:—
Boilmg- point. Specific Gravity. Rotation. Refractive

Index.
Semmler's Thujene —
60° to 63° (14 mm.) 0-8508 at 15° 1-47600
Wallach's Thujene —
170° to 172° (760 mm.) 0-8360 „ 15° 1-47145
Tschugaeff's Thujene —
151° to 152-5° (670 mm.) 0-8275 „ 15° 1-45042
Kondakoff's Hydrocarbon—
1. 147° to 150° 8-8258 18° + 48° 32' 1-44929
2. 150° „ 151-5° 0-8260 18° + 40° 15' 1-45001
3. 151-5° to 152-5° 0-8279 17° + 28° 12' 1-44999
4. 152-5° „ 156° 0-8286 17° + 12° V 1-44909
5. 156° to 168° 0-8286 17° + 3° 33' 1-45259
Kondakoff and Skworzow3 have recently rein'vestigated the subject

and are of the opinion that all the thujenes so described are mixtures and
not uniform bodies. They consider that the lower boiling fractions pre-
pared from thujyl xanthogenate consist of two stereoisomers, and the
higher boiling fractions to consist of isothujene with some terpinene.
They do not consider that any pure thujene has been prepared, but
dextro-thujene in as great a state of purity as they have been able to
prepare it has the following characters : —
1
Berichte, 25, 3345. ., 33, 3118. *Chem. Zentral., 1910, ii. 467.
THE CONSTITUENTS |OF ESSENTIAL OILS 59
Isothujene dihydrochloridei isl stated to have the following char-
acters :—
Boiling-point 121-5° to 122-5° at 16 mm.
When this is treated with sodium acetate in alcoholic solution, it
yields a hydrocarbon (isothujene ?) having the following characters :—
It is obvious that the chemistry of the thujene isomers requires further
investigation.
The following formula has been suggested for thujene, which is in
accord with its obvious relationship with sabinene :—
C . CH3
HC/ VJH
\v
xCH,
C . CH(CH3)2
DlPENTENE AND LlMONENE.
Dipentene is the racemic form of the optically active ^-limonene

and Z-limonene, terpenes which are found to a very large extent in
essential oils. Since an equal mixture of d-iimonene and Z-limonene is
dipentene, it is obvious that whenever optically active limonene is found
with a rotation below the maximum, it must contain dipentene. Mix-
tures of equal quantities of a compound of the optically active limonenes
are identical with the corresponding compound prepared from dipenten^
It is therefore obvious that the nomenclature is unfortunate and dipentene
should be termed ^-limonene.
Limonene occurs freely in nature, forming the greater part of oils
of lemon and orange, and found to a large extent in caraway, dill,
bergamot, and many other essential oils.
It has frequently been stated that dipentene has a higher boil ing-point
than its optically active components, but this is not so, any observation
in this direction being undoubtedly due to the presence of minute traces
of impurities.
The following are the characters of the most highly purified speci-
mens of limonene which have been prepared :—
e£-limonene. Z-lirnoiiene.
Specific gravity 0-850 0*8472
Optical rotation +105° - 105°
A specimen obtained by the reduction of limonene tetrabromide by
Godlewski and Koshanowitsch1 had a specific rotation + 125° 36' which
is practically equal to an observed rotation of + 106° 30', thus confirming
the purity of the specimens prepared by fractional distillation.
For the identification of limonene, one of the most useful compounds
is the crystalline tetrabromide, C10H16Br4. This body is best prepared as
follows : the fraction of the oil containing much limonene is mixed with
four times its volume of glacial acetic acid, and the mixture cooled in
ice. Bromine is then added, drop by drop, so long as it becomes de-
colorised at once. The mixture is then allowed to stand until crystals
separate. These are filtered off, pressed between porous paper, and re-
crystallised from acetic ether. Limonene tetrabromide melts at 104-5°
and is optically active, its specific rotation being + 73'3°. The inactive,
or dipentene, tetrabromide melts at 124° to 125°. In the preparation of the
tetrabromide traces of moisture are advisable, as the use of absolutely
anhydrous material renders the compound very difficult to crystallise.
When the limonene to be identified is of high optical rotation, that is,
of a high degree of purity in one of its optical forms, the tetrabromide is
easy to identify; but in the presence of much dipentene, it is necessary
to recrystallise the compound repeatedly before a pure limonene tetra-
bromide is obtained.
Both limonenes yield nitrosochlorides, C10H1(.NOC1, each of which
can be separated into two modifications. There are thus four limonene
nitrosochlorides : they are known as the a- and /?- varieties of the dextro-
and Zam>-rotatory forms of the terpenes. The a- and /3- forms, however,
yield the same carvoxime on treatment with alcoholic potash.
Here, as in every other case, the only difference between the derivatives
of the two limonenes is that they are equally active optically in the
opposite directions, and differ in the usual way in crystalline form. The
nitrosochlorides, on boiling with alcoholic potash, yield nitroso-limonenes,
C10H15NO. These are identical with the two carvoximes, and their con-
stitution is probably C10H14 . NOH. They both melt at 72° The car-
voxime prepared from d0#£ro-limonene-nitrosochloride is Zaeô-rotatory,
whilst that from Zaô-limonene-nitrosochloride is dextro-rotatory.
Tilden and Leech have prepared nitrosocyanides of limonene by the
action of potassium cyanide on the nitroso compounds. The table on
opposite page gives the melting-points and optical rotation of the prin-
cipal of these and other limonene compounds.
For the preparation and separation of the limonene nitrosochlorides
the following method should be employed :—
Five parts of the terpene, 7 of amyl nitrite, and 12 of glacial
acetic acid are mixed and cooled with ice and salt, and a mixture of
6 parts of hydrochloric acid and 6 parts of glacial acetic acid added in
small quantities at a time. Five parts of alcohol are then added and the
mixture allowed to stand in a freezing mixture for a itime. A mass of
crystals separates, which consists of the crude nitrosochlorides. This is
filtered off and washed with alcohol. When perfectly dry 100 grams of
the crystals are digested with 200 c.c. of chloroform for a few moments and
at once filtered. The chloroform dissolves a-nitrosochloride, which is
precipitated by the addition of excess of methyl alcohol. The crude
compound is filtered off, dried and digested with anhydrous ether for
l
Chem. Zentral., 1899, i. 1241.
fifteen minutes, the ethereal solution filtered off and the ether allowed
to evaporate spontaneously. The a-nitrosochloride separates in large
crystals, which are again dissolved in ether and methyl alcohol added in
small quantity. The solvent is now allowed to evaporate slowly, when
the pure compound crystallises out. It melts at 103° to 104°.
Dextro- Inactive Specific Specific

Compounds. and Laevo- Melting- De.xtro- Laevo-
Melting- point. Rotatiou.
point. Rotatiou.
Limoneoe . . . . + 125° - 125°

a-nitrosochloride . 103° to 104° 103° to 104° + 313-4° - 314-8°
j8-nitrosochloride . 100° — + 240-3° - 242-2°
a-nitrosocyanide . 90° to 91° 81° + 152-7° - 152-2°
Benzoyl-a-nitrosocyanide 108° 96° + 126-3° - 127-2°
j3-nitrosocyanide . 140° to 141° 159° to 160° - 31-6° + 30-6°
Benzoyl-0-nitrosocyanide 121° 98° - 108-2° + 108-7°
o-amide . . . . 138° 155° + 174-9° - 174°
Benzoyl-o-amide . 152° 150° + 241-7° - 242°
a-carboxylic acid . 97° 116° + 102-9° - 103-9°
Dihydro-carvoxime 88-5° 115° + 9-46° - 9-25°
Tetrabromide 104° 125° to 126° + 73-3° - 76-4°
Carvoxime . . . . 72° 93° - 39*3° + 39-7°
Monohydrochlori 1 e — - 40° + 39-5°
Nitrobenzylamine . 92° —
110° -f 163-8° - 163-6°
The portion of the mixture of crude nitrosochlorides which was not

dissolved by chloroform consists of crude /3-nitrosochloride. This is
dissolved by shaking with ten times its weight of chloroform. The
solution is then filtered and methyl alcohol added and the precipitate
filtered off, washed with ether, and dried. The dried compound is dis-
solved in ether and on evaporation of the solvent pure /5-nitrosochloride
separates. This body melts at 100°.
According to Wallach the nitrosochlorides are physical isomerides of
the formula : —
Very characteristic derivatives are obtained by the action of organic

bases on the limonene nitrosochlorides. If d-a-limonene nitrosochloride
be so treated, two nitrolamines are obtained, a-nitrolamine (dextro-rota-
tory), and /2-nitrolamine (laevo-rotatory). If d-/3-limonene nitrosochloride
be treated in the same manner, exactly the same reaction products are
obtained. If, on the other hand Z-a-nitrosochloride or Z-/3-nitrosochloride
be treated in the same manner, a mixture of a-nitrolamine (laevo-
rotatory) and /3-nitrolamine (dextro-rotatory) is obtained.
The anilides and piperidides are the most characteristic of these com-
pounds. They are prepared by similar methods, of which that for the
piperidides is as follows : 20 grams of purified a-limonene nitroso-
chloride are mixed with 20 grams of piperidine and 60 grams of alcohol,
and gently warmed with frequent shaking. When the solution is clear,
the warm liquid is poured into an evaporating dish and a small amount
of water added. On cooling, crystals of the sparingly soluble impure
/?-base separate. These are filtered off, and water added to the filtrate
62 THE CHBMISTEY OP ESSENTIAL OILS
which precipates the more soluble a-base. The crude a-compound is
dissolved in acetic acid, filtered, and precipitated by aftimonia. It is
thrown out as an oil, which afterwards solidifies, and is then dissolved in
a little petroleum ether, which leaves traces of the /^-compound undis-
solved, and the a-base separates on evaporation of the petroleum ether,
and is recrystallised from alcohol. The crude /^-compound is dried,
digested with cold petroleum ether, which dissolves any a-base present,
and the undissolved portion recrystallised from warm petroleum ether
with the addition of a little methyl alcohol.
a-limonene nitrol-piperdide forms orthorhombic crystals melting at
93° to 94°, whilst /Mimonene piperidide melts at 110° to 111°.
The nitroanilid.es are very characteristic crystalline compounds of
limonene. These have the constitution —
1015
\NHC6H5
To prepare them, 20 grams of pure a-limonene, nitrosochloride are
powdered and warmed with 20 c.c. of aniline and 30 c.c. of alcohol, under
a reflux condenser. The mixture is heated with constant shaking, and
after violent reaction is over the mass is allowed to cool, and when cold,
excess of concentrated hydrochloric acid is added. The resulting crystals
are filtered off and washed with ether-alcohol. They consist of the
hydrochloric acid salt of a-limonene nitrolanilide, and on treatment with
ammonia the free base is liberated. When recrystallised from alcohol it
melts at 112° to 113°. The filtrate from the hydrochloric acid salt of the
a-base is poured into a large volume of water containing free ammonia.
The /3-anilide gradually becomes solid and is dissolved in three times its
weight of warm benzene in order to remove traces of aniline. The
yS-anilide separates from this solution and forms fine needles melting
at 153°.
Limonene forms a monohydrochloride, which is a liquid, and which
exists in both optically active modifications. By the action of moist
hydrochloric acid on the acetic or alcoholic solution of limonene, no
optically active dihydrochloride is formed, the terpene becoming inactive
and dipentene dihydrochloride, C10H162HC1, results. This body is pre-
pared when limonene is mixed with half its volume of glacial acetic acid,
and a current of hydrochloric acid gas is passed over (not into) the well-
cooled liquid, with frequent shaking. The resulting mass is pressed on a
porous plate, dissolved in alcohol, and precipitated with water. It melts
sharply at 50°.
Forster and van Gelderen 1 have prepared a characteristic nitro-
derivative of dipentene by treating dipentene nitrosochloride with sodium
azide. , The resulting body, C10H15(NOH)N3, dipentene nitroso-azide,
melts at 72° to 73°. The corresponding active limonene derivatives melt
at 52° to 53°.
Dipentene, the inactive form of limonene, not only occurs naturally
in essential oils, but results by the action of heat on several other ter-
penes, and to a considerable extent by the action of sulphuric acid on
pinene.
Pure dipentene may be prepared by boiling 1 part of pure dipentene
dihydrochloride with 1 part of anhydrous sodium acetate and 2 parts
1
Proc. Chem. Soc., 27 (1911), 195.
of glacial acetic acid for half an hour under a reflux condenser. The
dipeptene is distilled with steam and then heated with caustic potash and
finally redistilled.
The weight of chemical evidence is strongly in favour of dipentene,
being actually i'-limonene, that is, merely the racemic form of the active
limonenes. Semmler has suggested, however, that a slight difference
may exist between the constitutions of these terpenes. •
He suggested a nomenclature for the terpenes by which those com-
pounds which contain a double linkage between the nucleus and the side
chain should be called pseudo-compounds, whilst the compounds with
the double linkage in the nucleus should be the ortho-compounds. He
suggested the following formulae : —
CH, CH,
I II- *
c c
JCH, H
CH CH
CHo
Ortko-limonene. Pseudo-limonene.
Semmler then suggested that ortho-limonene might be ordinary limo-
nene, and that dipentene had the pseudo-formula, and that both these com-
pounds would yield identical halogen derivatives with the breaking of
the double linkage. He subsequently modified his view to some extent
and considered that terpinene was represented by the pseudo-limonene
formula.
There seems no room for doubt that the above formula for " ortho-
limonene " is the correct formula for limonene, and the classical synthesis
of dipentene by W. H. Perkin, Jun., and his colleagues has proved beyond
doubt that it is the correct formula for dipentene or ^-limonene.
These researches on the synthesis of the terpenes were commenced in
1900, and has been carried on with considerable success and conspicuous
ability ever since. It was considered necessary to synthesise terpineol,
and so establish the formula which analytic reactions supported. The
first necessary step was to synthetically prepare the l-methyl-A'-cyclo-
hexene-4-carboxylic acid,1 of the formula—
/,CH . CH2X
CMef >CH. C09H
\CH 2 . CH/
and as this acid was at that time unknown, the first problem was to dis*
cover some means by which its synthesis could be accomplished.
The acid was prepared in considerable quantities by the following
rather complicated series of reactions.2 When ethyl /2-iodopropionate
and the sodium derivative of ethyl cyanacetate are allowed to interact in
1
W. H. Perkin, Lecture to tJie Pharmaceut'ical Society, May, 1912. .
2
Jour. Chem. Soc., 85 (1904), 416 and 654.
molecular proportions at the ordinary temperature, a reaction takes place

which results in the formation of ethyl y-cyanopentane-aye-tricarboxylate
and regeneration of half of the ethyl cyanoacetate : —
2C02Et .,CHNa . ON + 2ICH2 . CH2 . CO2Et =
CO 2 Et.C(CN)(CH 2 .CH 2 .C0 2 Et) 2 + CO 2 Et.CH 2 .CN + 2NaI.
This cyano-ester is hydrolysed by boiling with concentrated hydro-
chloric acid with the formation of pentane-ay€-tricarboxylic acid, CO2H .CH
(CH2 . CH2 . CO2H)2 and i when the sodium salt of this acid is heated with
acetic anhydride and distilled, decomposition takes place with the forma-
tion of 8-ketohexahydrobenzoic acid or cyclohexanone-4-carboxylic acid —
CO2H . CH2 . CH2X
>CH . CO.H =
C02H . CH2 . CH/
,CH2 . CH2N^
CO( >CH . CO2H + CO., + H2O
X
CH2 . CH/
The next step was to convert cyclohexanone-4-carboxylic acid into
l-methyl-cyclohexanol-4-carboxylic acid, and this is readily accomplished
by heating the ester of the ketonic acid with magnesium methyl iodide in
the usual manner —
OH.CMe<X >CH.CO 2 H
CH2 . CH/
If the hydroxy-acid is heated with hydrobromic acid, it is converted
into l-methyl-l-bromocyclohexane-4-carboxylic acid, and this is decom-
posed by boiling with sodium carbonate with loss of hydrogen bromide
and with formation of 1-methyl-A' cyclohexene-4-carboxylic acid —
x,V>--L_L . OH^v
CM< )CH . C09H

^CH,
The last step was to convert the unsaturated acid into its ester and to
act on this with an ethereal solution of magnesium methyl iodide, when
an almost quantitative yield of an oil was obtained which, on examina-
tion, proved to be terpineol—
,CH—CH2,
MeCf >CH . CMe,. OH
X
CH 2 .CH/
the change being simply the conversion of the —CO 2 Et group into the
group —CMe 2 . OH.
In order that there might be no doubt as to the identity of the syn-
thetical product, it was converted into the nitrosochloride, C10H18O, NOC1
(melting-point 122°), and phenylurethane, C10Hj7O . CO . NH . C6H5 (melt-
ing-point 113°), and these were compared with specimens made from
ordinary terpineol, with the result that the preparations obtained from the
two sources were found to be absolutely identical.
The next step was to convert the synthetic terpineol into dipentene,
which was readily accomplished by heating with potassium hydrogen
sulphate, when water was eliminated and dipentene formed—
MeC^ ^CH . G{
\r<TT n~u /
\j±4-2 • v^-n.2
\r<TT
-^3
Dipentene.
The dipentene produced in this way was converted into the tetra-
bromide, C10H16Br4 (melting-point 125°), the dihydrochloride, C]0H16, 2HC1
(melting-point 48° to 50°), and the nitrosochloride, Ci0H16, NOC1 (melting-
point 106°), and these derivatives were compared with the corresponding
specimens obtained from ordinary dipentene, with which they ^were found
to be identical in all respects.
Attempts to prepare the active limonenes were unsuccessful, as during
the reactions, even when the various acids and the terpineol were separated
into their active components, racemisation takes place^during the dehydra-
tion and the most active product obtained had a rotation of - 5°, so that
it consisted essentially of dipentene, with a very small amount of laevo-
limonene.
CARVESTRENE AND SYLVESTRENE.
Sylvestrene is a well-recognised terpene, which is found in various
turpentine and pine oils, but only in its dextro-rotatory form. Carvestrene
is merely the optically inactive variety of sylvestrene, and is another
instance of unfortunate nomenclature: it should be properly called
t-sylvestrene.
There appear to exist two very closely allied terpenes, which have so
similar constitutions and characters that it is almost impossible, if not
quite so, to separate them when existing together naturally. The syn-
thetically prepared sylvestrene is, of course a distinct individual, the con-
stitution of which will be dealt with directly.
To prepare natural sylvestrene, the fraction of Swedish oil of turpen-
tine boiling between 175° to 180° is diluted writh an equal volume of ether
which has been previously saturated with hydrochloric acid gas. The
mixture is allowed to stand for two or three days, the ether distilled off,
and the residue is left in a very cold place for some months, when syl-
vestrene dihydrochloride is obtained. This body, C10H162HC1, when re-
crystallised from alcohol melts at 72° and has an optical rotation [a]D =
+ 22°. If this body be distilled with aniline it yields sylvestrene, which
This body, so isolated is probably a mixture of the two isomerides, the
optical rotation varying with the relative proportions of the two bodies..
The two isomers have the following constitutions :—
C—CH3 C—CH,
H0C CH—CK BLC CH—C/

CH0
Sylvestrene. Isosylvestrene.
They are therefore meta-menthadienes.
VOL. II, 5
Sylvestrene yields the following characteristic reaction. If a drop of
concentrated sulphuric acid be added to a solution of one drop of syl-
vestrene in acetic anhydride, a deep blue coloration results. No other
terpene appears to give this reaction.
Sylvestrene is a very stable terpene, but on heating to 250° it is par-
tially polymerised. In addition to the dihydrochloride mentioned above,
it yields the following characteristic compounds : —
The dihydrobromide, C10H1(52HBr, is obtained in a similar way to the
dihydrochloride. It melts at 72° and has a specific rotatory power
+ 17-9°.
The dihydriodide C10H102HI is prepared in a similar manner, and
melts at 66° to 67°.
Sylvestrene tetrabromide, C10H10Br4, is prepared when pure Sylvestrene,
regenerated from itstlihydrochloride and dissolved in acetic acid, is heated
with bromine until a permanent yellow colour is produced. Water is
added to the reaction product, but not sufficient to precipitate the bromide,
and the vessel allowed to stand in a cold place. The bromide separates
and can be purified by recrystallisation from alcohol. It forms mono-
symmetric crystals melting at 135° to 136°, and having a specific rota-
tion + 73-7°.
Sylvestrene nitrosochloride, C10H1(5 . NOC1, is prepared from pure
Sylvestrene, regenerated from the dihydrochloride in the following
manner : Four volumes of the terpene are dissolved in six of amyl
nitrite and five volumes of strong hydrochloric acid are added, with con-
stant shaking. The heavy oil which separates is shaken with a little
ethyl alcohol, when it solidifies, and can be purified by dissolving it in
chloroform and precipitating it with petroleum ether. It is finally re-
crystallised from methyl alcohol, when it melts at 106° to 107°.
When the last-described body is warmed with benzylamine, in alcoholic
solution, Sylvestrene nitrol -benzylamine
. CH2C6H5
is formed. This, when recrystallised from methyl alcohol, forms well-
defined crystals melting at 71° to 72° and having a specific rotation
+ 185-6°.
Carvestrene, or i-sylvestrene, was first prepared by Baeyer l from
carvone, the ketone characteristic of oil of caraway. This body, when
reduced with sodium and alcohol yields dihydrocarveol, which, on oxida-
tion is converted into dihydrocarvone. The formulae of these three bodies
are as follows : —
,CO . CH,,v
CMe/ " )CH . CMe : CH,
VJH.CH/
Carvone.
X CH(OH) . CH 2V
CHMe( >CH . CMe : CH.,
\CH 2 - CH/
Dihydrocarveol.
1
Berichte, 27, 3485.
/CO—CH, x
CHMe( >CH.CMe:CH 9
X
CH 2 . CH/
Dihydrocarvone.
Hydrobromic acid converts dihydrocarvone into a hydrobromide,
C10H17OBr, which, when treated with cold alcoholic potash, readily loses
hydrogen bromide. Instead, however, of the unsaturated substance,
.dihydrocarvone, being regenerated as the result of this decomposition,
a remarkable formation of a cyclopropane ring takes place and carone is
produced—
/CO—CH 2 x
CHMe( >CH . CBrMe2
\CH 2 . CH/
Hydrobrorniie of dihydrocarvone.
/CO CHX
CHMe< I >CMe,
\CH 2 . CH 2 . CH/
Carone.
Carone is then converted into its oxime, which is reduced by sodium
and alcohol, and yields carylamine, C10H17NH2, which has the following
constitution :—
/ Vy JL-1-^^.1 -l_J-2 I . VVXILx
CHMe<X >CMe2
CH2 . CH2 . CH/
Carylamine is decomposed when its solution in dilute acids is evapor-
ated, during which process the dimethylci/cZopropane ring suffers dis-
ruption and the unsaturated isomeric base, vestrylamine,
/CH(NH2) . CH . CMe : CH2
CHMe<X |
CH 2 -CH 2 -CH 2
is formed. The hydrochloride of vestrylamine is readily decomposed on
distillation, with elimination of ammonium chloride and formation of
cwvestrene.
The properties of carvestrene or t-sylvestrene are as follows :—
Boiling-point .......... 178°
Dihydro3hloride melting-point ...... 52'5°
Dihydrobromide „ ....... 48° to 50°
The constitution of carvestrene has been determined, subject to the
limitation above referred to as to the constitution of isocarvestrene, by the
masterly synthesis achieved by W. H Perkin, Jr., and his colleagues.
The starting-point of this synthesis wras m-hydroxy-benzoic acid, which
was reduced by sodium and alcohol to cyclohexanol-3-carboxylic acid,
of the formula —
CH2
CH.COOH
By oxidation with chromic acid, this is converted into cyclohexanone-
3-carboxylic acid, in which the —CH . OH— group is converted into
the —CO— group. This is converted into its ethyl ester and treated
with magnesium methyl iodide, and the product, on hydrolysis, yields
l-methyl-cyclohexane-l-ol-3-carboxylic acid, which is converted byhydro-
bromic acid into 1-bromo-l - methyl - cyclohexane - 3 - carboxylic acid.
When this is digested with pyridine, hydrobromic acid is eliminated and
yields l-methyl-A'-cyelohexane-3-carboxylic acid of the formula—
CH CH. COOH
/r— \
C(CH,)f >CH2
CH2
The ethyl ester of this acid was treated with magnesium methyl
iodide, and thus yielded dihydrocarvestrenol—
CH CH . C(CH3)2OH
>CH2
X
c'H2 OHQ
which on dehydration with potassium bisulphate yields carvestrene.
A further synthesis of carvestrene has been effected by Perkin and
Fisher.1
It is probable that the carvestrene so synthesised is in reality a
mixture of the two bodies described above as carvestrene and isocar-
vestrene.
The active variety of the terpene ^-sylvestrene has been prepared
synthetically by preparing the methyl-cyclohexane-carboxylic acid de-
scribed above, and recrystallising its brucine salt. The acid contains a
small quantity of the A6 acid, although the A1 variety predominates.
The A6 acid was resolved by the brucine crystallisations, and an acid of
rotation + 90° obtained. The synthetic process was then proceeded
with, and the resulting terpene was found to be d-sylvestrene, having a
rotation of 4- 66°.
PHELLANDRENE.
Two isomeric terpenes are known under the name of phellandrene.
Before the distinction between the two bodies was recognised, phellan-
drene had been discovered and reported in a number of essential oils,
so that in many cases it is impossible at present to decide which isomer
is that actually present in a given oil. The two terpenes—still another
case of the absurd nomenclature which has been retained for so many
of the terpenes—are known as a-phellandrene and /?-phellandrene. The
constitutions of the two hydrocarbons are probably as follows :—
1
Jour. Chem. Soc., 93 (1908), 1876.
C.CH, C:CH 2
H2C CH
CH H2C CH
CH. C3H7 CH . (C3H7)
o-Phellandrene. £-Phellandrene.
These terpenes have been exhaustively studied by Wallach,1 who

particularly examined phellandrenes from the following sources :—
1. Z-phellandrene from eucalyptus oil.
2. d-phellandrene from elemi oil.
3. d-phellandrene from bitter fennel oil.
4. d-phellandrene from water fennel oil.
He found that the d-phellandrene from elemi and bitter fennel oils
were identical, and that Z-phellandrene from eucalyptus oil is the laevo-
rotatory variety of the same terpene. To these he assigned the names
d-a-phellandrene and Z-a-phellandrene. The d-phellandrene from water
fennel oil differs from these and is named d-/?-phellandrene. The follow-
ing are the characters of the purest specimens of natural phellandrene
yet obtained:—
d-a-phellandrene. rf-j8-phellandrene. /- a- phellandrene .
Specific gravity 0-844 at 19° 0-852 at 20° 0-848 at 15°

Refractive index 1-4732 1-4788 1-4769
Boiling-point . 61° at 11 mm. 50° to 52° at 5 mm.
175° „ 760 mm. 174° at 760 mm.
Optical rotation + 40° 40' + 14° 45' to + 18° 30' - 84° 10'
All varieties of phellandrene are somewhat unstable and are easily

susceptible of isomerisation.
All varieties readily yield a nitrite of the formula C10H16N2O3, which
is prepared in the following manner, and is a most useful compound for
characterising these terpenes. A solution of 5 grams of sodium nitrite
in 8 c.c. of water is added to a solution of 5 c.c. of the fraction of the
oil containing much phellandrene in 10 c.c. of petroleum ether, and 5 c.c.
of glacial acetic acid is slowly added to the mixture with constant
stirring. The resulting crystals are filtered, washed with water and
methyl alcohol, and purified by dissolving in chloroform and precipitating
with methyl alcohol. The final purification is effected by triturating
the crystals with a cold mixture of methyl alcohol and ether, and re-
crystallising several times from acetic ether. The phellandrene nitrite
so obtained is not a homogeneous substance, but a mixture of two physical
isomerides, which is true for both a- and /^-phellandrene. These physical
isomerides are known as the a- and /^-varieties, so that the following
very confused nomenclature arises, the specific rotation and melting
points of the six known modifications being given :—
J
Annalen, 324 (1902), 269, and 336 (1904), 9.
Specific Melting-
Rotation, point.
Dextro-a-phellandrene a-nitrite . . - 138-4° 112° to 113°
Laevo-a-phellandrene a-nitrite + 135-9° 112° „ 113°
Dextro-a-phellandrene /8-nitrite + 45-9° 105°
Laevo-a-phellandrene ^-nitrite . -40-8° 1C5°
Dextro-j8-phellandrene a-nitrite 159-3° 102°
Dextro-j8-phellandrene ^-nitrite + 0° 97° to 98°
As laevo-^-phellandrene has not yet been isolated, the corresponding

two nitrites have not, of course, been prepared.
The separation of the physical isomerides is effected in the following
manner: the mixed nitrites are dissolved in acetone and precipitated by
the addition of water, the mixture being cooled to 0°. This process is
repeated several times, when eventually the more soluble or /2-nitrite is
separated from the less soluble or a-variety.
yS-phellandrene, which was originally obtained from water fennel
oil, is also found in the essential oil of Bupleurum fruticosum.1 Fran-
cesconi and Sernagiotto have prepared from it the corresponding physically
isomeric nitrosochlorides. They find that the yield of nitrosochlorides
prepared in the same way as pinene nitrosochloride (q*v.), is greater as
the optical rotation of the terpene is lower. Through a series of re-
crystallisations, the two isomers were separated, and found to have the
Specific Melting-
Rotation, point.
/8-phellandrene-a-nitrosochloride . . . - 175° 101° t o 102°
/8-phellandrene-8-nitrosochloride . . . - 285° 100°
No crystalline nitrosochlorides have, so far, been prepared from a-phel-

landrene.
If a-phellandrene be oxidised by potassium permanganate, the princi-
pal body resulting is a-oxy-/?-isopropyl glutaric acid. If /2-phellandrene
be oxidised, closely related acids result, but if a 1 per cent, solution of
permanganate be used and the oxidation effected very carefully in the
cold, with the terpene always in excess, a glycol, C10H16(OH)2, results,
which when dehydrated with dilute sulphuric acid yields tetrahydro-
cuminic aldehyde.
This aldehyde is identical with the naturally occurring phellandral,
an aldehyde found in oil of water fennel. If the nitrosochloride of /?-
phellandrene be decomposed by acetic acid, dehydrocuminic aldehyde and
carvacrol result.
The phellandrene nitrites are converted, by heating with strong
hydrochloric acid at 40°, into mono- and di-chlorthymo-quinone.
If the a-phellandrene nitrite be heated with an alcoholic solution of
potash, it is converted into nitrophellandrene, C10H15(NO2). This body is
converted by reduction with sodium and alcohol into tetrahydrocarvone,
or by less energetic reduction with zinc and acetic acid, into carvotan-
acetone. The relationship between these bodies is shown by the follow-
ing formulae:—
2
Gazz. Chim. Ital., 46 (1916), 119.
CH CH3 CH, CHQ
C C C
HNO,
H,C CH H2C CHNO H.7C CH
CH—CH(CH3), CH—CH(CH3)2 CH—CH(CH8)2 CH—CH(CH3)2
Carvotanacetone. Nitro- a-Phellandrene- a-Phellandrene.
a-phellandrene. nitrite.
Wallachl has prepared a-phellandrene synthetically from sabinenic acid
by oxidising it to sabina ketone with potassium permanganate. This
ketone was converted into its semicarbazone, and the latter compound
treated with dilute sulphuric acid, when sabina ketone is not regenerated,
but an isomer, which was found to be isopropyl-hexenone. By the
interaction of this body with methyl-magnesium iodide, loss of water
occurs with a simultaneous conversion into a-phellandrene, which appears
to be a mixture of the dextro- and laevo- varieties. This synthetically
prepared a-phellandrene has the following characters :—
Melting-point of nitrite 113°
Clover2 has isolated a terpene from elemi oil, which he claims to be pure
a-phellandrene, and which has an optical rotation of + 129*8°.
TEKPINENE.
The chemistry of the hydrocarbons known under this name is in a
very unsettled condition. There are at least three well-defined terpenes
known by this name, a-terpinene, /3-terpinene, and y-terpinene, which
have the following constitutions :—
CH., CH., CH<>
C C
H2C H2C R,C
HCk /CH., , / 2
C C C
CH(CH3)2 CH(CH8), CH(CH3)2
a-Terpinene. j8-Terpinene. 7-Terpinene.
Apparently only a-terpinene and y-terpinene have been found occurring
naturally in essential oils. All the terpinenes are formed artificially from
other terpinenes, or from geraniol, cineol, terpin hydrate, linalol, dihydro-
carveol, and numerous other compounds.
In 1908-1909 F. W. Semmler 3 made a critical study of the question
of the characters of the terpinenes with a view to clearing up some of the
]
Annalen, 359, 265. - Amer. Chem. Journal, 39, 613.
*Berichte, 41 (1908), 4474 ; 42 (1909), 522.
72 THE CHEMIST.KY OF ESSENTIAL OILS
contradictory statements which had been published in regard to them.
By acting on carvenone with phosphorus pentachloride and reducing the
carvenene chloride formed, he obtained a hydrocarbon which he termed
carvenene, which by its method of production should be a dihydrocymene,
and is considered by Semmler to be a-terpinene, possibly mixed with
some of the other modifications. By boiling carvenene for two hours
with alcoholic sulphuric acid, he inverted it to isocarvenene, which
Semmler considers to be /2-terpinene. Wallach, however, does not con-
sider that these bodies are identical with the a-terpinene and /2-terpinene
above mentioned. Semmler's two terpinenes (carvenenes) have the follow-
ing characters:—
Carvenene Lsocarvenene
(a-terpinene). (j9-terpinene).
Specific gravity at 20° . . . 0-844 0*845
Boiling-point . . . . 180° a t 7 3 5 m m . —
„ . . . . 61° to 63° at 10 mm. 59° to 62°
Refractive index . . . . 1-4910 ' 1*4800
Auwers l has paid considerable attention to the terpinene question,
and especially in regard to the tact that the molecular refraction of the
terpinenes shows considerable variation according to the method of pre-
paration, and often appears to indicate that the terpinenes are excep-
tions to Briihl's laws of refraction. He came to the conclusion that the
terpinenes are usually mixtures of more than one modification, together
with a certain amount of a hydrocarbon of the formula :—
GH3
CH
CH,
Im (CH3)2
Auwers considers that terpinene produced from terpin hydrate is
a mixture in which a-terpinene cannot be regarded as the characteristic
constituent. From the terpinene hydrochloride, the a-terpinene-content
cannot be expected to exceed 50 per cent, in the most favourable case.
For obtaining a-terpinene which, although not pure, is of a comparatively
high percentage, Auwers regards the method from carvone via dihydro-
carveol as the best. Semmler regards carvenene as a particularly pure
a-terpinene, but Auwers does not agree with this, because in its preparation
the action of nascent hydrochloric acid produces conditions which afford
no guarantee of a uniform final product. Carvenene does not appear to
be identical with a-terpinene from o-cresol which Auwers prepared by
acting on o-cresol with chloroform and alkali, thus producing methyl-
dichloromethyl-keto-dihydrobenzene. This body was converted into its
higher homologues by the action of magnesium alkyl iodide, and the
resulting bodies were isomerised by concentrated sulphuric acid, and the
^Bericlite, 42 (1909),. 2404, 2424.
isomers, on treatment with alcoholic potash yield the corresponding
hydrocarbons. By using magnesium propyl iodide, he obtained A1 y
menthadiene, i.e. a-terpinene. Auwers and his pupils have also prepared
a-terpinene synthetically by other methods, and find it to have the follow-
ing characters:—
Boiling-point 65° to 66° at 13'5 mm.
19°
Specific gravity at -0- 0-8353
Henderson and Sutherlandl have prepared a hydrocarbon synthetic-
ally which is possibly a modification of terpinene. They reduced thymo-
hydroquinone, thus obtaining menthane-2-5-diol, which was heated for
half an hour with twice its weight of sulphate of potash under a reflux
condenser, and so yielded a terpene boiling at 179°, of specific gravity
about 0-840 and refractive index 1-4779.
It may be accepted that a-terpinene has characters falling within the
following limits:—
Specific gravity 0*842 to 0-846 at 20°
Refractive index about 1-4720 to 1-4800
A specimen of y-terpinene obtained by Schimmel & Co. from coriander
oil, and probably consisting of a mixture of the a- and y-varieties, had the
The most characteristic derivative for the identification of a-
terpinene is the nitrosite, C10H16N2O3, which melts at 155°. It is pre-
s pared as follows: 2 to 3 grams of the product to be identified are
dissolved in an equal volume of petroleum ether, and an aqueous solution
of 2 to 3 grams of sodium nitrite added. Glacial acetic acid is then
added gradually with constant stirring, the vessel being immersed in
warm water for a few moments and then allowed to stand in a cool place.
Terpinene nitrosite separates, usually in a few hours, but always in two
days. The crystals are filtered off, washed with water, and then with
cold alcohol, and dried on a porous plate. The crystals can be puri-
fied by recrystallisation from hot alcohol, and melt sharply at 155°.
With piperidine, it yields a nitrolpiperidine melting at 153° to 154°, and
with benzylamine a nitrolbenzylamine melting at 137°. These two
compounds are prepared in the same manner as the corresponding
pinene derivatives (q.v.).
It is probable that y-terpinene has not been isolated in a state of
purity, but it can be recognised, by yielding erythritol melting at 236° to
237°, on oxidation with potassium permanganate. In order to obtain
this, 140 grams of the product to be identified are shaken for several
hours with 280 grams of caustic potash and 660 grams of potassium per-
manganate, 8 litres of water, and 8 kilos of ice. The erythritol resulting
is recrystallised from 25 per cent, alcohol, when it melts at 236° to 237°.
y-terpinene does not yield a crystalline nitrosite.
l
Jour. Chan. Soc., 97 (1910), 1616.
TERPINOLENE.
This terpene is very rarely met with in nature, but is formed by the
dehydration of various alcohols, such as terpineol and linalol. It has
been identified in the essential oil of Manila elemi.
The constitution of terpinolene is probably as follows :—
CH;i
H,C
H,Cv >CH,
This terpene wras discovered by Wallach,1 and was prepared by heat-

ing turpentine oil with alcoholic sulphuric acid. It is also yielded in
satisfactory quantity by dehydrating terpineol by means of oxalic acid.
Melted terpineol (melting-point 35°) is added very gradually to a boiling
saturated solution of oxalic acid, through which a current of steam is
passed. About 1 gram of terpineol should be added, drop by drop, pel-
minute, so that dehydration is complete, and the resulting terpinolene
is at once removed by the current of steam before it is isomerised to any
extent.
Semmler 2 has succeeded in preparing pure terpinolene by the reduc-
tion of terpinolene tetrabromide by means of zinc-dust in alcoholic
medium (not in presence of acetic acid, as in that case a mixture of hydro-
carbons is obtained). The constants of the pure hydrocarbon are :—
Refractive index . 1-484°
,, ,, ,, 760 mm. 183° ,, 185°
Optical rotation . + 0"
Terpinolene therefore appears to be, of all the monocyclic terpenes r
the one which possesses the highest specific gravity and the highest boil-
ing-point.
For the identification of terpinolene, its tetrabromide is the most
characteristic compound. This body is prepared by adding gradually four
atoms of bromine to a solution of the terpene in glacial acetic acid,
maintained at a low temperature. Terpinolene tetrabromide, C]0H1(;Br4,
melts at 116° to 117°, when recrystallised from alcohol.
ORIGANENE.
This terpene has been isolated from the oil of Oriyanwm kirtum by
Pickles.^ It is an oil possessing a distinct odour of lemons, and has the
Boiling-point . . . . . . . 160 t o 164 a t 7 5 0 m m .
Optical rotation . . . . . . + 1 50'
l
Aniialeu, 227, 283 ; 230, 262. « Uerickte, 42, 4644.
-Jour. Ghein. Soc., 93 (1908), 862.
It is possible that this slight optical rotation may be due to traces of
impurities.
Origanene yields a crystalline nitrosochloride, melting at 91° to 94°,
and a nitrolpiperidine melting at 198°. These derivatives are prepared
in the same manner as the corresponding compounds of pinene (q.i'.).
Pickles has suggested that origanene has the constitution which
Wallach has assigned to a-terpinene, but there is not sufficient experi
mental evidence to support this suggestion.
CRITHMENE.
Francesconi and Sernagiotto1 have isolated a terpene from the
essential oil of Crithmum maritimum distilled from plants grown in
Sardinia.
It has the following characters : —
Boiling-point ......... 178° to 180°
Specific gravity . ........ 0-8658
Refractive index . . . . . . . . . 1'4S06
Crithmene yields an a-nitrosochloride, crystallising in laminae, and
melting at 101° to 102°, and a ^-nitrosochloride, C10H16ONC1, forming
quadratic plates and melting at 103° to 104°. Both are devoid of optical
activity. The nitrosite melts at 89° to 90° and the nitrosate at 104° to
105°. A tetrabromide is formed, C10H1gBr4, but could not be obtained in
the crystalline condition. The isomeric nitrolpiperides, prepared from
the nitrosochlorides, melt in both instances at 138°. The benzylamine
compound melts at 103° to 104°. If the nitrosochloride be hydrolysed by
means of alcoholic alkali and the resulting products distilled in a current
of steam, a solid body, forming minute crystals melting at 131°, is left
behind. It contains nitrogen. Crithmene yields a dihydrochloride,
C10H16(HClj2, melting at 52°, and apparently identical with that of
terpinene. The constitution of crithmene is probably that of a A1>7~4'8
joara-menthadiene, as follows : —
C:CH 2
H2C/\CH2
C : C(CH3)2
CARENE.
This terpene has been isolated by Simonsen 2 from Indian turpentine
oil, from Pinus longifolia. It is identical with the terpene previously
described by Eobinson 3 as a terpene yielding sylvestrene hydrochloride
when treated with hydrogen chloride. Its characters are as follows : —
30°
Specific gravity at —5 ....... 0*8586
oO
Eefractive index at 30° ....... 1-4690
Optical rotation ......... + 7 -69°
Boiling point at 705 inm ........ 168° to 169°
„ ,, 200 ,, ....... 123° „ 124°
1 2
All. R. Acad. Line. (1913),
:i
231, 312. Jour. Chem. Soc., 1920, 570.
Proc. Chem. Soc., 1911, 27, 247.
Dextro-carene is a colourless oil with a sweet odour. Its nitrosate,
C10H1(.O3N2, melts at 141-5°.
On treatment in ethereal solution with hydrogen chloride, it yields
a mixture of sylvestrene and dipentene hydrochlorides. Its constitution
is probably represented by one of the two following formulae :—
CH3 CH3
I
c c
I
HC CH2 H2C CH
I I I !
H2C CH H2C CH
CH—C(CH3)2 CH-—C(CH3)2
DACRYDENE.
Baker and Smithl have isolated a terpene from the essential oil of the
leaves of Dacrydrium Franklini (the huon pine of Tasmania) which
Optical rotation . +12-3°
It forms a nitrosochloride melting sharply, but with decomposition,
at 120° to 121°. It has been named dacrydene.
In addition to the above-described terpenes proper, there are a few
other hydrocarbons which may be conveniently dealt with here. These
are salvene, the so-called olefinic terpenes, myrcene and ocimene, the
terpene homologues, cantharene,santene, and a hydrocarbon of the formula
C11H18 found in sandal wood oil, and the diterpene phyllocladene.
SALVENE.
Salvene is a hydrocarbon of the formula C10H18 found in oil of sage2.
by Seyler. It has the following approximate characters —-
Its constitution is as follows :—
C . CH(CH3)2
CH . CH3
1
The Pines of Australia, 397 (1st edition). *Ber;chte, 35 (L902>, 550.
MYRCENE.
Myrcene is a compound of the formula C10H16 which has been found
in a number of essential oils, such as bay oil, West Indian lemon-grass
oil, the oil of Lippia citriodora, etc., etc. It has sufficient resemblance to
the terpenes proper to have been classified as an " olefinic" terpene, its
constitution being that of an open chain, and not a ring compound.
Myrcene has one of the two following constitutions :—
CH,v
>C : CH . CH 0 . CH 9 . C(CH2). CH : CH2
CH/
or
CH.
. CH 2 . CH 2 . CH2 . C(CH2) . CH : CH2
CH/'
Myrcene can be obtained, according to Power and Kleber,1 from oil
of bay in the following manner: The oil is first shaken with a 5 per
cent, solution of caustic soda to remove phenols, and is then fractionally
distilled in vacuo. Eventually, by repeated fractionation a colourless
liquid results, which distils at 67° to 68° at 20 mm. pressure, and is
practically pure myrcene.
Myrcene has the following characters :—
Boiling-point 167°
,, ,, at 20 mm. 67° to 63°
By reduction with sodium alcohol, myrcene yields dihydromyrcene,
C^H^, a liquid, which yields a tetrabromide melting at 88°, which is a
useful compound for the identification of myrcene. The olefinic terpene
ocimene (q.v.) yields the same body on reduction, so that dihydromyrcene
and dihydro-ocimene are identical. By acting upon linalol with sodium
alcohol, a hydrocarbon of the formula C10H18 is formed by abstraction of
the oxygen, which is also identical with dihydromyrcene, although it has
been named linalolene. It yields the characteristic tetrabromide melting
at 88°. The physical characters of the dihydromyrcenes prepared from
these various sources are as follows :—2
Linalolene Dihy dro my rcene Dihydromyrcene Dihydro-ocimene Dihydromyrcene

(Seinmler). (Enk .aar). (Schimmel & Co.).
B.-p. 165° to 163° 171-5° to 173-5° 166° to 168° 166° to 168° 168°
8p.gr. 0-7882 (20°) 0-7802 (? °) 0-7852 (15°) 0-7750 (15°) 0-7824 (15°)
Befr. 1-455 (20°) 1-4501 1-4514 (17°) 1-4507 (17°) 1-45251 (15°1
The preparation of dihydromyrcene tetrabromide is often attended by

difficulties. The method recommended by Enklaar, and recently also
adopted by Semmler, of dissolving the hydrocarbon in glacial acetic acid,
has not stood the test of practice, because according to Schimmel & Co.
. Rund., New York, 1895, 13.
'2 Schimmel & Co., Report, Oct. 1911, 129.
it generally gives rise to oily bromides. Hydrobromic acid appears to
be evolved as soon as the bromine is added to the glacial acetic acid
solution. The reaction is accomplished more quickly and effectively by
dissolving the hydrocarbon in a mixture of 1 part by volume of amyl
alcohol and 2 parts by volume of ether. Soon after the addition of
the calculated quantity of bromine the tetrabromide separates out.
If myrcene be heated with glacial acetic acid to 40° for three to four
hours, with the addition of a little sulphuric acid, hydration takes place, and
an alcohol, which is termed myrcenol is formed. This body is an oil, of
specific gravity 0'9032, refractive index 1*4806 at 15°, and boiling-point
99° at 10 mm. pressure. It yields a phenylurethane melting at 68°.
Myrcenol probably has the constitution : —
C : CH . CH2 . CH., . C(CH3)(OH) . CH : CH,

CH
or
C . CH., . CH., . CH, . C(CH3)(OH) . CH : CH,
GH.f
The resemblance of myrcene to the terpenes proper may possibly be
connected with the fact that, like geraniol and linalol, they show a marked
tendency towards closing the open chain into a six carbon ring. For
example, when dihydromyrcene C10H18 is treated with acetic and sul-
phuric acids, an alcohol is formed, together with the isomeric hydrocarbon,
C10H1S, where a six carbon ring has been formed, and which is termed
cyclo-dihydromyrcene. This body is an odorous oil having the following
characters : —
Boiling-point ......... 169° to 172°
Specific gravity ........ 0-828 at 20°
Refractive index ........ 1-4620 ,, 20°
Molecular refraction ........ 45° to 63°
Myrcene is easily polymerised, and it is probable that this fact
accounts for the decrease in solubility of essential oils which contain
myrcene, when they have been kept for any length of time.
Koschelew 1 has recently prepared a closely related olefinic terpene,
which he has termed /3-myrcene, by treating isoprene in a sealed tube to
80° to 90° for five days. This body has the constitution : —
,CR
CH, : CH . C(CH3) : CH . CH., . C
It is a colourless oil having an odour very similar to that of myrcene,

and boiling at 63° at 20 mm.
OCIMENE.
This body is very closely related to myrcene, and has been found in
the oil of basil distilled in Java. It has the following constitution : —
CH3 . C(CH3) : CH . CH2 . CH : C(CH3) . CH : CH2
Its characters are as follows : —
]
Chem. Zentral. (1916), i. 1068, 1136.
Boiling point 172° at 750 mm.
73° to 74° at 20 min.
As stated above it yields dihydromyrcene (dihydro-ocimene) when
reduced by sodium alcohol. On hydration by means of acetic and sul-
phuric acids it yields an alcohol, ocimenol, which has the following char-
acters :—
Specific g r a v i t y . . . . 0-901
Boiling-point . . . . 97° at 10 mm.
Melting-point of phenylurethane 72°
By heat, ocimerie is converted into allo-ocimene, which is probably
a stereoisomeric compound.
CANTHARENE.
l
Haworth has described a lower homologue of the terpenes which he
obtained by the dehydration of the alcohol cantharenol. Cantharene,
C8H12, was first prepared by Piccard during his classical work on can-
tharidine, and it so closely resembled the terpenes in character that
Piccard regarded it as the first artificially prepared terpene. The close
relationship of these bodies, which are dihydroxylenes, to the terpenes,
made it of interest to carry out a careful examination of them, and with
this object in view a general method has been devised for the preparation
of pure hydrocarbons of this group. If methyl-cyclo-hexenone is treated
with magnesium methyl iodide the alcohol cantharenol is obtained, which
is the " terpineol " of the group. The dehydration of the alcohol leads to
the formation of the corresponding hydrocarbon, which, chemically, is
1:2 dimethyl A 2 • 6 cyclohexadiene. This body boils at 135*5,° and
20°
has a specific gravity 0-852 at -j-0-, and refractive index 1*4895; and ap-
pears to agree in all its characters with Placard's cantharene. It has a
high refractive index, and gives similar colour reactions, and yields ortho-
toluic acid on oxidation,. There are, of course, three isomeric dihydroxy-
lenes, and the other two were also prepared, and have the following
characters:—
Dihvdro- Dihydro- Dihydro-

o-xylene. ///-xylene. 7>-xylene.
Boiling-point . . . . 135-5° 135° 135° to 138°

20°
Specific gravity —^ 0-8521 0-8373 0-830
Refractive index . . . . 1-4895 1-4856 1-4797
Molecular refraction . 36-62 37-01 36-94
SANTENE.
This hydrocarbon, also known as nor-camphene, is an immediate
lower homologue of the terpenes, of the formula C9H14. It was dis-
l
Jour. Chem. Soc., 1913,1242 ; P. and E.O.R., 1913, 254.
covered in oil of sandalwood by Mtiller.1 It is also present in Siberian
pine-needle oil, and in several other pine oils.
According to Semmler 2 it has the constitution :—
CH
H 3 C.C
CH,
H3C . G! CH.,
CH
This constitution is confirmed by the conversion of camphenylone
into santene by Komppa and Hintikka.3
Santene has also been examined by Aschan.4 The following are the
characters of the purest specimens which have been isolated from
sandalwood and Siberian t)ine oils : —
I
; Sandalwood.
Siberian Pine.
Semmler. Aschan
Boiling-point . 131° to 33° (9 mm.) 140° 140°

Specific gravity . 1 0-863 (20°) 0-8708 (15°) 0-8698 (15°)
Refractive index . i 1-46658 (20°) 1-4688 (17-5°) 1-4696 (19° >
Rotation . . ; +0° + 0° + 0°
Santene forms a nitrosochloride, prepared in the usual manner, melt-

ing at 109° to 110°, and a nitrosite melting at 125°. It also forms a
hydrochloride melting at 80° to 81°. By hydration with sulphuric and
acetic acids it yields an alcohol C9H15OH, which is termed santenol
(isosantenol, nor-borneol). This body melts at 97° to 98° and boils at
195° to 196°.
Kondakow 5 has carried out an investigation on the haloid derivatives
of santene, and finds that mixtures of liquid and solid hydrochlorides and
hydrobromides are usually obtained so that the haloid derivatives are
unsatisfactory for identification purposes.
Santenyl acetate, C9H15. OOC . CH8, is a liquid of specific gravity
0-9859 at 20°, refractive index 1-45929, and boils at 85° to 89° at 8 mm.
HYDROCARBONS CnH18, FROM SANDALWOOD OIL.

Schimmel & Co.6 have isolated a hydrocarbon of the formula C n H ia
from sandalwood oil. This body is completely saturated and is un-
affected by potassium permanganate at ordinary temperatures.
Semmler7 in the course of his researches on the constitution of the
l
Archiv.d Pharm. 238 (1900), 36<x
2
Berichte, 40 (1907), -465, 4594, 4844; 41 (1908), 121, 385.
4
3 Bull. Soc. Chim. [4], 21, 13.
5
Ibid., 4918.
Jour Russ.phys. Chem. Ges., 43 (1911), 1107.
fi
7
Berichte, 40 (1907), 1124 ; 43 (1910), 1722.
santalols, obtained from triq/c/oeksantalic acid, by splitting off carbon
dioxide gas, a hydrocarbon which he termed nor-tricT/ctoeksantalane. The
most recent investigations of Semmler have shown that tricT/c/oeksantalic
acid posseses twelve carbon atoms, from which it would seem that the
correct formula of nor-tricT/cZoeksantalane is C11H18, and Semmler's.
analyses agree with this view.
The following are the characters of the two hydrocarbons :—
Hydrocarbon from Nor-tric?/cZoeksantalaiie
Sandalwood Oil. (according to Semmler).
Boiling-point . . . 183° 183-5°
Specific gravity at 20° . 0-9092 0-885
Rotation . . . . - 2 3 ° 55' -11°
Refractive index . . 1-4786 1-46856
Molecular refraction. . 46'74 47-15.
It is probable that the tricyclic hydrocarbon from sandalwood oil is
identical with, or at least closely allied to, Semmler's nor-tric^/doeksanta-
lane.
PHYLLOCLADENE.
Baker and Smith have isolated from the essential oil of the leaves
of Phyllocladvis Rhomboidalis a diterpene, which they have named
phyllocladene It has the formula C20H32, and melts at 95°. It is,
dextro-rotatory, its specific rotation being + 16*06°.
2. SESQUITERPENES,
The sesquiterpenes are compounds of the formula C15H24, which are
of higher specific gravity, boiling point, and refractive index than the
terpenes. They are of complicated constitution, and are less well under-
stood in this respect than the terpenes, although modern research is
gradually elucidating many of the problems connected with this inter-
esting group of compounds. Apart from the so-called aliphatic sesquiter-
penes, which appear to bear the same relationships to the sesquiterpenes
proper as do the aliphatic terpenes to the true terpenes, the sesquiterpenes
are classified according to the number of closed rings existing in the mole-
' cule, which, where the constitution is not clearly understood, may be
deduced from the molecular refraction of the compound. The following
figures generally hold good :—
Molecular Refraction Specific Gravity-
Calculated.
Monocyclic 67'76 0-875 to 0-890
Bicyclic 66-15 0'900 „ 0-920-
Tricyclic . . . . . . 64-45 0'930 ,, 0-94O
BlSABOLENE.
This sesquiterpene is a monocyclic compound, first isolated from the

essential oil of Bisabol myrrh by Tucholka.1 It was found in oil of limes,
and described by Burgess under the name limene. It occurs in several
other essential oils. When separated by fractional distillation from
lemon oil, Gildemeister and Miiller 2 found it to have the following
characters:—
1
Arch. der. Pharm., 235 (1897), 292.
'2 Schimmel, Bericht, October, 1909, 50.
VOL. II. 6
Optical rotation . , - 41° 31'
When prepared by regeneration from the trihydrochloride, the sesqui-
terpene is inactive, a pure specimen having the following characters:—
Optical rotation . . . . . . . . 0°
If a current of hydrochloric acid gas be passed through an ice-cold solu-
tion of the sesquiterpene dissolved in ether a crystalline trihydrochloride
is obtained, which melts at 79° to 80°, and has the formula C15H24 . 3HC1.
ZINGIBERENE.
This sesquiterpene
1
was isolated from oil of ginger by Von Soden
and Kojahn and has been examined by them and by Schreiner and
Kremers.2 It is obtained by fractional distillation under reduced pressure
and is a colourless and nearly odourless oil. Its characters are as
follows:—
Boiling-point 270° (with decomposition)
at 32 mm. 160° to 161°
14 mm. 134°
Specific rotation -73° (approximate).
Zingiberene forms a dihydrochloride, C15H24, 2HC1, when its solution
in an equal volume of glacial acetic acid is saturated at 0° with dry
hydrochloric acid gas. It crystallises from hot alcohol in fine white
needles melting at 168° to 169°.
The nitrosochloride, C15H24 . NOC1, prepared in the usual manner, is a
\vhite powder melting with decomposition at 96° to 97°.
The nitrosite, C15H24N2O3, is formed when zingiberene is dissolved
in ten times its volume of petroleum ether, the solution well cooled and
treated with a solution of sodium nitrite, and acetic acid added. It
crystallises from hot methyl alcohol, and melts at 97° to 98°.
Zingiberene also forms a nitrosate, CJ15H24 . N2O4, when the sesquiter-
pene dissolved in an equal volume of glacial acetic acid, is cooled to 0°,
and ethyl nitrite, and then nitric acid added. The nitrosate is dissolved
in acetic ether and precipitated with alcohol. It forms a yellow powder,
melting with decomposition at 86°.
When the dihydrochloride above mentioned is produced, it is probable
that molecular rearrangement takes place and that the compound is really
the dihydrochloride of a bicyclic iso-zingiberene. According to Semmler
and Becker 3 when zingiberene is treated with acetic and sulphuric acids,
it is converted into iso-zingiberene. This sesquiterpene has the following
characters:—
Boiling-point at 7 mm. • . . . . . . 118°
Specific gravity 0-911* at 20°
rotation - 51° 36'
]
Pharm. Zeit., 45, 414. '2Pharm. Arch., 4, 141, 161.
*Berichte94& (1912), 1814.
Zingiberene and wo-zingiberene probably have the following con-

stitutions :—
CH CH2
H,C/\H>CH
OH.,
H2C. AH"
H 3 C.CH CH CH, CH,
Zingibereue. Iso-zingiberene.
CADINENE.
Cadinene owes its name to its occurrence in considerable quantity
in oil of cade—which, of course, is not a true essential oil, but the pro-
duct of destructive distillation. It is found in numerous essential oils,
including those of patchouli, savin, galbanum, camphor, cedar wood,
West Indian santal, juniper, and many others. Cadinene is best pre-
pared as follows:—
The fraction of oil of cade boiling at 260° to 280° is converted into
cadinene dihydrochloride by saturating its solution in dry ether with dry
hydrochloric acid gas. The hydrochloride is separated, dried, and
jrecrystallised, and the hydrochloric acid removed by heating it with
aniline or with sodium acetate in glacial acetic acid. The liberated
•cadinene is rectified in a current of steam. Cadinene from oil of cade
is highly laevo-rotatory, the dextro-rotatory variety being obtained from
Atlas cedar oil and West Indian sandal wood oil.
The purest specimens of cadinene prepared have the following char-
acters :—
Optical rotation , -105° 30'
Lepeschkine1 prefers the use of sodium ethylate for the regeneration
of the sesquiterpene, and gives the following figures for pure cadinene
.so produced:—
Cadinene yields a beautiful colour reaction when a few drops are
dissolved in chloroform and shaken with a few drops of concentrated
sulphuric acid. The liquid turns dark green, passing to blue and be-
coming red on warming. If acetic acid be used instead of sulphuric
acid, the blue colour is more marked.
Cadinene forms a well - defined crystalline dihydrochloride,
C15H24 . 2HC1. In order to prepare it most successfully the fraction of
oil of cade boiling between 260° and 280°, as mentioned above, is dis-
solved in twice its volume of dry ether, and saturated with dry hydro-
chloric acid gas. The mixture is allowed to stand for several days and
1
Jour. Soc. phys. chim. Russ., 40, 698.
a portion of the ether is distilled off. On further evaporation, the
dihydrochloride crystallises out. The crystals are separated, washed
with a little alcohol, and recrystallissd from ethyl acetate. Cadinene
dihydrochloride melts at 117° to 118° and has a specific rotation (in
5 per cent, chloroform solution) — 37°.
Cadinene dihydrobromide, C J 5 H 2 4 . 2HBr, is obtained by shaking cad-
ine dissolved in acetic acid with fuming hydrobromic acid. It forms
white needles melting at 124° to 125°, and having a specific rotation
- 36*13°. The dihydriodide, C15H24 . 2HI, prepared in a similar manner,
melts at 105° to 106° and has a specific rotation - 48°.
Cadinsne nitrosochloride, C15H24NOC1, is prepared by mixing a
solution of cadinene in glacial acetic acid, kept in ice, with ethyl nitrite,
and then adding a saturated solution of hydrochloric acid gas in acetic
acid. It forms crystals melting, with decomposition, at 93° to 94°. The
nitrosate, C15H24 . N2O4, is prepared by treating a well-cooled mixture of
the sesquiterpene dissolved in glacial acatic acid, and ethyl nitrite, with
a mixture of nitric acid and acetic acid. This compound melts with
decomposition at 105° to 110°.
Cadinene is a bicyclic sesquiterpene, whose constitution is not
definitely understood.
CAKYOPHYLLENE.
Caryophyllene, as isolated from essential oils, and as usually described
in literature is, without the slightest doubt, a mixture of at least two,
if not three distinct chemical individuals.
This sesquiterpene, or mixture of sesquiterpenes, is found to a con-
siderable extent in nature, especially in clove oil, pimento oil, pepper oil,
cinnamon oil, bstel oil, copaiba oil, and numerous other essential oils. As
isolated from these oils the sesquiterpene has the following characters :—
Optical rotation rro go
Deussen and Lewinsohnl were the first chemists to show con-
clusively that at least two sesquiterpenes are present in this body. By
repeated fractional distillation they separated it into two bodies having the
following characters, suggesting that the former might be an optically
inactive sesquiterpene, slightly contaminated with the optically active
variety:—
Boiling-pMnt (16 mm.) , 132° to 13 i° C. Boiling-point (17 mm.) 128° to 128-5°
Specific gravity at 20° , 0-90346 Specific gravity at 17° 0-91034
- 4-67° [a]1D . . . . - 23-57°
1-43973 no ' 1-49899
The former of these bodies gave a yield of 20 per cent, of a nitroso-
chloride and 8*2 per cent, of a blue nitrosite. The second gives only a
very small quantity of nitrosochloride and only 0*5 per cent, of nitrosite.
Deussen termed the inactive caryophyllene, as further experiments
showed it to be, a-caryophyllene, and the laevo-rotatory compound, /?-
caryophyllene. A third body was obtained, which yielded no blue nitrosite
at all, to which Deussen assigned the name y-caryophyllene. This body
1
Annalen, 356, 1; 359, 245.
was obtained by heating the alcoholic solution of /?-caryophyllene nitrosite.
It is identical with the body previously known as isocaryophyllene, and
Semmler and Mayer l have taken up the study of this complicated

question, and have agreed with Deussen in the main, but have further
complicated the question by introducing fresh nomenclature of a scarcely
scientific character. They consider, as Deussen proved, that crude caryo-
phyllene consists of three distinct chemical individuals: (1) the inactive
a-caryophyllene isolated by Deussen, which is probably identical with the
sesquiterpene from oil of hops described as humulene; (2) terj>caryo-
phyllene, so called because Semmler considers it to be in some degree
related to terpinolene, and (3) ^'w-caryophyllene, so called on account of
its believed relationship in some remote manner to limonene. The follow-
ing formulae have been suggested for the last named two modifications :—
C—CH. CH,
CH,
CH., CH,
T0rp-caryophyllene.
CH,
HC<
jLi?M-caryophyllene.
T0rp-caryophyllene and Zm-caryophyllene can be converted the one

into the other by the preparation of their nitrosites or their nitroso-
chlorides, and subsequent regeneration of the sesquiterpene. They also
both yield the same hydrochloride, melting at 69°.
Schimmel & Co.2 showed that by treating caryophyllene hydro-
chloride melting at 69° (68° to 70°) with sodium ethylate, an unsaturated
tricyclic sesquiterpene resulted. This body has the following characters :—
1 2
Berichte, 44, 3657. Report, October, 1910, 180.
If milk of lime be used as the regenerating reagent, a different sesqui-
terpene results, which has the following characters :—
Refra3tive index 1-49941
Semmler and Mayer l agree that the reagent used and the conditions
of temperature, etc., govern the character of the sesquiterpene, or mixture
of sesquiterpenes which result. By using sodium methylate very cau-
tiously, they obtained a caryophyllene having the following characters :—
Boiling-point at 12 mm 121° to 122-5°
Specific gravity at . 0 . 0-8996
So that by suitable procedure it is possible to regenerate dextro-
caryophyllene from the crystalline hydrochloride.
By using pyridine to split off the hydrochloric acid, Semmler and
Mayer obtained a caryophyllene substantially identical with that obtained
by Schimmel, but of optical rotation - 57°, indicating that Schimmel's.
body was a mixture of the two compounds. Semmler and Mayer give
the following formulae for the caryophyllenes indicated by the above,
together with that of the hydrochloride, to indicate the transpositions,
which occur:—
CH9 CH CH2 CH
H
/\" /\ /CH3 /\ H
H2C C C< H9C C : C
[ | CH2|\CH3 <--> "| | CH2| \CH,
C \j | CH9 \j\j\ \j\\j CH9
II NX
r^TT /ITT TT (^/\rlTT /^TT
\\//^TT
2 W±12UJLJL -tj-3^ O±lgO±lgO±l
(1) Bicyclic regenerated caryophyllene. ^^^ Dihydrochloride.
tS
CH2 CH CH, CH
HC C ,/
CI^\
H2 \CH,
C C I CtL, C G CH2
H3C CH2CH3CH LLS.
(2) Tricyclic caryophyllene. ^3) The caryophyllene which yields a
blue nitrosite.
Formula (1) would thus indicate the natural dextro-caryophyllene
of clove stems; formula (2) indicates the highly laevo-rotatory caryo-
phyllene resulting from regeneration by means of pyridine, and (3) may
represent the a-caryophyllene of Deussen.
l
Berichte, 43(1910), 3451.
If these assumptions be correct, there must be at least four natural
sesquiterpenes of the caryophyllene character, namely, those represented
by formulae (1) and (3), and the terp-caryophyllene and Zzm-caryo-
phyllene of Semmler. The most characteristic derivatives of the
caryophyllenes are the following :—
Caryophyllene dihydrochloride, Cj5H24.2HCl, may be obtained by
saturating a quite dry ethereal solution of the sesquiterpene with dry
hydrochloric acid gas, and exposing the mixture to very intense cold. It
Caryophyllenic alcohol, Clf,H26O, is the easiest crystalline derivative to
obtain for purposes of identification. The fraction of the oil containing
caryophyllene is heated for a considerable time on the water-bath, using
25 grams with a mixture of 20 grams of strong sulphuric acid, 40 grams
of water, and 1000 c.c. of glacial acetic acid. When the reaction is com-
plete, the mixture is steam-distilled. At first acetic acid and a mobile
oil pass over, and then a much less volatile product, which solidifies on
cooling. This is collected and purified by crystallisation from alcohol.
It is caryophyllenic alcohol, and melts at 94° to 96°. It forms a phenyl-
urethane melting at 136° to 137°. On treatment with dehydrating agents
this alcohol yields not any modification of caryophyllene above described,
but a sesquiterpene which is known as clovene, but which is probably just
as accurately described as an isomeric caryophyllene as any of the other
sesquiterpenes in question. It is, however, described below under a
separate heading in order to be in conformity with the current, although
unsatisfactory, nomenclature.
Caryophyllene nitrosochloride, (C15H24)2N2O9C12, is obtained when a
mixture of the sesquiterpene, alcohol, ethyl acetate, and ethyl nitrite is
cooled in a freezing mixture, and then treated with a saturated solution
of hydrochloric acid in alcohol. The reaction mass is allowed to stand
on ice for an hour and is then exposed to sunlight. Thus prepared it
melts at about 158° to 163°, and can be separated into two compounds,
one being that of a-caryophyllene and the other that of /^-caryophyllene
Deussen's sesquiterpenes of natural caryophyllene from clove oil), a-
caryophyllene nitrosochloride melts at 177°, and ^-caryophyllene nitroso-
chloride at 159°. They can be separated by fractional crystallisation.
The corresponding a-nitrolbenzylamine melts at 126° to 128°, and the /?-
nitrolbenzylamine at 172° to 173°. The bimolecular formula given above
is probable but not certain.
Nitroso-caryophyllene, C15H2gNO, is prepared by splitting off hydro-
chloric acid from the corresponding nitrosochloride, by means of sodium
methylate. a-Nitrosocaryophyllene melts at 116° and is optically in-
active (as is the a-nitrosochloride), and /3-nitrosocaryophyllene melts at
120° to 121° and has a specific rotation + 61-77° (as against - 98'07° for
the /?-nitrosochloride).
Caryophyllene nitrosite is an interesting compound. It has the
formula C15H24N2O3, and was first produced by Schreiner and Kremers.1
It is formed by treating a mixture of equal volumes of the sesquiter-
pene and petroleum ether with a concentrated solution of sodium nitrite
and glacial acetic acid. It crystallises in fine blue needles; when re-
crystallised from alcohol it melts at 115° and has a specific rotation
+ 103°.
1
Pharm. Archives, 2 (1899), 283.
By treating this blue nitrosite, which Deussen calls /?-caryophyllene
nitrosite, with alcoholic potash at 0°, it is converted to a colourless isomer,
melting at 139°, which Deussen terms /:?-caryophyllene isonitrosite. By
treatment with boiling petroleum ether decomposition takes place and a
compound melting at 159° is formed, of formula not yet established, and
a nitro-compound of the formula C15H22N2O4, melting at 13O5°.
From the mother liquors of the preparation of the nitrosite from
caryophyllene, a sesquiterpene is obtained, which may be the product of
inversion by acids, or may be naturally present. It has the following
characters :—
This body has been termed by Deussen isocaryophyllene. It yields
two nitrosochlorides, a-isocaryophyllene nitrosochloride melting at 122°,
and /2-isocaryophyllene nitrosochloride melting at 146°.
A study of the oxidation products and nitroso-derivatives of caryophyl-
lene, leads Deussen to consider that this sesquiterpene is a naphthalene
derivative of the formula—
CH
OH,
CH,
\/CH\ x
c c
c CH,
CH, CH,
The above considerations indicate the complex nature of the hydrocarbons
known as caryophyllene. For practical purposes, however, the compounds
indicated are obtained of practically definite melting-points, and, in spite
of the complicated isomerism existing amongst most of them, are useful
for identification of the sesquiterpene or mixture of sesquiterpenes, occur-
ring naturally and known as "caryophyllene".
HUMULENE.
Humulene is the name .assigned by Chapman l to the sesquiterpene
which he isolated from essential oil of hops'. Its characters are as
follows:—
It is probably optically inactive, The following derivatives of humulene
were prepared :—
1
Journ. Chem. Soc., 67 (1P95), 54. 7^0.
Humulene nitrosochloride, C15H24NOC1, melts at 164° to 165°, and
yields a nitrolpiperidine, C15H24NO . N . C5H10, melting at 153°, and a
nitrolbenzylamine, C15H24NO . N . C7H7, melting at 136°.
Humulene nitrosate, C15H24N2O4, melts at 162° to 163°.
Humulene nitrosite, C15H24N2O3, was obtained in two modifications,
one forming blue crystals melting at 120°, and the other colourless melt-
ing at 166° to1 168°.
Deussen considers that the nitrosate above described is identical
•with that of a-caryophyllene, and that the nitrosochloride is identical
with that of the same sesquiterpene. He therefore considers that
ihumulene is, at all events iin greater part, actually a-caryophyllene.
The similarity between humulene and caryophyllene had not escaped
•Chapman's notice at the time that he isolated humulene, but as he was
tunable to prepare a hydrate, which is one of the easiest of the caryo-
phyllene derivatives to obtain in a pure state, he concluded that the
•sesquiterpene was not identical with caryophyllene. Eecent work by
Semmler does not tend to establish the identity of the two sesquiterpenes,
and unless and until further evidence to the contrary is forthcoming,
humulene may be regarded as a definite chemical individual.
SELINENE*
Selinene is a bicyclic sesquiterpene occurring in essential oil of celery.
Its presence was first indicated by Ciamician and Silber2 who announced
the isolation of a sesquiterpene boiling at 262° to 269°, but no charac-
teristic derivatives were prepared. Schimmel & Co.3 examined this
sesquiterpene to which they assigned the name selinene. They prepared
a solid dihydrochloride melting at 72° to 74° and having a specific rota-
tion + 18°. The pure sesquiterpene, regenerated from the dihydrochloride
by means of sodium ethylate had the following characters :—
Eefractive index . 1-50483
The most recent work, however, on the sesquiterpene is that of

Semmler and Eisse.4 From the crude selinene, prepared by fractional
distillation, they prepared the crystalline dihydrochloride, C15H24 . 2HC1,
melting at 72° to 74°, by passing a mixture of 1 part of dry hydro-
chloric acid gas with 3 parts of air, into the sesquiterpene dissolved in
ether. This compound on digestion at very gentle heat, with a solution
of caustic potash in methyl alcohol, yields selinene, which the authors
Conclude is a doubly unsaturated bicyclic compound. The characters of
.the selinene thus obtained are as follows :—
By reducing selinene with sodium alcohol, tetrahydroselinene was

1 2
Jour, prakt. Chim. [2], 83, 483. Berichte, 30, 496.
4
J Report, April, 1910, 32. Berichte, 45, 3301; 46, 599.
obtained, of the formula C15H28. This body has the following char-
acters :—
In a second specimen prepared the optical rotation was -f 7°.

Selinol, an alcohol of the formula C15H26O, was prepared from the
dihydrochloride by shaking it for thwrty-six hours at a temperature of 95°
with milk of lime. It is a yellow oil, boiling at 155° to 163°. This
alcohol yields dihydroselinol, C15H28O, when reduced by hydrogen in the
presence of finely divided platinum. This body melts, after crystallisation
from diluted acetic acid, at 86° to 87°.
They have also carried out the oxidation of selinene by means of
ozone and potassium permanganate and have thus been able to establish
that the regenerated selinene is not absolutely identical with the natural
selinene. They are the first to record the existence of a hemi-cyclic-
sesquiterpene; this compound is termed pseudo-(/3)-selinene. By passing
a current of ozone into a solution of natural selinene (pseudo-(/3)-selinene)^
in acetic acid, there is obtained a diketone, C13H20O2, which is purified by
treatment with permanganate in acetone solution. Its properties are as-
follows:—
Its disemicarbazone, C15H26N0O2, melts at 228° C. with decomposition..

The diketone regenerated by the action of oxalic acid on the disemicar-
bazone has the following properties :—
Specific gravity 1O566 at 20°
Optical rotation . . . . . . . . + 15°
The principal oxidation product of the selinene regenerated fronl the

dihydrochloride is a diketocarboxylic acid, of the formula C14H2404,
melting at 226°.
Semmler deduces from these results that natural selinene is composed
of a mixture containing principally the hemicyclic pseudo-(/2)-selinene,
together with a small quantity of ortho-(a)-selinene. By passing through,
the dihydrochloride it is possible to convert the pseudo-(/3)-selinene into
the ortho-(a)-selinene or regenerated selinene, which contains only a
small proportion of the fi form. Both yield the same solid dihydro-
chloride. Selinene affords a typical example of the possibility of the
displacement of the double bond from the side chain into the nucleus.
The following structural formulae represent, according to Semmler,,
the constitutions of the two forms of selinene and illustrate how they
both yield the same dihydrochloride and the same tetrahydroselinene.
Selinene is still another case of unhappy nomenclature. The natural
body is first known as selinene. The regenerated sesquiterpene is termed
ortho-a-selinene, and because the natural, originally named selinene does*
not agree with the artificial body, it is now called " pseudo-Beliuene "..
CH,
CH2
Pseudo-(j8)-selinene Ortho-(a)-selinene
hemi-cyclic (natural). selinene).-
CH
CH3
Tetrahydroselinene.
CH C09H
CH, CO
CH,
Diketone. Diketomon-ocarbo-
xylic acid.
THE SANTALENES.
Two distinct sesquiterpenes exist in the essential oil of Santalum
album, known as a-santalene and yS-santaleme. /3-santalene is probably
a bicyclic and a-santalene a tricyclic sesquiterpene. These sesquiter-
penes were discovered by Guerbet.1 From the method of their prepara-
tion it is doubtful whether they have been obtained in a state of purity,
so that the characters assigned to them must be accepted with some
reserve, and as probably being only approximate.
a-santalene has, according to Semmler, the following characters :—
„ „ 760mm. 253° „ 254°
/3-santalene has, according to Semmler, the following characters :—
,, ,, „ 760 mm. 261° „ 262°
a-santalene, according to Schimmel & Co., has the following char-
acters :—
Boiling-point at 7 mm. . 118°
„ „ „ 753 mm. . 252°
Specific gravity at 15°. . 0-9132
Optical rotation . . . - 3° 34'
whilst Schimmel's values for /3-santalene are as follows :—
/2-santalene has been synthesised by Semmler and Jonas by heating
-Z-a-phellandrene and isoprene in a sealed tube.
No crystalline hydrochlorides could be obtained from either santalene.
a-Santalene forms a liquid dihydrochloride of optical rotation + 6°, when
dry hydrochloric acid is passed through its ethereal solution. It also
forms a crystalline nitrosochloride melting with decomposition at 122°,
and a nitrol-piperidide melting at 108° to 109°. /2-santalene forms
-corresponding compounds, the dihydrochloride having a rotatory power
+ 8°. It forms, however, two isomeric nitrosochlorides, C15H24NOC1.
They may be separated by fractional crystallisation from alcohol. One
melts at 106°, the other at 152°. The corresponding nitrol-piperidides
melt at 105° and 101° respectively.
By the dehydration of the isomeric santalols contained in sandalwood
oil, Guerbet obtained two sesquiterpenes, which he designates a-isosantalene
and /3-isosantalene, according to the santalol from which they are re-
spectively obtained. He assigns to them the following characters :—
Boiling-point Optical Rotation.
a-isosantalene 255° to 256° + 0-2°
£-isosantalene 259° „ 260° + 6-1°
1
Compt. Rend., 130 (1900), 417, 1324.
ATRACTYLENE.
Gadamer and Amenomiya l have prepared a well-defined sesquiterpene
which they term atractylene, by dehydrating atractylol, a crystalline
sesquiterpene alcohol separated from the oil of Atractylis ovata. It is
an oil with an odour of cedar wood, and is probably bicyclic. It poly-
merises on keeping and has the following characters :—
BoiliDg-point at 10 mm 125° to 126°
It yields a liquid dihydrochloride, from which, by the action of
aniline, hydrochloric acid is split off. The regenerated sesquiterpene,,
however, differs in character from atractylene.
GUAIENE.
By dehydrating guaiol, the sesquiterpene alcohol present in guaiac
wood oil, Wallach and Tuttle 2 obtained a bicyclic sesquiterpene which
they called guaiene. It has been obtained by different methods by other
observers from guaiol, and its characters are recorded as follows :—
Specific gravity about 0-910 at 20°
Refractive index „ 1*5010
Optical rotation from - 40-35° to - 66-11°
Boiling-point 124° to 128° (at 9 to 13 mm.).
No crystalline derivatives have been prepared.
CAPARRAPENE.
3
Tapia has prepared this bicyclic sesquiterpene by distilling capar-
rapiol,the sesquiterpene alcohol present in caparrapi oil, with phosphoric
anhydride. It is a colourless oil having the following characters :—
Specific rotation . - 2-21°
Its glacial acetic acid solution gives a rose-violet coloration on the-
addition of a few drops of sulphuric acid.
CYPRESSENE.
Odell4 has isolated from the wood of Taxodium distichum (the so-
called southern cypress) a sesquiterpene which he terms cypressene. It
„ „ 778 mm 295° „ 300°
It yields, on oxidation with nitric acid, an acid having the odour of
isovaleric acid. It is probably trycyclic.
1 2
Arch, der Pharm., 241 (1903), 33. 4
Annalen, 279 (1894), 396.
*Bull. Soc. Chim., 19 (iii.), 638. Jour. Amer. Chem. Soc., 33, 755..
GURJUNENE.
1
Deussen and Philipp have separated the sesquiterpene fraction of
gurjun balsam oil into two distinct sesquiterpenes which they term
a-gurjunene and /3-gurjunene. The former is a tricyclic and the latter
a bicyclic compound. By repeated fractionation they obtained a-gur-
junene, boiling at about 119° at 12 mm., and which had an optical rota-
tion of not less than - 61°. They found /2-gurjunene to boil at 123° at2
12 mm., and to be slightly dextro-rotatory. Semmler and Spornitz
Tiave, however, prepared /2-gurjunene in a state of purity. By oxidising
"the mixed sesquiterpenesin acetone solution with potassium permanganate
the a-sesquiterpene is readily oxidised, whilst /3-gurjunene is attacked
•only with difficulty. The latter was obtained in a state of purity and
Boiling-poiDt 113-5° to 114° at 7 mm.
Optical rotation more than + 19°
<
When reduced by spongy platinum it yields dihydro-/2-gurjunene,
O15H26, having the following characters :—
Semmler considers /?-gurjunene to resemble the tricyclic sesquiterpene,
•cedrene, so that it is doubtful whether it is bicyclic or tricyclic.
According to Deussen, both a- and /3-gurjunene yield, on oxidation, a
ketone C15H24O, which yields a semicarbazone melting at 234°, and has
When rectified gurjun balsam oil, that is, a mixture of a- and /?-gur-
junene, is saturated in ethereal solution with hydrochloric acid gas, and
the mixture is left standing for two days at room temperature, and the
hydrochloric acid abstracted by heating with sodium acetate, the re-
generated sesquiterpene appears to be a bicyclic compound having the
Boiling-point 129-5° to 132° at 12 mm.
Refractive i n d e x . . . . . . . 1-5057
Deussen and Philipp term this sesquiterpene isogurjunene.
Semmler and Jakubowick 3 have isolated a tricyclic gurjunene from
the oil having the following characters :—
Refractive index , 1-50275
l 2 s
Annaleny 374 (1910), 105. Berichte, 47 (1914), 1029. Ibid., 1141.
COPAENE.
Semmler and Stenzell have isolated a sesquiterpene which they term

«jopaene, from African copaiba oil. It is probably a tricyclic compound.
Its physical characters are as follows :—
„ rotation - 13° 35'
It does not yield a solid nitrosochloride, nor a nitrosite, but it yields
& crystalline hydrochloride, melting at 117° to 118°, which is identical
with cadinene hydrochloride. Semmler considers copaene to have the
iormula—
C-CH(CH3).2 CH
x^\ / \\
HC^
/ \\/ / v\
\\rTT
CH \ JCH-^
rw
^n. \\i'/-( /-ITT
2 /\ ~\j . \_/ji..
\ /\ X '
CH(CH3) CH,
Copaene.
It yields on reduction dihydrocopaene, a compound boiling at 118° to
121° at 12 mm. By oxidation by ozone or by permanganate of potas-
sium it yields a ketonic acid of the formula C15H24O3, which forms a
isemicarbazone melting at 221°. These derivatives characterise copaene
AS a new sesquiterpene. Its characters, however, have only been very
alightly investigated at present.
SESQUICAMPHENE.
Semmler and Eosenberg2 have identified a new sesquiterpene in the
iligher boiling fractions of camphor, oil, to which they have given the
name sesquicamphene. This compound has the following characters :—
Refractive index . . . . . . . . . 1-50058
It is a doubly unsaturated bicyclic sesquiterpene from which no
•crystalline derivatives have, so far, been prepared.
CEDKENE.
Cedrene is the naturally occurring sesquiterpene of cedar wood oil
«of which it forms the principal constituent. It is a tricyclic compound
Jiaving the following characters :—
1 2
Berichte, 47 11914), 2555. Ibid., 46 (1913), 768.
„ 760 mm 262° ,, 263°
The above figures are for the purest specimen of natural cedrene which
has been prepared.
Semmler and Hoffmann l have examined this sesquiterpene in con-
siderable detail. It was dissolved in acetone and oxidised with potassium
permanganate, and the indifferent products thus obtained were separated
by fractional distillation. Cedrene glycol, C15H26O2, was obtained to the
extent of 12 to 15 per cent. ; it crystallises from acetone in prisms, melt-
ing at 160°.
In addition to the glycol, a compound, C15H24O2, was formed, which
Semmler and Hoffman regard as a keto aldehyde, or a diketone, of
specific gravity 1*055.
When cedrene was oxidised with permanganate, there were chiefly
formed products of an acid nature, from which a cedrene keto acid,
C15H24O3, was isolated, which boiled at 215° to 222° (11 mm. press.).
Its semicarbazone melts at 245° and its oxime at 60°.
When cedrene is oxidised by chromic acid, in acetic acid solution,
a mixture of two ketones is obtained, of which the principal is a body to
which the name cedrone has been assigned. Cedrone has the following
characters:—
Boiling-point at 9 mm 147° to 150-5°
Specific gravity 1-0110° at 12-5°
It is a yellowish liquid having a strong odour of cedar wood, and forms
a semicarbazone, melting at 242° to 243°.
By the reduction of cedrone by means of sodium and alcohol, there
is formed dihydro-isocedrol, C15H26O, boiling at 148° to 151° C. under a
pressure of 9*5 mm. When cedrene is heated at 180° to 210° C. with
hydriodic acid and red phosphorus, and the product formed is reduced
by sodium and alcohol, a body C15H26 is obtained, which Semmler de-
scribes by the name dihydro-cedrene. It boils at 116° to 122° C. under
12 mm. pressure; its specific gravity is O9052 at 15° C.
Although the constitution of cedrene is not understood, Semmler and
Hoffmann consider that the following complexes are present in the
various bodies described :—
C C C C
C CH C CHOH C COOH C CO
C—CH3 C(OH) . CH3 CO—CH3 C—CH3
I II III IV
in cedrene (I), cedrene-glycol (II), the ketonic acid (III), and cedrone (IV).
Semmler and Eisse2 have studied the oxidation of cedrene by means
of ozone. They obtained the keto-acid, C15H24O3, which on further oxida-
tion either by means of bromine or nitric acid yields a dicarboxylic acid,
1 2
Berichte, 40 (1907), 3511. Ibid., 45 (1912), 355.
C14H2204, melting at 182'5. The formation of this cedrene-dicarboxylic
acid serves for the detection of cedrene in essential oils. It is sufficient
if the fraction to be examined be oxidised by permanganate or ozone, and
the acid obtained (boiling-point at 10 mm. - 200° to 220° C.) be then
oxidised further, either by an alkaline solution of bromine or by nitric
acid. Even very small proportions of cedrene have definitely led to the
obtaining of this acid melting at 182'5° C.
Semmler and Mayer 1 have isolated from the oil of cedar wood an
alcohol, pseudocedrol. There also exists in the oil a sesquiterpene
alcohol, cedrol. The latter, on dehydration yields cedrene, which is-
probably identical with, or very closely allied to, natural cedrene, whilst,
pseudocedrol yields a mixture, when heated in a sealed tube, of cedrene
and dihydrocedrene. Dihydrocedrene is a colourless oil having the
By reducing natural cedrene with hydrogen in the presence of spongy
platinum, a dihydrocedrene is obtained which has the following char-

Specific gravity at 20 0 9201
No crystalline halogen derivatives of cedrene have been prepared, only
liquid compounds being obtained when the sesquiterpene is treated by
the usual processes.
CLOVENE.
When caryophyllene alcohol is dehydrated by means of zinc chloride
or phosphorus pentoxide, a hydrocarbon results, which does not appear
to be identical with any of the sesquiterpenes described under the name
caryophyllene. It has therefore been named " clovene ". Clovene has
Molecular refraction . . . . . . . . 64'77
VETIVENE.
A sesquiterpene was isolated from oil of vetivert by Genvresse and
Langlois,2 and was named by them vetivene. This body, or mixture of
bodies, has, more recently, been examined by Semmler, Bisse, and
Schroeter.3 There is no evidence, however, that the sesquiterpenes de-
scribed as vetivene were obtained in a state of purity. From a German
distilled oil they prepared a tricyclic "vetivene" and a bicyclic vetivene,
1 2
Berichte, 45 (1912), 1384. Comptes rend., 135, 1059.
3
Berichte, 45, 2347
VOL. II. 7
Tricyclic Bicyclic
Vetivene. Vetivene.
Boiling-point at 16 mm. . . . 123° to U0° 137° to 140°
Specific gravity at 20° . . . . 0-9355 0-9321
The sesquiterpenes obtained from an oil distilled in Bourbon had the

A. B.
Boiling point at 9 mm. . . . 124° to 127° 128° to 132°
Specific gravity at 20° . . . . 0-9299 0-9322
Optical rotation - 2° - 12° 36'
The former is considered to contain mostly tricyclic vetivene, and the

latter bicyclic vetivene. The great differences in the characters of these
sesquiterpenes are strong evidence of their impurity, and the above
characters must be accepted with considerable reserve.
Two isomeric alcohols, known as vetivenol, also exist in the oil.
By treatment with phosphorus pentachloride this mixture of
alcohols is converted into a chloride, or mixture of chlorides, which
on reduction yields an artificial vetivene, having the following char-
acters :—
In another experiment the resulting sesquiterpene, after treatment

with permanganate of potassium, had a dextro-rotation, + 6° 12'.
SUGININE.
The wood of Cryptomeria japonica, a Japanese cedar tree, yields an
oil which contains a sesquiterpene to which the name suginene has been
assigned. It has the following characters :—
„ rotation . . . - 10° 34'
It yields a liquid hydrobromide of specific gravity 0'988 and specific
rotation - 11° 15'.
SESQUICITRONELLENE.
Semmler and Spornitz l have isolated a sesquiterpene from Java
citronella oil, which they have named sesquicitronellene. It has the
•Optical rotation + 0° 36'
, 4025.
CALAMENE.
l
Semmler and Spornitz have isolated a sesquiterpene from the oil of
Acorus calamus, which they have termed calamene. This body has the
Boiling-point at 10-5 mm 123° to 126°
20°
Specific gravity at . 0-9224
iy
HEBABOLENE.
This body is apparently a tricyclic sesquiterpene. It was isolated
from essential oil of Herabol myrrh by Von Friedrichs,'2 who found it to
Boiling-point at 16 mm. . 130° to 136°
Specific gravity at 20° . . 0'943
Optical rotation . . -14° 12'
Refractive index . . . 1*5125
Molecular refraction . . 64-98
It yields a dihydrochloride melting at 98° to 99°.
ABOMADENDBENE.
Baker and Smith 3 have isolated from a number of eucalyptus oils,
* sesquiterpene to which they have given the name aromadendrene.
This compound was separated from the oil of eucalyptus nova-angelica
in the dextrorotatory form, and from the oil of eucalyptus bailey ana
in the laevorotatory form. The two specimens had the following
characters:—
1. 2.
„ ,, at 10 mm. 124° to 125° 123° to 125°
Optical rotation + 4-7° - 3-7°
Refractive index at 20° 1-4964 1-4964.
It yields a characteristic reaction with bromine. If a few drops are
.dissolved in 3 c.c. of glacial acetic acid and a little bromine vapour
allowed to pass down the tube, a fine crimson colour forms which
rapidly extends to the whole of the liquid and soon changes to violet and
then to indigo blue; with phosphoric acid, the acetic acid solution gives
a rose madder colour at the junction of the liquids, and when the liquids
are mixed, the colour changes to crimson and then slowly to violet.
Baker and Smith consider that the sesquiterpene contains one double
linkage. Semmler considers that it is a mixture of at least two bodies,
one a bicyclic and the other a tricyclic sesquiterpene.
LlBBOCEDBENE.
A sesquiterpene has been isolated from the oil of the leaves and twigs
of the Californian incense cedar tree, Li!,rocedrus decurrens, which has
been named librocedrene. it has the following characters :—
2
*Berichte, 46 (1913), 3700. Arch, der Pharm., 245 (1907), 208.
B
A Research on the Eucalypts, 2nd edition, 416.
Boiling-point . 270° (approximate)
FERULENE.
Semmler, Jones, and Koenisch1 have isolated a sesquiterpene from
the oil of Peucedanum ammoniaciim, which they have termed ferulene.
This substance has the following characters :—
Boiling point at 10 mm. 126° to 128°
It is possible that it is not an individual compound, but a mixture of
two bodies.
COSTENE AND ISOCOSTENE.
Semmler and Feldstein 2 have isolated three isomeric sesquiterpenes

from the oil of costus root. These have been named a-costene, /2-costene,
and isocostene. They have the following characters:—
a-costene. #-costene. Isocostene.
Boiling-point 122° to 126° at 12 mm. 144° to 149° at 19 mm. 130° to 135° at 12 mm.
Specific gravity . 0-9014 at 21° 0-8728 at 22° 0-906 at 21°
Optical rotation . - 12° + 6° 4- 31°
i
ELEMENE.
Elemene is a monocyclic sesquiterpene resulting from the reduction
of elemol, the sesquiterpene alcohol present in Manila elemi oil.3 It has.
It is possibly a mixture of more than one sesquiterpene.
OPOPONAX SESQUITERPENE.
The fraction of opoponax oil boiling at 135° to 137° in vacuo contains
a sesquiterpene, which has been examined by Schimmel & Co.4 On
fractionation at ordinary pressure, it boiled at about 260° to 270°, and in
this impure condition was dissolved in ether and saturated with hydro-
chloric acid gas. The crystalline hydrochloride which resulted melted
at 80°, and was optically inactive. It has the composition C15H24. 3HC1.
The sesquiterpene is apparently one containing three double linkages.
When regenerated from the hydrochloride by boiling with sodium acetate
in glacial acetic acid, it has the following characters:—
1 2
Berichte, 50, 1823. Ibid., 47(1914), 2687.
3 4
Ibid., 49 (1916), 794. Report, October, 1904,
PATCHOULENE.
This sesquiterpene has not been found naturally. It is formed by the
dehydration of the so-called patchouli camphor, a sesquiterpene alcohol,
C16H260, found in oil of patchouli. It has the following characters:—
Von Soden and Eojahn l have isolated two sesquiterpenes from
patchouli oil, which have the following characters :—
1. 2.
Specific gravity 0-9335 0*930
Optical rotation -58° 45' +0° 45'
MAALI SESQUITERPENE.
Schimmel & Co. 2 have isolated a sesquiterpene alcohol from Samoan
resin, known as Maali resin, and by dehydrating it by means of formic
acid have obtained a sesquiterpene which has not been named other
than as Maali sesquiterpene. It has the following characters :—
Refractive index . . . ' 1-52252
Boiling-point 271°
ClTEONELLA SESQUITERPENE.
Ceylon citronella oil contains an olefinic sesquiterpene having the

Optical rotation +1° 28'
Boiling-point . . . . . . . 280°, with decomposition
No crystalline derivatives have been prepared.
CANNABIS SESQUITERPENE.
A sesquiterpene has been isolated from the essential oil of Cannabis
Indica. This may fairly be considered a definite body, as it has been
isolated by many different observers and described by them at different
times. Valenta3 first mentions it. Vignolo 4 describes it as a mobile
liquid boiling at 256°, of specific gravity *897 at 15°, and slightly laevo-
rotatory. Wood, Spivey, and Easterfield5 give the boiling-point as 258°
to 259°, the specific gravity as '898 at 18°, and the rotation as - 8*6°.
1 2
Berichte, 37 (1904), 3353. Report, November, 1908, 137.
3 4
5
Gazzetta, 1880, 540. Ibid, 1895, HO.
Jour. Chem. Soc., 1896, 543.
The name cannibene may be applied to this hydrocarbon. Personne first
gave this name to what is now known to be an impure compound obtained
from the oil.
GONOSTYLENE.
This sesquiterpene is obtained by the dehydration of the sesquiterpene

alcohol gonostylol. It has the following characters :—
„ rotation + 40° (in alcohol)
Molecular refraction . . . . . . . 66*7
EUDESMENE.
Eudesmene is a sesquiterpene obtained by the dehydration of eudesmol,

the sesquiterpene alcohol found by Baker and Smith in several species of
eucalyptus oil. It has the following characters :—
„ rotation +49°
It forms a dihydrochloride melting at 79° to 80°. The sesquiterpene re-
generated from the dihydrochloride has slightly different characters, so
that a molecular rearrangement is probable; and the regenerated " eudes-
mene" may contain another sesquiterpene. Its characters are as
follows:—
,, rotation -f 54° 6'
On reduction it yields tetrahydro-eudesmene, C15H30, having the follow-
ing characters :—
„ rotation 4-10° 12'
CHINESE PINE SESQUITERPENE.

The essential oil from the oleo-resin of Chinese turpentine l (botanical
origin unknown) contains a tricyclic sesquiterpene, having the following
characters:—
It forms a monohydrochloride melting at 58° to 59°.
1
Jour. Chem. Ind. Tokyo, 23, 45.
LONGIFOLENE.
Longifolene in its dextrorotatory form is a sesquiterpene isolated by

Simonsen1 from Indian turpentine oil from Pinus longifolia. It is a
colourless viscous liquid having the following characters :—
„ „ 36 mm 150° to 151°
30°
Specific gravity at —0 0-9284
It yields a crystalline hydrochloride melting at 59° to 60°; a hydro-
bromide melting at 69° to 70°, and a hydriodide melting at 71°.
AZULENE.
This hydrocarbon is not a sesquiterpene, but may be conveniently
dealt with here. It has been thoroughly investigated by Sherndal.2 In
many essential oils, especially those containing sesquiterpenes, a blue
coloration is observed, which becomes concentrated in the higher boiling
fractions. This is especially marked in oil of chamomiles. The body
responsible for this blue colour was separated by taking advantage of
its ready solubility in mineral acids. A very blue fraction wras shaken
out with one-fifth of its weight of 63 per cent, sulphuric acid. After
standing the acid layer was separated, diluted with water, and shaken
with petroleum ether until no more colour was extracted. The dark
blue petroleum was then extracted with phosphoric acid, 85 per cent.
The acid extract, diluted with water, was shaken with ether. On
evaporating the solvent, azulene was left. It was further purified by
steam distillation, and, finally, by distilling in vacuo. It is a viscid
liquid, with a weak phenolic odour, suggestive of thymol. It is a hydro-
carbon, having the formula C15H18. Its specific gravity is 0*9738 at 25°.
Under normal pressure the boiling-point is 295° to 300° C. with decom-
position ; under 25 mm. pressure azulene distils between 185° and 195° C.,
leaving a brown residue.
When azulene is heated with sulphuric acid and acetic anhydride a
sulphonic acid, soluble in water, is formed. This acid forms a fine violet
sodium salt. This sodium salt is not very stable ; when kept for three
months it decomposes into a mixture of oil and resin. Its aqueous solu-
tion gives blue precipitates with calcium and barium salts.
Sherndal considers the formation of a crystalline picrate, melting
at 122°, the best method of identifying azulene. On reduction azulene
yields a dihydro-sesquiterpene, C15H20, and in Sherndal's opinion, it is
closely related to a-gurjunene in constitution.
APLOTAXENE.
3
Semmler and Feldstein have isolated from the oil of costus root a
hydrocarbon of the formula C17H28, to which they have given the name
aplotaxene. Its characters are approximately as follows :—
1
Jour.Chem. Soc. 1920, 570.
2
Jour.
Amer. Chem. Soc., 37 (1915), 167, 1537.
3
Berichte, 47 (1914), 2687.
Refi active index 1-4830
Its low specific gravity indicates that it is an open-chain compound, and

from its easy reduction by sodium and alcohol, into dihydroaplotaxene,
C17H30, and by hydrogen and platinum black into normal heptadecane
CI7H20, it is evident that aplotaxene is a tetraolefinic normal chain hydro-
carbon.
3. ALCOHOLS.
Bodies of an alcholic nature play a very important part in both
natural and synthetic perfumery. They are found to a very large ex-
tent in essential oils, both in the free state and also in the form of esters.
Some that have not so far been recognised as constituents of essential
oils, have been found to be so highly odorous, and so useful as perfume
materials, that they are prepared artificially, and enter largely into the
composition of the synthetic perfumes which to-day are indispensable to
the manufacturer of perfumes. It is obvious that those alcohols which
are soluble in water, such as methyl and ethyl alcohols, although they
may be original constituents of some essential oils, are removed by the
ordinary distillation processes, so that they do not, in fact, appear in the
êssential oil as found in commerce.
The higher homologues of the methane series of alcohols are found,
•sometimes in the merest traces only, in certain essential oils, but their
value in perfumery has been so well established that a number of them
are now manufactured as " synthetics ".
The alcohols of the geraniol series and those of the closed-chain series
are practically insoluble in water, and, where they occur as natural
constituents of essential oils, are present in the distilled oil.
E. Emmet Eeid l describes a method of separating alcohols from
a mixture which may contain primary, secondary, and tertiary alcohols.
It consists in esterifying with phthalic anhydride, and converting the
acid ester into the sodium salt, which reacts with ^-nitrobenzyl bromide,
forming an ester which serves for identification. Primary alcohols com-
bine with phthalic anhydride below 100°, whilst secondary react rapidly
only above 120°. An excess of the alcohol is heated for one hour with
1 gram of phthalic anhydride (a sealed tube being used for the lower
alcohols), and the product is transferred to a separating funnel contain-
ing 10 c.c. of water. About 15 c.c. of ether and 5 c.c. of normal solution
of caustic soda are added, and the whole shaken for five minutes. The
water is drawn off and the ether solution washed with a little water. The
water solution is again extracted with ether. The aqueous solution is
evaporated to dryness, and the sodium salt is transferred to a 100 c.c.
flask with 5 c.c. of water and 10 c.c. of 95 per cent, alcohol. To this is
added 1 gram of j?-nitrobenzyl bromide, and,the mixture is boiled for one
hour on a steam bath under a reflux condenser. The product is then
obtained by evaporation of the liquid, and recrystallised from 63 per cent,
alcohol. The following are the results obtained :—
1
Jour. Amcr. Ghent. Soc. (1917), 1249 ; Krogh, P. and O.E.R.
Melting-point of No of c.c. of
Alcohol. ^-nitrobenzyl Strength oi Alcohol Required
Phthalate. Alcohol Solvent. for about 1 *3
Grams.
Degrees. Per Cent.

Methyl 105 63 9
Ethyl . 80 63 9
Propyl . 53 63 27
Isopropyl 74 63 30
Allyl . 61-5 71 17
N-butyl 62 76 40
N-octyl 41 70 30
Benzyl 83 76 28
"Ehenylethyl 84-3 76 21
Borneol 100 80 20
Isoborneol 87 — —
Isobutyl, isoamyl, and cinnamic alcohols, menthol and geraniol gave

j)-nitrobenzyl phthalates which were oily liquids and could not be
crystallised.
METHYL ALCOHOL.
This alcohol, the lowest of the paraffin series, is found in the dis-
tillation waters of a number of essential oils, being soluble in all pro-
portions in water. It does not therefore form a constituent of essential
oils in the form in which they are found in commerce. In the form of
esters, methyl alcohol is found as a constituent of a number of essential
oils, such as, for example, oil of wintergreen, which consists almost en-
tirely of methyl salicylate. Methyl alcohol, CH3OH, is a liquid of specific
gravity 0'810, boiling at 64°.
ETHYL ALCOHOL.
Ethyl alcohol, C2H5OH, is also a natural constituent of a number
of essential oils, but being, like methyl alcohol, soluble in water in
all proportions, it is washed away in the distillation waters. It is an
inflammable liquid of specific gravity 0'794, and boiling at 78°.
ISOBUTYL ALCOHOL.
This alcohol, of the formula (CH3)2CH . CH2OH, is found in the
free state in the distillation water of the oil of Eucalyptus Amygdalina.
It boils at 108*5°, and has a specific gravity 0*8003. It yields a phenyl-
urethane melting at 80°.
ISOAMYL ALCOHOL.
Isoamyl alcohol, (CH3)2. CH . CH2CH2OH, has been found in the free
state in various eucalyptus oils, and also in geranium, lavender, and
peppermint oils. It boils at 131° and yields a phenyl-urethane, melting
at 53°.
HEXYL ALCOHOLS.
Normal hexyl alcohol, CH 3 . CH 2 . CH 2 . CH 2 . CH 2 . CH2OH, is found,
principally in the form of esters, in a few essential oils, especially the oil
of Heracleum giganteum. It is a liquid of specific gravity 0*824, and'
boils at 157°.
An isohexyl alcohol, (C2H5) (CH3) . CH . CH2 . CH2 . OH (methyl-ethyl -
propyl alcohol), is found in the form of esters in Roman chamomile oil.
This body is an oil of specific gravity O829, optical rotation [a]D =
+ 8-2°, and boiling at 154°.
HEPTYL ALCOHOL.
One of the heptyl alcohols, methyl-amyl carbinol, of the formula
CH
)>CHOH, has been isolated from oil of cloves. It has a
CH3(CH2)/
specific gravity 0*8244, and boils at 157° to 158°. On oxidation by
chromic acid, it yields methyl-amyl-ketone, which gives a semicarbazone,
melting at 122° to 123°.
ETHYL- AMYL CARBINOL.
Ethyl-amyl carbinol, ^>CHOH, one of the isomeric octyi'

CH3(CH2)4/
alcohols, has been found as a constituent of Japanese peppermint oil.
It has been prepared synthetically by Pickard and Kenyon 1 by passing
the vapour of a mixture of 145 grams of normal caproic acid and 180
grams of propionic acid through a tube charged with thorium oxide
heated to 400°. By this means they obtained 124 grams of ethyl-amyl-
ketone. This was reduced in a solution of moist ether with sodium, and
the carbinol resulted. It has the following characters : —
20°
Specific gravity at -^ ....... 0-8247
»» »» » 16 mm. 76°
Optical rotation . + 6-79°
Melting-point of phthalate 66° to 68°
Boiling-point of the ketone 165° „ 166°
Melting-point of semicarbazone 112°
HIGHER ALIPHATIC ALCOHOLS.

The higher aliphatic alcohols, from octyl alcohol upwards, have-
recently been introduced as perfume materials with considerable success.
Only one or two of them, such as nonyl and undecylenic alcohols, have
so far been detected as natural constituents of essential oils, but other
members of the series are prepared artificially, and are employed in
minute quantities in the preparation of perfumes with characteristic;
fruity bouquets. These alcohols are greatly diminished in perfume value
by traces of impurities. According to H. J. Prins,2 the first interesting
member of the series is octyl alcohol; it has a very sweet, rose-like
odour, and is especially suitable for giving a rose perfume that peculiar
sweet smell which distinguishes a rose from a rose perfume. This-
feature of the aliphatic alcohols diminishes in the series from C8 to 012»
1 2
Jour. Chem. Soc., 103 (1913), 1923. P. and E.O.E., 1917, 68.
Laurinic or duodecylic alcohol has a soft and not very strong but
delicate odour. These alcohols can be used in much greater quantities
than the corresponding aldehydes. The latter are only admissible in a
perfume base to the extent of from 1 to 2 per cent. The alcohols may
be used in quantities up to 5 per cent. Laurinic alcohol is very suitable
as a basis for perfumes of the lily type, owing to its delicate odour ; it
has, moreover, very powerful fixative properties.
Prins (loc. cit.) considers that the melting and boiling-points of these
alcohols are amongst the best criteria of their purity. He gives the
following values for the more important of them :—
Meltiug-poiut. Boiling-point
at 13 mm.
Octyl alcohol . - 22° to - 21° 95°
Nonyl - 11° „ - 10° 102°
Decyl - 10° ,, - 8° 110°
Duodecyl alcohol 13° ,, 15° 142°
Undecylenic ,, - 12° „ - 11° 128°
It is strange that only the normal alcohols amongst the higher

aliphatic alcohols are of any value as perfumes, the iso-alcohols being
useless.
The following are the only members of the series which have, so far,
been utilised as perfume materials :—
Octyl Alcohol.—this is the primary normal alcohol of the formula
CH3(CH2)6CH2OH. It has an odour recalling that of opoponax, and is
useful in the blending of perfumes of this type. It boils at 196° to 197°,
and has a specific gravity 0*8278. It yields octyl aldehyde on oxidation,
whose naphtho-cinchoninic acid compound melts at 234°.
Nonyl Alcohol.—This is the normal alcohol of the formula
CH3(CH2)7CH2OH.
This alcohol has a marked rose odour, resembling that of citronellol,
and has also a suggestion of orange in it. It can be extracted from
orange oil by saponifying the high boiling constituents and extracting
the alcohol in the form of its phthalic acid compound. It has a specific
gravity 0*840, and refractive index 1-43582. It boils at 98° to 101° at
12 mm. It can be identified by its phenyl-urethane, melting at 62° to 64°.
There is a secondary nonyl alcohol, methyl-heptyl carbinol, which exists
in certain essential oils. It is a liquid of specific gravity 0*8273, and
boils at 198° to 200°. It is of little use, however, for perfumery purposes.
Decyl Alcohol.—This alcohol, of the formula CH3(CH2)8CH2OH, is
often considered to be the most useful of this series. It boils at 110° at
13 mm., and melts at - 10°. Its odour is hardly describable, and al-
though very expensive it is used in such small amounts as to render its cost
but small. It is very useful in modifying the bouquet of numerous flower
odours, and has been well described by an American perfumer as ".an
alcohol which the up-to-date manufacturer uses to deceive the copier of
odours".
Undecylic Alcohol.—This alcohol, CH3(CH2)9CH2OH, may be de-
scribed as of the same general characters as decylic alcohol, useful for
the same purpose, but giving a slightly different modification to the
bouquets. It occurs in Algerian Eue oil and in oil of Trawas. It boils
at 231° to 233°.
Undecylenic Alcohol.—This alcohol is an unsaturated 11-carbon
alcohol, and therefore not a homologue of ethyl alcohol. It is, however,
so closely related to the series, and so similar to the two last described,
that its inclusion here is convenient. It boils at 128° at 13 mm. and
melts at - 12°. Its constitution is CH 2 : CH(CH2)8CH2OH. It is being
used to a fairly considerable extent by the more skilful perfumers in the
same way as decyl alcohol.
Duodecylic Alcohol.—This alcohol has the formula CH3(CH2)10CH2OH,
and is used exactly as are the last three described bodies. It is a liquid
boiling at 142° at 13 mm. It 'crystallises at low temperatures, and melts
.at 14°.
The above series of alcohols are exceedingly difficult to manufacture,
hence their expense. The general method of their preparation would
theoretically be by distilling the calcium salts of the corresponding fatty
acid with calcium formate, in vacuo. This would yield the correspond-
ing aldehyde, which on reduction would yield the corresponding alcohol.
In practice, however, many technical difficulties arise, and special pro-
cesses have to be used which are kept carefully as trade secrets.
The next group of alcoholic bodies to be studied are those which,
although open-chainl alcohols, show considerable tendency to easily pass
into closed-chain compounds, so that they occupy a definite position of
their own, midway between the ordinary aliphatic series and the closed-
^chain series. The principal members of this important group are
geraniol, nerol, linalol, and citronellol, together with the so-called ali-
phatic sesquiterpene alcohols, farnesol and nerolidol.
GERANIOL.
Geraniol, C10H17OH, is a constituent of many essential oils, both in
the free state and in the form of esters. It is present to a very large
extent in palmarosa oil, ginger-grass oil, and citronella oil, principally in
the free state, and in geranium oil, to some extent in the free state, but
principally in the form of esters. It is also an important constituent of
otto of rose, and is present in numerous other oils belonging to the most
distantly related groups.
This alcohol is of the highest importance in artificial perfumery, and
is manufactured on a very large scale from either palmarosa or citronella
oil. It can be separated from essential oils containing it by intimately
mixing them with an equal weight of dry powdered calcium chloride,
and keeping the mixture in a desiccator at - 4° for 16 hours. The soft
mass is then rubbed down with dry petroleum ether, and the liquid por-
tion removed by means of a suction filter. The calcium chloride com-
pound of geraniol is then treated with water, which decomposes the
compound, and the oil purified by fractional distillation. The geraniol
comes over between 228° and 230°. In the case of palmarosa oil the
geraniol can be prepared in a state of fair purity by first saponifying the
oil and then fractionally distilling it. It can be prepared in a state of
absolute purity by treating it with sodium and then with dry ether and
phthalic anhydride. The resulting geraniol sodium phthalate is hy-
drolysed by alcoholic potash, and the pure geraniol precipitated by water.
Geraniol is a colourless liquid of sweet odour, recalling that of the
rose, principally, and to a lesser extent the pelargonium. It is an opeji-
^chain alcohol, having one of the two following constitutional formulae :-4-
. CH 2 . CH2CH2C(CH3) : CH . CH2OH
or
\C : CH . CH,. CH,C(CH3): CH . CH,OH
H3C/
Pure geraniol has the following physical characters:—
Specific gravity at 15° 0'880 to 0'883
Refractive index at 20° 1-4766 to 1-4786
Boiling-point at 760 mm 228° „ 230°
At 10 mm. it boils at 110° to 111°, and at 18 mm. at 121°. This,
alcohol is, of course, an essential constituent of synthetic otto of rose
and all odours of a similar type.
The following are the most satisfactory methods of recognising it..
It yields, as above described, a characteristic compound with calcium
chloride, from which the geraniol may be regenerated and examined as
to its physical characters. It also yields a characteristic diphenylure-
thane, (C(.H5)2N . COOC10H17, melting sharply at 82°. It may be pre-
pared as follows: 1 gram of the oil, 1*5 gram of diphenylcarbamine
chloride and 1-3 gram of pyridine are heated in a water-bath for two
hours. The reaction product is submitted to a current of steam to*
remove unaltered products, and the solid residue recrystallised from
alcohol. If citronellol is present as well as geraniol, it is necessary to
recrystallise several times before the product is pure and melts at 82°.
The naphthyl-urethane is also characteristic and easily prepared. Equi-
molecular proportions of naphthyl-isocyanide and geraniol are allowed
to stand for twelve hours, when the mass will be found to be solid.
Eecrystallised from diluted methyl alcohol, the product melts at 47° to
48°. One of the most characteristic derivatives for identification pur-
poses is geranyl-phthalate of silver. This salt is prepared as follows : 90
grams of phthalic anhydride and 90 c.c. of geraniol are heated in a
water-bath for forty-five minutes; 100 c.c. of boiling water are then
added. The whole is well shaken and the water separated, and the
oil washed five or six times in the same manner. 100 c.c. of water
and 35 c.c. of ammonia are then added. Neutral compounds are then
extracted with ether. After separation of the ether, the liquid is diluted
with 200 c.c. of alcohol, and then 175 c.c. of a normal solution of nitrate
of silver added. A white, crystalline precipitate rapidly settles out.
This is washed with alcohol and then with ether, and then dried in
vacuo. The resulting crystals, recrystallised from a mixture of alcohol
and benzene, melt at 133°. The salt has the formula C6H4(COOC10tl17)
(COOAg).
The identification of geraniol can be confirmed by its conversion
into citral, C10H16O, its aldehyde, which has a very characteristic odour
and yields well-defined crystalline derivatives. Five parts of the alcohol
fraction are shaken with 2'5 parts of chromic acid and four parts of con-
centrated sulphuric acid dissolved in 100 parts of water. The mixture
is warmed in the water-bath for a few minutes, when crude citral
separates on the surface of the liquid. This is purified by steam
distillation and conversion into its sulphonic acid compound in the
usual manner and then yields characteristic crystalline compounds,
which are described under " citral".
Geraniol is converted into the isomeric alcohol, linalol, by heat, and
both alcohols yield the same chloride when treated with dry hydrochloric
acid gas. Dupont and Labaune first prepared this chloride,: which they
considered was linalyl chloride, but Forster and Cardwell have shown
that it is geranyl chloride.
These chemists prepared it by acting upon either geraniol or linalol
with thionyl chloride in the presence of pyridine. It is a colourless
liquid, having the following characters :—
Boiling-point at 14 mm 103°
By heating geranyl chloride with sodium alcoholate geranyl ethyl
ethe^r was obtained. This body, C10H17. O . C2H5, is an oil with a faint
rose odour, having the following characters :—
Specific gravity at 25° 0'8(>4
Boiling-point a t 1 9 m m . . . . . . . . . 115°
Refractive iodex 1-4662
Prileshajeff 2 has prepared the oxide and dioxide of geraniol by direct
oxidation by means of hydrated benzoyl peroxide. By using the
equivalent of 9 grams of active oxygen on 100 grams of geraniol, geraniol
monoxide was formed, which has the following constitution :—
O
CH,— C - CH— CH2— CHo— C =CH— CH9OH

| - - |
CH3 CH3
The yield was 55 per cent. It is a viscous mass with feeble odour,
and having the following characters : —
Boiling-point at 25 mm ........ 157° to 158°
Specific gravity at 16° ....... 0-9610
Refractive index at 16C ....... 1-4681
When heated with ac tic anhydride at 150° C., this oxide yields the
•ester C10H1703(COCH3)3, boiling at 208° C., under 25 mm. pressure.
Geraniol dioxide —
O O
/ \ / \
CH3— C - CH—CH2— CH2—C -- CH— CH2OH
is obtained when 50 grams of geraniol are oxidised by means of 8

grams of active oxygen. The dioxide occurs as a colourless mobile
liquid having the following characters :—
Specific gravity at 16° ..... . . 1-0472
Refractive index at 16° ....... 1-4653
l
Journ. Chem. Soc., iQ3, 1338.
Jour. Soc. Chem. Phys. Buss., 44, 613.
Geraniol, as will be seen below, is the alcohol corresponding to one
of the stereoisomeric forms of citral, nerol being the isomeric alcohol,
corresponding with the other stereoisomeric citral. Semmler l and
Schossberjer have recently succeeded in enolising citral, that is, causing
.a migration of the double linkage towards a CH2 group, and from the
enolic form of citral thus obtained preparing an isomeric alcohol which
he terms isogeraniol.
When citral is heated with acetic anhydride, the migration of the
double bond takes place towards the CH2 group and the acetic ester of
.awo/-citral is formed. This acetate is resinified by all saponifying agents
and therefore does not regenerate citral. By reducing it with sodium
amalgam and methyl alcohol slightly acidified with acetic acid, an
alcohol was obtained which is not identical with geraniol nor with nerol,
and which has therefore been named isogeraniol.
This alcohol possesses a very pleasant odour of roses, and after puri-
fication ha's the following characters :—
The passage from citral to isogeraniol through 0w)Z-citral may be re-
presented by the following formulae :—
C C
Ai /^TT
O±10 CH2
OHC, (HO)HC (HO)H2C \CH,
HC HC ,CH H2C CH
V
CH3 CH3 CH3
Citral. Enolic form I. Isogeraniol I.
or possibly—
, x,
\j
CH9
(HO)HC \CH2 (HO)H2C CH2
and yields
HC H9C •CH2
CH2 CH2
Enolic form II. Isogeraniol II.
1
Berichte, 44, 991.
and probably passing in a primary stage through a body of the con-
stitution : —
C
CH
(HO)HC
CH3
Isogeraniol yields isogeraniol-diphenylurethane, C10H17O . CON(C6H5)2,.
melting at 73° C., free from geranyl- and nerylurethanes. By the saporii-
fication of this derivative isogeraniol is again liberated.
The properties of isogeraniol, geraniol, and nerol are compared
below:—
Geraniol. Nerol. Isogeraniol.
Boiling-point . 104° to 108° C. 111° C. 102° to 103° C.

(8-5 mm. pressure) (llmm. pressure) (9 mm. pressure)
Specific gravity 0-882 at 15° C. 0-881 at 15° C. 0-879 at 20° C.
Melting-point of the di
phenylurethane . 82-5° C. 52° to 53° C. 73° C.
Melting-point of the tetra
bromide 70° to 71° C. 118° to 119° C. oily
The tetrabromide and the phenylurethane of isogeraniol have so far

only been obtained in the oily condition.
NEKOL.
Nerol is an alcohol, isomeric with geraniol, of the formula C10H180.
It was discovered by Hesse and Zeitschel in neroli and petit-grain oils,
by freeing the oil as far as possible from geraniol and then preparing
diphenylurethanes of the residuary mixed alcohols. By fractional
crystallisation from a mixture of methyl alcohol and petroleum ether, the
nerol compound can be obtained in a state of purity, and the alcohol is.
obtained by saponification in the usual manner. Nerol has the following
characters :—
The diphenylurethane melts at 52° to 53° (that of geraniol melts at 81°)
and the tetrabromide at 118° to 119°. Nerol is a stereoisomer of geraniol,
related to it as shown by the appended formulae, and their corresponding
aldehydes are probably a-citral (= geraniol) and /3-citral (= neral):— L
1
But see also under citral for alternative constitutions.
Geraniol.
CH3 . C . CH.,. CH,. CH : C(CH3),
II
CH,(OH)C . H
a- Citral.
CH 3 . C . CH«,. CH.,. CH : C(CH3),
II
CHO . C . H
Nerol.
CH,. C . CH 2 . CH 2 . CH : C(CH3)2
HC : CH2OH
0-Citral.
CH 3 . C . CH2 . CH., . CH : C(CH3)2
II
HC. CHO
Considerable difference of opinion has been expressed as to the re-

lationships of nerol and geraniol, and Soden and Treff have considered
the isomerism of a structural nature. The question of this isomerism
has, however, been definitely solved by Blumann and Zeitschel,1 who-
have applied the degradation-oxidation method of Tiemann and Semmler '2
to both geraniol and nerol. If the two bodies are stereoisomers, there
should be obtained under identical experimental conditions, from both
compounds, the same products of degradation in the same proportions,,
according to the following diagrammatic equation :—
CH3
CHa
}=CH—CH,—CH2—C =LCH—CH2OH=
OH.,
Geraniol or Nerol.
CH,
CH3
>CO + HO—CO—CH,—CH,—CO + HO—CO—CO—OH
CH,
Acetone. Laevulinic acid. Oxalic acid.
Blumann and Zeitschel have obtained these degradation products in

practically equal amounts from both geraniol and nerol, so that there no
longer exists the slightest doubt as to the constitution of nerol.
The nerol used for these experiments was extracted from the oil of
Helichrysum angustifolium. Its characters were :—
Boiling-point . . . . 225° to 226f
Optical rotation ± 0°
Coeff. of sapon. of the acetylated produc ; 286
Tetrabromide, melting-point . 118° to 119° C:
DiphenyJurethane, melting-point 52° „ 58° C.
1
Berichte, 44, 2590. *Ibid., 28, 2130.
VOL. II.
THE CHEMISTKY OF ESSENTIAL OILS
The geraniol, purified by means of calcium chloride, had the follow-
ing characters :—
Boiling-point . . . . 230°
Tetrabromide, melting-point . 70° to 71° C.
Diphenyluretnane, melting-point . 82° C.
In regard to the crystallisation of these two derivatives of nerol and

geraniol, Blumann and Zeitschel have made a curious observation: one
of the bodies corresponding to one of the modifications of the two
alcohols is readily obtained in the solid state, whilst the other crystallises
with difficulty. Thus, the tetrabromide of nerol solidifies fairly quickly
whilst the tetrabromide of geraniol remains oily for a very long time;
in the case of the diphenylurethanes these conditions are reversed.
However, nerol and geraniol yield on oxidation exactly the same pro-
ducts.
The identity of the two alcohols from a chemical point of view is
shown by the following results, obtained from 25 grams of each of the
two bodies :—
Geraniol. Nerol.
Acetone, identified by its

£>-bromophenylhydrazone m.p. 94° to 95° C. m.p. 94° to 95° C.
Lsevulinic acid, identified by its 18 grams = 54 per cent, 18-5 grams = 55-5 per cent,
of theoretical of theoretical
phenylhydrazone . . . . m.p. 108° C. m.p. 108° C.
A-isonitrosovaleric acid m.p. 95° C. m.p. 95° C.
Lsevulinic acid regenerated m.p. 32° to 33° C. m.p. 28° to 32° C.
Alcohol regenerated . . . . 4-2 grams 4*1 grams.
LlNALOL.
Linalol, C10H18O, is isomeric with geraniol and nerol, but it is

structurally isomeric, and not stereoisomeric, as it is known in both
optical forms. It was first isolated by Morin l from oil of linaloe. The
same body has been isolated from various other essential oils, ancf has
been described under the names licareol, coriandrol, lavendol, etc., all
of which have been found to be more or less impure forms of linalol.
Linalol is found very widely distributed in essential oils. It forms
the principal constituent, in the free state, of oil of linaloe, and the
chief odorous constituent, in the form of esters, in bergamot and lavender
oils. It is also found in ylang-ylang, rose, champaca leaf, cinnamon,
petit-grain, spike, geranium, lemon, spearmint, and numerous .other
essential oils.
Jt is a tertiary open-chain alcohol, probably of the constitution—
: CH . CH 2 . CH 2 . C(CH3)OH . CH : CH,
CH,
l
Ann. Chem. Phys., [5], 25, 427.
although it is possible that the alternative formula—
CH3
^C . CH2 . CH 2 . CH 2 . C(CH3)OH . CH : CH2
CHo
correctly represents its constitution.
Behal l considers that linalol is not an alcohol but an oxide of the
following constitution : —
3
: CH . CH2 . CH"0 . C(CH3) . CH2 . CH2
Linalol is not particularly easy to purify, as it yields practically no

crystalline compounds suitable for purification purposes. The charac-
ters of the various specimens prepared therefore vary, especially in
regard to their optical rotation. The following figures, for example,
have been recorded for linalol with a laevo-rotation :—
From
Lavender Oil. Bergamot Oil. Linaloe Oil. Lime Oil.
Boiling-point . 197° to 199° 197° to 199° 197° to 200° 198° to 199°

Specific gravity 0-8725 0-8720 0-877 0-870
Refractive index 1-4640 1-4629 1-4630 1-4668
Optical rotation - 10° 35' - 16° - 2° - 17° 37'
A specimen from lime oil, however, has been isolated with an optical
rotation - 20° 7', and a specimen of dextro-linalol from orange oil, with
a rotation of + 19° 18'. The characters of pure linalol, therefore, may
be taken approximately as follows :—
Optical rotation + or - 20°
Tiemann 2 prepares linalol in a state of approximate purity by the
following method. The linalol fraction of the essential oil is heated
with sodium, and the liquid heated under reduced pressure so long as
sodium continues to be dissolved. After cooling, the unchanged metallic
sodium is removed and the sodium compound of linalol is suspended
in ether and treated with phthalic anhydride. After standing for several
days, the mixture is shaken with water, which dissolves the linalyl
sodium phthalate, unchanged linalol and terpenes remaining dissolved
in the ether. The aqueous liquid is washed several times with ether,
the solution acidified and again extracted with ether. The resulting
linalyl acid phthalate is hydrolysed by alcoholic potash, and the pure
linalol is extracted with ether.
Optically inactive linalol can be artifically prepared by heating
l
Comptes Rendus., 1919, 168, 945. *Berichte, 29, 901; 31, 837.
geraniol in an autoclave for some time to a temperature of 200°, or it
can be obtained by treating geraniol with hydrochloric acid and treating
the resulting chlorides with alcoholic potash. The conversion of geraniol
into linalol has been very fully studied by Dupont and Labaune, who
give the following results of their work :—l
The geraniol with which they worked was extracted from palmarosa
oil, and purified by means of its phthalic acid ether and finally by means
of calcium chloride. Its characters were as follows :—
Rotation 0°
After reaction with hydrochloric acid, and repeated fractional distil-
lation, a product was obtained which contained 97*3 per cent, of chloride
of the formula C10H17C1. This body had the following characters :—
Boiling-point (6 mm.) 94° to 96° C.
bpecific gravity at 20° 0-9293
Refractive index v 1-4798
Optical rotation Prastically inactive
If the physical properties of this monochlorinated compound be
compared with those of the corresponding chloride from linalol, they
are found to be practically identical with the latter. The identity of the
two bodies derived from distinct chemical individuals is therefore almost
certain.
In order to clear up this question it was important to restore the
alcoholic group, avoiding as far as possible any chance of a molecular
transposition. Since the action of alcoholic potash and of the acetates-
might leave the matter open to criticism from this point of view, the
authors had recourse to an alcoholic solution of silver nitrate. The elim-
ination of the chlorine is instantaneous, it takes place even below 10° C.
50 grams of the chloro derivative are dissolved in 250 grams of 90 per
cent, alcohol; to this solution there is added in the cold a solution of 55
grams of silver nitrate in 50 grams of water and 100 grams of alcohol.
The liquid becomes acid owing to the liberation of nitric acid. After
separating the silver chloride, the liquid is neutralised, the alcohol is.
evaporated on the water-bath and the residue is rectified in vacuo.
With the chloro derivative of linalol the result is extremely sharp.
The whole of the product passes over, under a pressure of 6 mm., at a
temperature of 82° to 86° C., the residue being insignificant. The con-
stants of this body are as follows :—
Boiling-point (760 mm.) 198° to 199° C.
„ (6 mm.) 82° „ 86° C.
,, rotation . + 0-65°
which are approximately those of linalol. It is therefore clear that the

ester is the hydrochloric ester of linalol of the formula—
(CH3)2C : CH . CH 2 . CH 2 . C(CH3)C1. CH : CH2.
The corresponding ester obtained from geraniol was not obtained in
1
Roure-Bertrand Fils, Report, October, 1909, 24.
a perfectly pure state, and on regenerating the alcohol, a small amount of
geraniol was obtained, but the main constituent was pure linalol.
Paolini and Divizia l have succeeded in partially resolving inactive
linalol into its optically active isomers^ but only to the extent of optical
rotations of + 1° 70' and - 1° 60' respectively. Linalol was converted
into its acid phthalate, and an alcoholic solution of this compound was
treated with the equivalent quantity of strychnine. By fractional
crystallisation the laevo-rotatory salt, yielding dextro-rotatory linalol,
separates first, leaving the more soluble dextro-rotatory strychnine salt,
which yielded laevo-rotatory linalol in the mother liquor.
Linalol yields a somewhat remarkable compound, by artificial oxida-
tion which appears also to be formed naturally. This body is termed
linalol monoxide, and has the formula C10HlgO2. It was first found in
oil of linaloe by Schimmel & Co., and it is probably to be explained
by the oxidation of the essential oil on exposure to the air at the surface
of the trunk of the tree. It has been prepared artificially by Prileshajeff2
by oxidising linalol with hydrated benzoyl peroxide. By further oxida-
tion with the same reagent, he obtained linalol dioxide.
Linalol monoxide has the following characters :—
„ „ (at 4 mm.) 63° „ 64°
Molecular refraction . 48-88
The two oxides have the following formulae :-
OH
XX
CH I / \
•C=CH—CH»—CH, ,—C—CH — CCHo
CH,
CH,
Linalol monoxide.
/ \
CH, _C CH—CH2—CH2— COH—CH —CH,
CH,
Linalol dioxide.
By the hydration of dihydromyrcene, Schimmel & Co. obtained di-
hydrolinalol. This body has the constitution—
3
\C : CH . CH 2 CH 2 . C(CH3)OH . CH 2 . CH3
CH/
or possibly the similar constitution related to the alternative formula
for linalol given above. Dihydrolinalol was also prepared by the action
of magnesium methyl-iodide on methyl-heptenone. The only difference
observed between the bodies thus produced was that the latter was less
easy to convert into a phenyl-urethane. This is probably due to the
fact that in the case of dihydrolinalol produced from methyl-heptenone,
1 2
Chem. Zentral., 1915, 1, 603. Jour. Soc. Chim. Phys. Russ., 44, 613.
the isomerism of the original citral is reproduced in the dihydrolinalol,
which may consist of two stereoisomeric forms, whilst in the case of
hydration of dihydromyrcene, no stereoisomerism results. The following
figures are recorded for dihydrolinalol prepared from various sources:—
Molecular Refraction.
Prepared ironi. Boiling-point. î«°- nD
15°
Found. Calculated.
Dihydromyrcene . 92° to 92-5° 0-8570 1-45531 49-47 49-438

(12 to 13 mm.)
Methyl-heptenone from 77° to 78° (7 mm.) 0-8588 1-45641 49-46 49-436
citral (by oxidation) .
Methyl-heptenone from 66° to 66-5° 0-8575 1-45661 49-558 49-438
lemon-grass oil . (4 mm.)
Methyl-heptenone from 67-5° (4 mm.) 0-8590 1-45611 49-424 49-438
citral (by boiling with
solution of carbonate
of potassium)
Linalol may be characterised by the following methods:—

1. By oxidation to citral (q.v.).
2. By converting it into geraniol. This is effected by boiling linalol
with acetic anhydride for two hours and then saponifying the resulting
ester. Pure geraniol can be .obtained by fractionating the regenerated
alcohol, and the geraniol so obtained can be identified by the usual
method.
3. Preparation of the urethane, C6H5. NH . COOC10H17. A mixture
of 2 or 3 grams of the alcohol is mixed with rather more than the
theoretical amount of phenyl-isocyanate, and allowed to stand in a
stoppered flask for a week. It is then mixed with water, and a current
of steam passed through the mixture, in order to remove the unaltered
linalol. The crystalline mass which remains is collected, dried on
a porous plate, and extracted with ether, which dissolves the phenyl-
urethane. The ethereal solution is allowed to evaporate spontaneously
when crystals of the urethane separate, which melt at 65°.
4. Preparation of the naphthyl-urethane. This compound is pre-
pared in a similar method to that just described, using a-naphthyl-
isocyanate. The naphthyl-urethane melts at 53°.
CITRONELLOL.
Citronellol, C10H20O, is an alcohol which was first obtained by Dodge,1
by reducing the aldehyde citronellal, C10H18O, by means of sodium
amalgam and acetic acid. It was then found to be a constituent of rose,
geranium, and other essential oils. The citronellol question has given
rise to a somewhat acrimonious and prolonged controversy, as Barbier
and Bouveault claimed that the body which they termed rhodinol was
a chemical individual differing from citronellol, whilst Tiemann and
Schmidt and other German chemists maintained that rhodinol was
nothing more than a mixture of geraniol and citronellol, and not a
chemical individual at all. The controversy developed, as indicated
in the previous edition of this work (p. 51) on the following lines:—
]
Jour. Amer. Chem. Soc., 1889, xL 463.
Rhodinol was announced by Eckart to be an essential ingredient of
Bulgarian and German rose oils. He regarded it as an unsaturated
open-chain alcohol. Markovnikoff thereupon urged that roseol,
C10H200, was the chief ingredient of rose oil. Bertram, in 1894,
claimed that it was in reality merely geraniol, but in 1896 Tiemann
and Schmidt showed that the alcohols of rose oil consisted of a mixture
of geraniol and citronellol, C10H20O, which latter body, they claimed,
had evidently been mistaken for the so-called " rhodinol" and '* roseol ".
The names geraniol and citronellol therefore appeared to be those
most entitled to remain in chemical literature. Poleck, however, com-
plained that the name geranioi had been substituted for the earlier
rhodinol, overlooking the fact that the old rhodinol was apparently a
mixture. Erdmann further complicated this matter by insisting on
treating geraniol of commerce as a more or less impure body of which
the principal constituent, C10H17OH, is called rhodinol, claiming that
geraniol (pure) and rhodinol are identical, and that the former name
should be expugned from chemical literature.
The last of these bodies announced as being alcoholic constituents
of rose and geranium oils was reuniol, found in various geranium
oils (Keunion, African, and Spanish) by A. Hesse. This had previously
been announced as a probable chemical individual by Barbier, but he
stated that he had not obtained it pure. Erdmann and Huth claimed
that it was more or less pure rhodinol.
Up till about three years ago, there appeared to be little reason to
doubt that rhodinol was in fact an impure form of citronellol, the reduc-
tion product of citronellal being dextro-citronellol, whilst the natural
alcohol, which the French chemists had termed rhodinol was considered
to be laevo-citronellol.
Citronellol was considered to have one of the two following alterna-
tive formulae:—
. CH 2 . CH 2 . CH 2 . CH(CH3)CH2. CH2OH
CH3'
(1)
or
CH3.
: CH . CH 2 . CH 2 . CH(CH3)CH2CH2OH
CH/
(2)
There seems, however, to-day, to be overwhelming evidence that the

French chemists were correct and that citronellol and rhodinol are two
very similar, but chemically different, compounds, citronellol being re-
presented by the formula (1) and rhodinol by formula (2). Consider-
able evidence of this is to be found in the work of Barbier and Locquin,1
Starting from the acetic esters of ordinary ^-citronellol and rhodinol
from oil of geranium or rose, they attached hydrogen chloride to the
double bond, and obtained the same additive product according to the
equations:—•
1
Comptes Rendus, 157, 1114.
CH 3 . C . CH 2 . CH 2 . CH 2 . CH . CH 2 . CH2OH
CH., CH.^
+ HX = CH3 ."OX . CH 0 . CH.,. CH2 . CH . CH 2 . CH2OH
CH8 " " CH3
Citronellol.
CH 3 . C : CH . CH 2 . CH 2 . CH . CH,,. CH,OH
CH3 " CH3
+ HX = CH 3 . CX . CH.,. CH,,. CH.,. CH . CH,. CH2OH
CH3 ' " CH3
Bhodinol.
The \ authors found that on elimination of the halogen acid from this
compound, rhodinol, and not citronellol, is regenerated, dextro-rhodinol
from dextro-citronellol, and laevo-rhodinol from the laevo-rotatory alcohol
from "oil of \roses»or geranium, the two bodies, in the latter case being
identical.
Further, d-citronellal, the corresponding aldehyde, may be converted
into citronellic acid through its oxime and nitrile. Citronellic acid,
when treated with thionyl chloride in benzene solution, yields a chloride
of a chlorinated acid which is converted by the action of alcohol into
the hydrochloride of ethyl citronellate, or hydrochloride of ethyl rhodinate,
(CH3)2CC1—CH2—CH2—CH2—CH(CH3)—CH2—CO2C2H^
This ester loses hydrogen chloride by the action of sodium acetate
giving ethyl rhodinate which when reduced by sodium and absolute
alcohol yields rhodinol.
\ Citronellal can thus be converted into rhodinol without being first
reduced to citronellol.
A third method of converting citronellol into rhodinol is by hydrating
citronellol by means of 30 per cent, sulphuric acid. This yields the
glycol 3-7-dimethyl octanediol-1-7, of the formula—
(CH3)2. O(OH). CH 2 . CH 2 . CH 2 . CH(CH3). CH 2 . CHOH
which is dehydrated by boiling with 5 per cent, sulphuric acid, yielding
rhodinol.
I \The three optical varieties of rhodinol have thus been obtained,
namely, laevo-rhodinol, the natural constituent of rose and geranium
oils; dextro-rhodinol by conversion of dextro-citronellol obtained by re-
duction of citronellal, and inactive rhodinol by the reduction of synthetic
ethyl rhodinate.
Further evidence of the difference between rhodinol and citronellol is
forthcoming, in that the former yields on oxidation an aldehyde, rhodinal,
whose oxime does not yield citronellic acid nitrile when treated with
acetic anhydride, nor citronellic acid when the nitrile is treated with
alkalis, wheras citronellal, the aldehyde of citronellol, does yield the
nitrile and citronellic acid.
Harries and Comberg1 have also supplied much evidence, which,
taken with the above-mentioned researches, places the chemical isomerism
of citronellol and rhodinol practically beyond dispute. By ozonisation
experiments decomposition products were obtained, which proved that
natural " citronellal/' obtained from citronella oil, is a mixture of about
1
Annalen, 1915, 410, 1.
40 per cent, of true citronellal and 60 per cent, of rhodinal. It is true
that only one semicarbazone can be obtained by crystallisation, but this
<jan be ozonised, and the ozonide decomposed by boiling water, yielding
two semicarbazones, one of which is a derivative of citronellal, and the
•other of rhodinal. It is obvious therefore that the semicarbazones of
natural " citronellal" is either a very difficultly separable mixture of two
'bodies, or an individual substance in which a shifting of the double bond
occurs by ozonisation.
H. J. Prinsl has now isolated the two isomeric citronellals from Java
•citronella oil (see under citronellal).
The physical characters, therefore, of the bodies which have hitherto
been described as citronellol or rhodinol must therefore be understood to
apply to the respective bodies in as pure a state as their separation has
rendered possible. At all events, it is clear that the two alcohols are
-very similar in their general characters. These characters are approxi-
mately as follows:—
From Eose Oil.
Refractive index , 1-45789
From Geranium Oil.
Boiling-point at 764 mm, 225° to 226°
Eefractive index at 22° 1-45611
'Optical rotation . - 1° 40'
From Citronella Oil.
Boiling-point at 7 inm. 109°
From Barosma Pulchella Oil.
Boiling-point at 5 to 6 mm. 93° to 95°
By Reduction of Citronellal
Refractive index at 17'5° 1-45659
Optical rotation , + 4°
Citronellol can be characterised by conversion into citronellyl-

•phthalate of silver, which is prepared in an exactly similar manner to
the corresponding geranyl compound, and melts at 125° to 126°. It can
also be oxidised in the same manner as geraniol, yielding the aldehyde
citronellal, which can be identified as described later (vide citronellal).
Citronellol and rhodinol have faint but sweet rose odours.
Citronellol occurs so frequently associated with geraniol, and is
absolutely necessary as an ingredient of artificial otto of rose and similar
synthetic perfumes, that it is sometimes a matter of importance to separ-
ate the two bodies quantitatively. This can be done in the following
manner : To a mixture of 100 grams of phosphorus trichloride and 100
grams of ether, 100 grams of the mixed alcohols, dissolved in an equal
amount of ether, are added, so that, by keeping the liquids in a freezing
mixture, the temperature does not rise above 0°. The mixture is then
allowed to stand at the ordinary temperature, and is then several times-
washed with iced water. The oily layer is shaken with dilute soda
solution, and the citronellyl-phosphoric acid is dissolved out, leaving the
geranyl chloride undissolved. The citronellyl-phosphoric acid may be
hydrolised by boiling with alcoholic potash and then distilled in a cur-
rent of steam.
Another separation of a mixture of alcohols is often necessary,
namely, that of geraniol, citronellol, and phenyl-ethyl-alcohol, all of
which occur in admixture in artificial otto of rose. In this case advan-
tage may be taken of the fact that phenyl-ethyl alcohol is easily soluble
in 30 per cent, alcohol, which is not the case with geraniol or citronellol.
For further details on the separation of geraniol and citronellol the
chapter on the analysis of essential oils should be consulted.
MENTHO-CITKONELLOL.
Mentho-citronellol or menthonyl alcohol, C10H20O, is an alcohol of
delicate rose odour, and is synthetically prepared as follows :—
Laevo-menthone is converted into its oxime by means of hydroxylamine,.
This is treated with strong sulphuric acid, and so inverted to isomenthone
oxime. This is treated with phosphorus trichloride in chloroform solu-
tion, when hydrochloric acid is given off, and menthonitrile is formed^
The last named is reduced by sodium into menthonylamine, and the
oxalic acid compound of this is warmed with sodium nitrite solution when,
menthonyl alcohol is formed. This body has the following characters :—
Refractive index . . . . . . . . . 1*4471
METHYL-HEPTENOL.
Methyl-heptenol is an alcohol with a delicate rose odour, of the1
formula C8H16O. It occurs in Mexican and Cayeme linaloe oil, and i&
prepared by reducing methyl-heptenone, and has the following
characters:—
Optical rotation . . . . . . . . - 1° 34'
METHYL-HEPTYLENE CAEBINOL.
Methyl-heptylene carbinol, C9H18O, has been obtained by the reduc-
tion of methyl-heptylene ketone by means of sodium and alcohol. It is.
an oil with an odour recalling those of rose and linaloe, and has the
THE CONSTITUENTS OF ESSENTIAL OILS
BuPLEUKOL.
This alcohol, of the formula C10H20O, occurs in the essential oil

Bupleurum 1fruticosum, from which it was isolated by Francesconi and
Sernagiotto. It was separated by means of its phthalic acid ester, and
is an oil of faint rose odour, having the following characters :—
It yields a phenyl-urethane, melting at 45°. On oxidation it yields an

aldehyde having an odour of lemons, which yields a semicarbazone, melt-
ing at 135°.
Bupleurol is a primary alcohol, which according to the authors must
have one of the three alternative constitutions :—
%3H—CH2—CH.,—CH2—C =CH—CH9OH
CH/ " |
(1) CH3
SX
>CH—CH2—CH2—CH =C—CH2—CH2OH
CH,'
(2) CH
)CH—CH2—CH0—CH9—C—CH2—CH2OH
il
(3) CH2
ANDKOL.
This alcohol, C10H20O, is, like bupleurol, isomeric with citronellol and
rhodinol. It is present in the oil of water fennel (Phellandrium aquaticum),.
and has an odour characteristic of the plant. It has the following char-
acters :—
It yields a phenyl-urethane melting at 42° to 43°.

No aldehyde or ketone has been obtained from it by oxidation. Its
constitution is probably allied to those of citronellol and rhodinol, but,
since it contains an asymmetric carbon atom, as shown by its optical
activity, the three formulae given under bupleurol obviously cannot repre-
sent androl.
1
Gazz. chim. ItaL, 43, 1, 153.
124 THE CHBMISTBY OF ESSENTIAL OILS
UNCINEOL.
l
Baker and Smith have isolated an alcohol of the formula C10H18O
from the " cajuput " oil, distilled from the leaves of Melaleuca uncinala.
The alcohol, which is probably an open-chain compound, forms snow-
white crystals, melting at 72'5°, and having a specific rotation + 36'99°.
FARNESOL-.
Farnesol, C15H26O, is an aliphatic sesquiterpene alcohol, which occurs
in ambrette seed oil, and flower oils of the type of acacia, lime flowers,
mignonette, and lilac flowers.
This alcohol is almost invariably present in those essential oils which
contain aliphatic terpene alcohols, but in most of these it is present in
very small amount, and it is only from ambrette seed oil that any quantity
has been prepared. Ambrette seeds contain about Ol per cent, of this
alcohol, which, when freed from decylic alcohol which is also present,
Boiling-point at 10 mm. 160°
Optical rotation . ±0°
This alcohol appears to be almost odourless, but when a dilute solu-
tion in alcohol is allowed to evaporate slowly, a very fine lily-of-the-
valley odour is developed, together with the suggestion of cedar-wood oil.
Oxidation of farnesol with chromic acid mixture gives rise to the
aldehyde farnesal, which has the following characters :—
Farnesal forms a semi-carbazone, which crystallises from acetic
ether in fine flakes, which melt at 133° to 135°. This body is parti-
cularly useful for the identification of farnesol.
Farnesol forms an acetate, farnesyl acetate, which is a nearly odour-
less oil, boiling at 169° to 170° at 10 mm.
When dehydrated with potassium hydrogen sulpnate, farnesol yields
a sesquiterpene, which has been named farnesene, and is a colourless
Kerschbaum2 has carried out a series of experiments in order to
determine the constitution of farnesol.
In order to establish the primary character of farnesol, farnesenic
acid was prepared from farnesal oxime and the corresponding nitrile.
"Saponification of the farnesene-nitrile with caustic soda solution yields
farnesenic acid and acetic acid, and also a ketone which was identified
us a dihydxopseudoionone. The semi-carbazone melts between 95° and
96°. The dihydrops^doionone from farnesene nitrile proved to be
1
Jour. and Proc. Royal Soc., N.S.W., 41 (1907), 196.
*Berlchte,46 (1913), 1732.
identical with the synthetic product which has been obtained from
geranyl chloride and sodium acetic ester. Farnesol wras prepared
synthetically from hydroxydihydrofarnesenic ester which was prepared
from magnesium bromoacetic ester and dihydropsewdoionone. When
heated with acetic anhydride and sodium acetate this ester afforded
farnesenic methylester. Synthetic farnesenic acids boils at 203° at
14 mm.
It is evident from these reactions that farnesol has the constitution
of an aliphatic sesquiterpene alcohol with three double bonds, and that
its formula is—
CH.
C : CH. CH 2 . CH 2 . C : CH . CH,. CH 2 . C : CH . CH.OH
CH. CH CH,
3
Farnesol.
that of dihydYOpseudoionoue being as follows :-
>C : CH . CH 9 . CH 2 . C : CH . CH 0 . CH 9 . CO
CH. CH, CH,
Dihyducopseudoiouone.
The above constitution of farnesol has been confirmed by the oxida-
tion experiments of Harries and Haarmann.1
NEBOLIDOL.
Nerolidol is an aliphatic sesquiterpene alcohol of the formula
C15H2(50, which has bsen isolated from the higher boiling fractions of
orange-flower oil. It has the following characters :—
,, ., .. 760mm. 276° „ 277°
It is an oil with a slight but sweeet odour.
In 1899 Thorns isolated an alcohol from Peru balsam oil, which he
termed peruviol. This body was stated to have powerful antiseptic
properties, but has nob been further investigated until Schirnmel &
Co. took up the subject. The oil after saponification was fractionated,
and after benzyl alcohol had distilled over, a light oil with characteristic
balsamic odour passed over. It boiled at 125° to 127° at 4 mm., and had
a specific gravity 0*8987, optical rotation + 12° 22', and refractive index
1-48982. This body appeared to be identical with Hesse's nerolidol,
whilst in physical and chemical properties it closely resembles peruviol.
The characters of the various preparations were as follows :—
Boiling-point. Specific Rotation. Refractive

Gravity. Index.
Peruviol (Thorns) . 140° (7 mm.) 0-886 + 13° _

Schimmel's body (1) 133° „ 0-882 + 14° —
„ (2) . 127° (4 mm.) 0-899 + 12° 1-4898
Nerolidol (Hesse) . 129° (6 mm.) 0-880 + 14°
,, (Schimmel) 127° (5 mm.) —
0-880 + 13° 1-4802
1
Berichte, 46 (1913), 1737.
It appeared that the impure alcohol isolated from balsam of Peru
was, in fact, identical with nerolidol. When allowed to stand for three
to four weeks with phenyl-isocyanate both alcohols yielded a phenyl-
urethane, melting at 37° to 38°. A mixture of the two bodies suffered no
•depression in melting-point. The alcohols have the formula C15H20O.
The alcohol from balsam of Peru is therefore mixed with a small quantity
of an alcohol of higher specific gravity, the nature of which is still un-
determined. Traces of benzyl alcohol were found in it, but not in
sufficient quantity to account for the differences observed. Oxidation
experiments did not throw any light on the question. It may therefore
be safely assumed that the peruviol of Thorns consisted in the main of
nerolidol, but contaminated with a substance of the same boiling-point
to such an extent that its combustion figures pointed to the formula
C13H2.2O instead of C15H26O.
CLOSED CHAIN ALCOHOLS.
The next series of alcohols to be examined is that in which the
members retain the benzene nucleus in a more or less substituted
condition, as distinguished from those in which the benzene nucleus
has (tbeen so altered as to bring the alcohols within the series known as
the terpene alcohols ". A certain number of these alcohols are found
"in nature, but some of them are prepared synthetically, and, although
not yet found naturally, are exceedingly useful in the preparation of
perfumes.
BENZYL ALCOHOL.
Benzyl alcohol, C 6 H 5 . CH2OH, is the lowest member of the normal
series of aromatic alcohols containing the benzene nucleus. It exists to
a certain extent in the free state, but more often in the form of esters,
principally of acetic, benzoic, and cinnamic acids, in a number of essential
-oils, such as those of jasmin, tuberose, cassie flowers, and ylang-ylang.
It is prepared artificially, for use as a synthetic perfume, by several
•methods, for example, by heating benzyl chloride with oxide of lead to
100°, or by heating benzyl chloride with potassium acetate and saponify-
ing the benzyl acetate so formed, with caustic potash.
Benzyl alcohol is an oil with a slight but very sweet floral odour, and
Boiling-point .' 205° to 207°
It is fairly soluble in dilute alcohol, and in about 35 parts of water.
It can therefore be fairly easily separated from less soluble constituents
by shaking with 5 or 10 per cent, alcohol. Apart from its actual per-
fume value, benzyl alcohol is of considerable value to the perfumer, since
it acts as a very valuable fixative, and is, moreover, one of the best-
known solvents for artificial musk.
Benzyl alcohol forms a solid compound with calcium chloride,
and also a phthalic acid compound. The latter is obtained by heating
2 grams of the alcohol with 2 grams of phthalic anhydride and 1 gram
ôf benzene. Caustic soda solution is then added, and the solution washed
•with ether. The benzyl acid phthalate is precipitated by sulphuric acid,
•and can be recrystallised from benzene. It then melts at 106° to 107°.
It also yields a phenyl-urethane, melting at 77° to 78°. Its esters are
•agreeably-smelling liquids, which will be described later.
PHENYL-ETHYL ALCOHOL.
Phenyl-ethyl alcohol, C6H5 . CH2 . CH2OH, is the next highest
'homologue of the benzyl alcohol series. It is found naturally in rose
.-and neroli oils; but as it is very soluble in water, it practically
disappears from the distilled otto of rose and is dissolved in the rose
water. Hence otto of rose with its beautiful perfume does not truly
represent the odour of the rose. By the use of various isolated and
synthetic bodies an artificial otto can be prepared which more closely
resembles the rose odour than does the natural otto itself. But it is
•doubtful whether any really good artificial otto of rose can be prepared
without some natural otto as its basis.
Phenyl-ethyl alcohol, or benzyl carbinol, has been known for many
years, but its powerful rose odour has been entirely overlooked, its dis-
covery having been made by an ordinary research chemist and not a
perfumery expert. Its preparation was described in the Berichte
(9, 373) in 1876, but the product there noted was evidently impure, as
its boiling-point is recorded as 212°. Commercial specimens vary
greatly in both their odour and their keeping properties, some samples
•deteriorating in odour very rapidly. It is, therefore, very important to
•obtain it in a state of the highest purity. It has the following char-
acters :—
Boiling-point . 220° to 222° at 740 mm.
„ 104° at 12 mm.
Optical rotation ±0 °
It yields a diphenyl-urethane, which melts at 99° to 100°, and is very
useful for identification purposes. The phenyl-urethane, melting at 80° is
less useful for this purpose, since its melting-point is almost identical
with those of benzyl and nonyl alcohols. It combines with phthalic
acid to form a phthalic acid ester, melting at 188° to 189°.
Phenyl-ethyl alcohol can be prepared by numerous methods, several
of which are the subject-matter of patents. It may be prepared, for
example, by the conversion of phenyl-bromo-lactic acid into phenyl-
acetaldehyde, and then reducing this body with sodium. Or it may be
prepared by reducing phenyl-acetic esters with sodium and absolute
alcohol in the following manner :—
It is obtained by allowing a solution of one molecule of phenol-acetic
•ester in three to four times its weight of absolute alcohol, to fall in drops
on a quantity of sodium calculated for six atoms. It is then heated for
several hours on an oil-bath, until the sodium has disappeared, if
necessary adding more alcohol. After cooling, water is added, and the
ester which is not attacked is saponified. The alcohol and phenyl-
ethyl alcohol are then distilled off with steam, when the latter is at
once obtained in the pure state.
It is a colourless, heavy oil, with a typical rose and "honey" odour.
It is easily soluble in all organic solvents, and to a considerable extent
in water. It is soluble in 2 volumes of 50 per eent. alcohol, in 18
volumes of 30 per cent, alcohol, and in 60 volumes of water. Its identi-
fication is, therefore, best effected by extracting the mixture of alcohols
in which it occurs, by means of dilute alcohol, which dissolves the phenyl-
ethyl alcohol but not much of the other alcohols.
It is suitable, not only for rose odours, but also for blending with
almost any flower oil. Phenyl-ethyl alcohol forms a solid compound
with chloride of calcium, which is very useful for its purification. On
oxidation it is converted into a mixture of phenyl-acetaldehyde and
phenyl-acetic acid. The last-named body forms an ethyl ester melting
at 28°, which serves for its identification.
There is an isomeric and closely associated alcohol, phenyl-methyl
carbinol, C6H5CH(OH)CH3, known to chemists. This is a liquid of
different odour, but which is not used very much in synthetic perfumery.
It is an oil boiling at 203°, and forms an acetate which is found natur-
ally in essential oil of gardenia. This ester is of use in blending per-
fumes of this type of flower.
PHENYL-PROPYL ALCOHOL.
Phenyl-propyl alcohol, C6H5 . CH 2 . CH2 . CH2 . OH, is the next
highest homologue of phenyl-ethyl alcohol, and is also known as hydro-
cinnamyl alcohol. Like the last described bodies it has been known
for many years, its first preparation being described in the Annalen
(188, 202). It occurs as a cinnamic acid ester in storax, and as an
acetic ester in cassia oil. It is prepared synthetically by the reduction
of cinnamyl alcohol with sodium amalgam and water, or by the reduc-
tion of cinnamic or benzyl acetic esters with sodium and absolute
alcohol. It has the following characters ;—
Boiling point at 12 mni 119°
„ „ 760mm 235°
It can be characterised by its phenyl-urethane, melting at 47° to 48°,
or by oxidising its acetic acid solution by means of chromic acid, when
it yields hydrocinnamic acid, melting at 49°.
It is a colourless, thick oil, with an odour recalling that of cinnamic
alcohol and hyacinths. It is useful in synthetic perfumery in the pre-
paration of bouquets, and it is extremely useful in odours of the type of
hyacinth, narcissus, jonquil, and the like.
There exist three isomers of phenyl-propyl alcohol, all of which have
been prepared and described, and, although not yet introduced into
commerce, may eventually be so. These are as follows; Benzyl-
methyl-carbinol, C6H5 . CH2 . CH(OH)CH3, boiling at 215°; phenyl-
ethyl-carbinol, C 6 H 5 . CH(OH)GH2. CH3, boiling at 221°; and benzyl-
dimethyl-carbinol, C6H5. C(OH)(CH3)2, melting at 21° and boiling at-
225°.
HIGHER HOMOLOGUES OF PHENYL-ETHYL ALCOHOL.
Braun l has shown that alcohols of the type of phenyl-ethyl alcohol,,
containing an aliphatic and an aromatic radicle, can be prepared by the
reduction of nitriles of the general formula X . ON with the corresponding
1
Berichte, 44, 2867.
bases X . CH2NH2. These are then benzoylated and the benzoyl com-
pound heated with phosphorus pentachloride, when the chlorides
X. CH2C1 are formed. These, of course, are directly convertible into the
corresponding alcohols. The following alcohols so prepared are of con-
siderable interest as being homologues of the well-know7n rose alcohol,
phenyl-ethyl alcohol;—
JMta-phenyl-butyl alcohol (boiling-point 140° at 14 mm.).
phenyl-amyl ,, ,, ,, 155° ,, 20 ,,
6-phenyl-hexyl ,, ,, ,, 160° ,,13 ,,
7-phenyl-heptyl „ „ „ 170° to 172° at 15 mm.).
Of these phenyl-amyl alcohol has a pleasant, but somewhat evanescent
lemon-like odour ; phenyl-hexyl alcohol has a very similar odour to this ;
and phenyl-heptyl alcohol has a slight, but extremely agreeable odour
of roses.
CINNAMIC ALCOHOL.
Cinnamic alcohol, C 6 H 5 . CH ; CH . CH2OH, or y-phenyl-allyl alcohol,
is found in the form of esters, principally of either aceiic or cinnamie
acid in storax, balsam of Peru, and in hyacinth and other essential oils.
It may be prepared synthetically by reducing cinnamie aldehyde
diacetate, and saponifying the resulting cinnamyl esters. Cinnamie
alcohol is a crystalline body, although commercial specimens frequently
contain traces of impurities which prevent crystallisation. It has the
Melting-point 33°
,, ,, 117° at 5 mm.
Specific gravity at 35° about 1-020
Commercial samples of good quality have a specific gravity between
1-010 and 1-030.
Cinnamic alcohol forms a phenyl-urethane, melting at 90° to 91°, and
a diphenyl-urethane, melting at 97° to 98°. On oxidation it yields cinna-
mie acid, melting at 133°, and by more thorough oxidation, benzoic acid,
melting at 120°.
Cinnamic alcohol has an odour, not very powerful, but exceedingly
delicate, recalling roses and hyacinths, in which types of perfume it is
exceedingly useful. It is fairly soluble in dilute alcohol, and can to some
extent be separated from alcohols of the geraniol type by means of 30
per cent, alcohol.
CuM]Nic ALCOHOL.
/CH2OH
Cuminic alcohol, C6H4<^ , has been found in the essential
\CH(CH3)2
oil of cumin. On oxidation it yields cuminic acid, melting at 112° to 113°.
ANISIC ALCOHOL.
yCH2OH
Anisic alcohol, CGH/ has been isolated from the volatile
\OCH3
VOL. II. 9
constituents of Tahiti vanillas. It boils at 117° to 118° at 5 mm., and
yields a pbenyl-urethane, melting at 93°.
PERILLIC ALCOHOL.
An alcohol of the formula C10H16O was isolated from oil of ginger-
grass by Schimmel & Co.,1 and described by them as dihydrocuminic
alcohol. It has, however, now been shown by Semmler and Zaar 2 not to
have the constitution assigned to it by Schimmel & Co., but to be identical
with the alcohol obtained by reducing perillic aldehyde, C10H14O, the
aldehyde characteristic of the essential oil of Perilla nankinensis.
It was separated from geraniol, which accompanies it in ginger- grass
oil by treatment with concentrated formic acid, which destroys the
geraniol, but does not attack the perillic alcohol. It has the following
characters ; —
Boiling point ....... 119° to 121° at 11 mm.
Specific gravity ....... 0-969 at 20°
Refractive index ....... 1-4996
Specific rotation ....... - 68-5°
Its constitution is closely related to that of limonene, since its
chloride passes at once, on reduction, into this terpene as shown in the
following formulae : —
CH CH CH
H2C/\CH, H2C/\CH2
ILC 'CH H2C
X/"" H2
°\/',CH
C O C
CH2OH CH2C1 CH3
Perillic alcohol. Chloride. Limonene.
By oxidation this alcohol yields perillic aldehyde which forms a
semi-carbazone, melting at 199° to 200°, and perillic acid, melting at
130° to 131°. It also yields a naphthyl-urethane, melting at 146° to
147°.
Terpene Alcohols.
TERPINEOL.
Terpineol, C10H17. OH, is an alcohol of the greatest interest from a
fscientific point of view, and of the highest practical importance from the
perfumer's point of view. Three well-defined modifications of the sub-
stance known as terpineol are recognised, but as their chemical constitu-
tions are different in each case, it is not a question of so close a relationship
.as might be expected from the clumsy and slip-shod nomenclature univer-
1 2
Bericlite, April, 1904, 53 ; October, 1904, 41. Ibid., 44, 460.
sally employed for them. These " terpineols " are known as a-terpineol,
/?-terpineol, and y-terpineol.
Terpineol of commerce is, in the main, a mixture of the isomers, in
which a-terpineol largely predominates.
Terpineol is an alcohol which is used to an enormous extent in
synthetic perfumery, and is the basis of all the perfumes of the type of
lily of the valley, lilac, and similar odours. It blends so well with
numerous other bodies that it is easy to produce a large number of
different odours, all with the main perfume of terpineol. Muguet, for
example, is terpineol with small quantities of modifying substances.
Syringol, lilacine, and artificial gardenia are all based on terpineol.
Geranium oil and heliotropine are,excellent substances to round off this
odour, and on account of its stability it is most useful in soap perfumery,
as neither heat, acids, nor alkalis have any appreciable effect on it.
Ylang-ylang, sandalwood, and rose are also excellent odours to blend
with it.
These alcohols have long been a puzzle to chemists. Terpineol was
first prepared by Tilden by the action of dilute acids on terpin hydrate.
Wallach first prepared it in really good yield, by acting on terpin hydrate
with dilute phosphoric acid. He stated that it was a monatomic alcohol,
boiling at 215° to 218°, and described it as a liquid. Bouchardat and
Tardy prepare! it by the action of very dilute sulphuric acid on terpin
hydrate, and found that it solidified on cooling and then melted at
30° to 32°, easily remaining in a state of superfusion. A closer examin-
ation by Wallach and Baeyer showed that the true melting-point of the
principal terpineol is 35°. A study of the two bodies, the "liquid " and
the "solid" terpineol, and of their oxidation products, has revealed that
ihere are at least twelve definite isomeric terpineols, capable of being
synthesised. The liquid terpineol of commerce consists of a mixture of
At least two of these, those melting at 35° and at 32° to 33°, with either
some trace of impurity, or else a third isomeric liquid form. The ter-
pineols all appear to possess an odour recalling hyacinths, hawthorn,
and lilac. They are, when prepared artificially, optically inactive, but
flemmler has recently prepared optically active terpineols, by replacing
the chlorine in the two limonene monohydrochlorides by the hydroxyl
.group. The resulting terpineol is optically active in the same direction
as the limonene from which it is produced. Baeyer has, in addition,
«ynthesised an isomeric terpineol, melting at 69° to 70°.
Terpineol (that is a-terpineol) has been prepared synthetically by
Perkin and his pupils, his method being described under the synthesis
of limonene.
a-terpineol is a solid compound, melting at 35°. It occurs in the
dextro-rotatory form in numerous essential oils, including those of petit-
grain, neroli, orange, and linaloe; whilst it is found in the laevo-
rotatory condition in camphor oil, certain pine oils, and in Mexican
linaloe oil. It also occurs in the optically inactive variety in cajuput oil.
The artificially prepared a-terpineol, which is a constituent of com-
mercial terpineol, is, of course, inactive.
Synthetic a-terpineol has the following characters:—
Melting-point 35°
at 10 mm. 104° „ 105°
Natural terpineol has an optical rotation of about + 100°.
The average characters of the commercial mixture known as ter-
pineol are as follows :—
Boiling-point 217° ,, 220°
Refractive index 1-46CO „ T4840
Optical activity . . . . . . + 0° or slightly active
It is soluble in two volumes of 70 per cent, alcohol.
Messrs. Schimmel & Co. give the following characters for the active
and inactive varieties of a-terpineol:—
Inactive Active
Varieties. Varieties.
Melting-point 35° 37° to 38°
,, of nitrosochloride . . . 112° to 113° 107° ,, 108°
„ „ nitrol-piperidine . . 159° „ 160° 151° „ 152°
,, ,, „ methoethyl-heptanonolide. 64° 46° ,, 47°
a-terpineol has the following constitution :—

GEL GEL
COH
CH
HG CH,
C
CH3
a-terpineol is characterised by being converted into dipentene di-
hydriodide, C10H18I2, melting at 77° to 78°, by being shaken with con-
centrated hydriodic acid.
It yields a well-defined phenyl-urethane, melting at 113°. It requires
considerable care to obtain this compound, which should be prepared
as follows: terpineol mixed with the theoretical amount of phenyl-
isocyanate is left for four days at the ordinary room temperature.
Crystals separate which are diphenyl urea, and are removed by treating
the product with anhydrous ether, in which the diphenyl urea is insol-
uble. If the liquid be very carefully and slowly evaporated fine needles
of terpinyl-phenyl urethane separate. This compound has the formula
Ct.H5. NH . COOC10H17. The corresponding naphthyl-urethane melts at
147° to 148°.
Terpineol nitrosochloride, C10H17OH. NOC1, is, perhaps, the most
suitable derivative to prepare for the identification of terpineol. To a
solution of 15 grams of terpineol in 15 c.c. of glacial acetic acid, 11 c.c.
of ethyl nitrite are added. The mixture is cooled in ice, and 6 c.c. of
hydrochloric acid mixed with 6 c.c. of glacial acetic acid are added drop
by drop, with continual shaking. Care must be taken to avoid a rise in
temperature. When the reaction is complete, water is added to pre-
cipitate the nitrosochloride. The oily liquid soon solidifies and may be
recrystallised from boiling acetic ether or from methyl alcohol. Ter-
pineol nitrosochloride melts at 112° to 113° in the case of the optically
inactive form, or at 107° to 108° in the case of the optically active variety.
As in the case of pinene, the nitrosochloride forms a nitrol-piperidine,
C10H17(OH)NO. N . C5H10, melting at 159° to 160° in the case of opti-
cally inactive terpineol. or at 151° to 152° in the case of the optically
active variety.
/3-terpineol is found with a-terpineol amongst the reaction products
of dilute acids on terpin hydrate, so that it is a constituent of com-
mercial terpineol.
It is, when pure, a crystalline compound melting at 32° to 33°, and
Specific gravity 0-923 (at 15°, supervised)
Boiling-point at 752 mm. . . . 209° to 210°
It*yields the following crystalline derivatives, which are suitable for
its identification: nitrosochloride melting at 103°, nitrol-piperidine melt-
ing at 108°, nitrol-anilide melting at 110°, and phenyl-urethane melting
at 85°.
/^-terpineol has the following constitution :—
H2
°\/COH
CH3
y-terpineol has not been found in nature. It has been prepared by
Baeyerl by the reduction of tribrom—1. 4 . 8—terpene, resulting from
the bromination of dipentene dihydrobromide. It also results from
the action of dilute phosphoric, or oxalic acid, on terpin hydrate.
It forms prisms melting at 69° to 70°. To identify this body it may
be converted into its acetate, which then yields a nitrosochloride in the
usual manner, which melts at 82°.
y-terpineol has the following constitution :—
COH
H2C
C
/
l
Berichte, 27 (1894), 443.
A useful method for the production of terpineol for use in perfumery
on a commercial scale is the following, due to Bertram and Walbaum :—
Two kilograms of acetic acid are mixed with 50 grams of sulphuric
acid and 50 grams of water. Into the mixture, which should not be
allowed to rise above 50°, 1 kilogram of rectified oil of turpentine is
poured, in portions of 200 grams at a time. After cooling and standing,
the liquid is diluted with water and shaken with soda solution. The
product consists of terpinene and terpineol esters, which are separated
by fractional distillation. The esters, on treatment with alcoholic
potash, yield terpineol.
THUJYL ALCOHOL.
Thujyl alcohol, C10H17OH, occurs in the oils of wormwood and thuja
leaves, etc., and also results from the reduction of its ketone, thujone,
by means of sodium. It is identical with the body originally described
by Semmler under the name tanacetyl alcohol.
It has, according to Semmler, the following characters :•—
„ at 13 mm 92'5°
It yields a chloride, thujyl chloride, O^H^Cl, by the action of phos-

phorus pentachloride, which on treatment with aniline yields up HC1,
with the formation of the terpene thujene.
Paolinil has separated from the reduction products of thujone the
acid phthalate of /3-thujyl alcohol, HOOC . C6H4 . COO . C10H17, melting
at 120°, and having a specific rotation + 91'27°. This body yields a
silver salt which melts at 85° to 86°, and a strychnine salt melting at
177° to 178°. On saponifying the phthalate /3-thujyl alcohol results,
Boiling-point 206°
Tschujaeff and Fromm 2 have shown that by the recrystallisation of the

cinchonine salt of the phthalic acid ester, and hydrolysis of the crystal-'
line salt, ^-thujyl alcohol can be obtained of specific rotation 4- 116'9°,
20°
and specific gravity 0'9187 at j^-, thus agreeing with Paolini's results.
The more soluble cinchonine salt remaining in the mother liquors, gave
a laevo-rotatory thujyl alcohol, but the highest rotation obtained was
- 9-12°.
Thujyl alcohol has the constitution :—
1
2
Atti.
R. Accad. dei Lincei, (v.), 20, i. 765.
Berichte, 45 (1912), 1293.
CHQ
.OH
H2C
CH3 CH3
It can be identified by oxidation with chromic acid, when its ketone,

thujone, results. This can then be characterised bj its oxime, melting
at 54°
SABINOL.
Sabinol, C10H15 . OH, is a secondary alcohol, existing in the oils of
savin, cypress and eucalyptus, either in the free state or in the form of
its acetic ester. Somewhat discordant values have been published for
this alcohol, its characters, according to Schimmell and Semmler2 being
as follows:—
Boiling point 210° to 213°
,, „ at 20 mm. 105° „ 107°
Specific gravity at 20° 0-94:32
Paolini and Eebern 3 have, however, prepared sabinol in a pure con-
dition by means of its hydrogen phthalate, in the hope of separating it
into its stereoisomeric forms. The hydrogen phthalate of sabinol which
they prepared, COOH . C6H4 . CO2 . C10H15, crystallised in white silky
needles melting at 95°, and having a specific rotation, in methyl alcohol,
- 14-6°. On hydrolysis, this yielded sabinol having the following char-
acters :—
Boiling-point 208°
Specific rotation + 7° 56'
No isomer appeared to be present in savin oil, since no separation
could be effected by conversion of the hydrogen phthalate into its
strychnine salt, and fractional crystallisation thereof. The strychnine
salt, C3?H40O6N2, melts at 200° to 201°.
Sabinol probably has the constitution :—
Berichte,3 October (1895), 40. '2 Ibid., 33 (1900), 1459.

Atti. R. Accad. del Lincei, 1916 (v.), 25, ii. 377.
136 THE CHEMISTEY OP ESSENTIAL OILS
CH,
II
C
/\
HC/ \CHOH
H.,C' CH.,
CH(CH3)2
On oxidation with permanganate of potassium it yields sabinol-
glycerine, C10H15(OH)3, melting at 152° to 153°, and by further oxidation,
tanacetogene-dicarboxylic acid, C9H14O3, melting at 140°. On reduction
with sodium and amyl alcohol, sabinol yields thujyl alcohol, C10H17OH.
TERPINBNOL.
Terpinenol, C10H18O, is found in the oils of marjoram, cardamoms,
cypress, and nutmeg, as well as in several others to a small extent. It
has the following constitution :—
CH
C
H2C/ ^CH
TT /~1j HTJ
H.C^CH,
C.OH
(CH3)2
It can be obtained artificially by treating sabinene or thujene with
dilute sulphuric acid, when the resulting alcohol is optically inactive.
The natural alcohol, isolated from juniper berry oil, has the following
characters :—
This was probably an impure preparation, and probably Wallach's
preparation J was in a much purer condition. This had the following
characters : —
Kefractive index at 19° 1-4785
Optical rotation . . + 25° 4'
whilst for the inactive variety Wallach gives the following figures :
1
Annalent 356 (1907), 215.
By oxidation with potassium permanganate, terpinenol yields trioxy-
terpane, C10H17(OH)3, melting at 114° to 116°, and by boiling with dilute
sulphuric acid carvenone results. This body yields a semi-carbazone,
melting at 202°.
The above-described compound is known as terpinenol-4 in accord-
ance with recognised nomenclature. A body known as terpinenol- 1
is present to a small extent in the artificially prepared commercial
terpinenol. This body has the following characters : —
Boiling-point ......... 208° to 210°
Specific gravity ......... 0-9265 at 18°
Kefractive index ........ 1-4781
It has been prepared synthetically by Wallach l from isopropyl-
hexenone. It has the constitution : —
CH3
C (OH)
C
CH(CH3)2
TERPINE HYDEATE.
Terpine hydrate, C10H18(OH)1J + H2O, is a crystalline alcohol re-
sulting from the action of dilute mineral acids on either pinene or
limonene. It can be prepared by several different methods, of which
the following is typical : A mixture of 8 parts of oil or turpentine,
:2 parts of alcohol, and 2 parts of nitric acid of specific gravity 1*255
is allowed to stand for several days in a flat basin. After standing for
& few days the mother liquor is poured off from the crystals of terpine
ihydrate, and neutralised with an alkali, after which a second crop of
•crystals is obtained.
Terpine hydrate crystallises in well-defined monoclinic prisms,
melting at 116° to 117°. On distillation, or on exposure to sulphuric
acid, terpine hydrate gives off the water of crystallisation and yields the
anhydrous alcohol terpine. It is probable that terpine exists in the
space isomeric forms, known as c^s-terpine and frrans-terpine. The
product resulting from the dehydration of terpine hydrate is that known
.as ds-terpine. It melts at 39°. Tnms-terpine melts at 64° and is pre-
pared by dissolving dipentene dihydrobromide in 10 times its amount
of glacial acetic acid and gradually adding silver acetate to the ice-cooled
solution. The product is filtered after standing for some time and the
filtrate is neutralised with soda and extracted with ether. The ethereal
solution is treated with alcoholic potash to saponify the acetyl compound
and the reaction product is distilled with steam, to remove hydrocarbons
and terpineol. Transterpine remains in the residue after this treatment.
Terpine has the following constitution : —
1
Annalen, 362 (1908), 280.
CH3
C.OH
CH. C(OH)(CH3)2
PlNOCAKVEOL.
Pinocarveol, C10H16O, is a bicyclic alcohol, which has been found in*

oil of Eucalyptus globulus, and is apparently \identical with the alcohol
obtained by the reduction of nitrosopinene. It can be prepared artificially
in the following manner :—
Seventy grams of pinylamine nitrate are treated with a solution of"
10 grams of sodium nitrite in 100 c.c. of water for some time. The
yellowish oil which separates is distilled with steam, and the distillate is
shaken with an oxalic acid solution in order to remove basic compounds,
and again distilled with steam. Pinocarveol has the following char-
acters :—
,, ,, at 12 mm. 92°
Refractive index l-4%3
It forms a phenylurethane which appears to consist of two isomers-
melting at 82° to 84° and at 94° to 95° respectively. The formation of
these two phenylurethanes makes it probable that pinocarveol is itself a.
mixture of two isomeric compounds. On oxidation with chromic acid
pinocarveol yields a compound C10H14O which forms two semi-carbazonesr
melting at 210° and 320° respectively.
Pinocarveol has the following constitution (probably) :—
C : CH,
HO.CH / {CHi \CH
c/
H2C
\\ /
/
/
/CH2
JH
PlNENOL.
This body has been described in detail by Genvresse,1 but its chemical
individuality cannot be regarded as established. Its formula is said to
be C10H15OH and it has the following characters :—
1
Comptes rendus, 130, 918.
„ „ 143° „ 88 mm.
Refractive index 1-4970°
It is prepared by passing nitrous fumes into ice-cold pinene. It
forms an acetate, C10H15O . COCH3, which has a marked lavender odour.
DlHYDKOCARVEOL.
Dihydrocarveol, C10H18O, is a natural constituent of caraway oil, and

is also obtained by the reduction of carvone.
To prepare it artificially, 20 grams of carvone are dissolved in 200 c.c.
of absolute alcohol and 24 grams of sodium are added. Towards the
end of the reaction water is added, and the product is then distilled
with steam.
Dihydrocarveol is an oil of agreeable odour, and haviogvthe following
characters:—
„ ,, „ 7 mm 100° „ 102°
The above values apply to natural dihydrocarveol from caraway oil.
A specimen prepared by the reduction of carvone had a specific gravity
0-927 at 20° and refractive index 1-48168. \ mn«L
Dihydrocarveol is obtained from both optical forms of carvone, \ and
is optically active in the same sense as the original carvone. It has the
following constitution :—
CH . CH
HoC\ /C!:L
(CH 2 ):C.(CH 3 )
On oxidation with chromic acid in acetic acid solution, dihydro-
carveol yields dihydrocarvone, which has a specific gravity 0*928 at 19°,
and refractive index 1-47174. The dihydrocarvone from laevo-dihyd.ro-
carveol is dextro-rotatory, and vice versa. Its oxime melts at 88° to 89°
for the optically active variety, and at 115° to 116° for the optically
inactive form.
Dihydrocarveol yields a phenylurethane, C6H5NH . CO . OC10H17,
melting at- 87° for the optically active variety, and 93° for the optically
inactive form.
TERESANTALOL.
Teresantalol is an alcohol of the formula C10H16O, which was isolated
from sandalwood oil by Schimmel & Co. It has been prepared artifici-
ally by Sem'mler and Bartelt,1 by reducing teresantalic acid with sodium.
l
Berichte (1907), 3321.
It is a solid body melting at 112° to 114°, forming exceedingly fine pris-
matic crystals. It forms a compound with phthalic acid, melting at 140°.
FENCHYL ALCOHOL.
The chemistry of fenchyl alcohol, C10H18O, must be regarded as in a
somewhat unsettled state, as questions of isomerism arise which are as
yet unsolved. It was originally prepared by Wallach by reducing the
ketone fenchone, a natural constituent of several essential oils, by means
of sodium. Later1 he obtained it in fairly large quantities as a by-
product in the preparation of fenchone-carboxylic acid, by passing a
current of CO2 through an ethereal solution of fenchone in the presence
of sodium. Fenchyl alcohol has, so far, been found in one essential oil
only, namely, that of the root wood of Pimis palustris.
Wallach gives the following characters for the laevo-rotatory fenchyl
alcohol:—
Boiling-point 201°
rotation - 10° 35'
Melting-point 45°
The naturally occurring fenchyl alcohol is optically inactive and

melts at 33° to 35°, which agrees with the observations of Wallach, a
mixture of the two optically active forms, each of which melted at 45°,
Pickard, Lewcock and Yates 2 have prepared fenchyl alcohol by the
reduction of ^-fenchone ; they found it to be laevo-rotatory. On con-
version into its hydrogen phthalate and fractionally crystallising the
magnesium and cinchonine salts, they obtained a fraction, which on
saponification yielded Zam)-fenchyl alcohol, having a specific rotation of
— 15*5°, which is probably the correct value for this figure.
Fenchyl alcohol yields a phenylurethane melting at 88° when pre-
pared from the optically inactive alcohol, and at 82-5° when prepared
from the optically active form. It yields fenchone on oxidation, which
can be identified by its crystalline combinations (vide fenchone).
Fenchyl alcohol has, according to Semmler, the following con-
stitution :—
C.CHo
CH(OH)
CH,
JC(CH3)2
Fenchyl alcohol yields an acetate, C10H170 . COCH3, boiling at 87° to

88° at 10 mm., and having a specific gravity O9748, and specific
rotation - 58°.
2
i Annalen (1895), 324. Jour. Chem. Soc., 29 (1913), 127.
According to Schimmel & Co., l if fenchene be treated with a mixture
of acetic and sulphuric acids, it is hydrated with the formation of iso-
fenchyl alcohol, C10H18O. This alcohol is a solid body, crystallising in
needles melting at 61° to 62°. On oxidation it gives rise to a ketone,
C10H1(.0, which is isomeric with fenchone, but which on reduction does
not yield either fenchyl or isofenchyl alcohols, but a third isomeric
alcohol. Isofenchyl alcohol forms a phenylurethane melting at 106° to
107°. The characters of the isomeric alcohols are compared in the
following table:—
Fenchyl Alcohol. Isofenchyl Alcohol.
Melting-point . . . . "45° 61° to 62°
of- phenylurethane
- - . 82° 106° „ 107°
,, hydrogen phthalate 145° 149° ,, 150°
Boiling-point . 91° to 92° (11 mm.) 97° to 98° (13 mm.)
Acetic ester, boiling-point 88° (10 mm.) 98° „ 99° (14 mm.)
Boiling-point of ketone formed 191° to 192° 193° to 194°
Melting-point,, ,, ,, 6° liquid
,, ,, ,, oxime of ketone 164° to 165° 82°
ISOPULEGOL.
Isopulegol, C10H18O, does not appear to exist in essential oils, but it

results from the action of acids on citronellal. The last-named body,
for example, when boiled with acetic anhydride yields isopulegyl acetate,
from which the alcohol is obtained by hydrolysis.
Isopulegol is an oil having an odour resembling that of menthol. Its
characters are as follows : —
Boiling-point ......... 91° at 13 mm.
Specific gravity ........ 0-9154 at 17'5°
Its optical rotation has usually been recorded as from - 2° to - 3°,
but recently Pickard, Lewcock, and Yates 2 have prepared /-isopulegol
by fractional crystallisation of the magnesium and cinchonine salts of
the hydrogen phthalate, and found its specific rotation to be - 22 '2°.
Isopulegol has the following constitution : —
CH3
CH
H2c CHOH
CH
(CH,) : C . (CH3)
On oxidation isopulegol yields isopulegone, which can be character-
ised by its oxime, which melts at 121° for the active, and about 140° for
the inactive variety ; or its semi-carbazone, which melts at 172° to 173°
for the active, and 182° to 183° for the inactive variety.
Isopulegyl hydrogen phthalate melts at 106° and has a specific rota-
tion - 18*7°, and its magnesium salt melts at 115°.
1
Report, October, 1898, 49 ; April, 1900, 55 and 60.
2
Jour. Chem. Soc., 29 (1913), 127.
Pulegone, on reduction, yields an alcohol, C10H18O, which is known
as pulegol. It is a viscous liquid, having the odour of terpineol, and
boiling at 215°. Its specific gravity is O912. It is difficult to obtain it
in a state of purity.
Schimmel & Co.1 treated isopulegol with aqueous and alcoholic solu-
tions of alkalis to try and convert isopulegol into pulegol. By the action
of sodium ethylate, instead of pulegol which might have been expected
to be produced, two totally different reactions took place ; on the one
hand there was rupture of the unsaturated side chain with the forma-
tion of methylcyclohexanol; on the other hand there was opening of
the hexagonal nucleus between the carbon atoms 3 and 4, with forma-
tion of citronellol, according to the following scheme :—
CH.
CH, CH
H.,C/\CH, /CH,
H + oc
H,C/\CH2 ^^ H2CX/CH(OH)
<,
,CH(O H) Methylcyclohexanol.
CH -
^\ OH H.,
^ CHg
-LoV^ \JJLJ-2 /
Isopulegol. H3C-CH<^
Citronellol.
It is probable that the isopulegol was first changed to pulegol and
.this to methylcyclohexanol.
MENTHOL.
Menthol, C10H19OH, is the characteristic alcohol of oil of pepper-
mint, from which it separates in fine crystals on cooling. It also results
from the reduction of the corresponding ketone, menthone, C10H180, and
.also of pulegone, C10Hj6O.
Natural menthol is laevo-rotatory. The reduction of both laevo-
menthone and dextro-menthone yields a mixture in which laevo-menthol
jpredominates. The constitution of menthol is as follows :—
CH3
CH
-CHOH
!H
CH(
£(CH3)2.
1
Its physical characters are as follows :—
Melting-point 43° to 14-5°
Boiling-point at 760° 215° ,, 216°
Specific gravity ~ 0*881
rotation . - 49° to - 50°
Various melting-points have been recorded for menthol, and the
recent work of F. E. Wright l throws some light upon these differences.
Wright describes the crystallisation of menthol in four different forms,
ivhich he terms a, b, c, and d. Three of these appear to bear monotropic
relations to the stable a form. On crystallisation, all forms of menthol
show a pronounced tendency to the development of radial spherulites;
ihese are roughly spherical in shape in the case of crystallisation from
the melt, but noticeably ellipsoidal on inversion of one crystal form into
a second. The four forms are readily distinguishable under the petro-
.graphic microscope. a-menthol shows dextro-rotatory polarisation,
while the melt is laevo-rotatory. In the formation of the different
monotropic forms the initial temperature of crystallisation appears to
be the determinative factor. The a form is stable between zero and its
melting temperature, 42*5° C. The other forms have lower melting
temperatures, namely, 35'5° (6), 33'5° (c), 31-5° (d), all of which invert
finally into the stable a form on standing; the d form may invert first
into the b and then into the a form. At a given temperature the rate of
growth of crystals of a given form from the undercooled melt is constant;
Also the rate of growth on inversion of an unstable form into one more
stable. The refractive index of melted menthol at 25° is approximately
1-458 for sodium light, whilst that of the crystals is greater. The specific
rotation of melted menthol at 15° is — 59*6°, corresponding to a laevo-
xotation of - 0*53° per mm. depth of liquid, whilst the crystals are
dextro-rotatory, the rotatory power of the stable a form being over five times
as great when measured for the D line. The melting-points were ob-
served in polarised light, the crystals being melted between two strips
of thin cover glass; the slide was immersed in a beaker of water placed
on the microscope stage and kept at a definite temperature by means of
a small electric resistance heating coil of fine enamelled constantan wire.
Melted menthol shows undercooling to a pronounced degree, and does
not crystallise within reasonable time until after a temperature of 32° or
lower has been reached. Crystals of the a form grow at an appreciable
rate at 42°. On crystallisation from the melt at the higher temperature
needles are commonly formed; these show a tendency toward radial
arrangement. At lower temperatures radial spherulites are almost in-
variably formed.
Menthol forms an acetate, menthyl acetate, C1()H19O . COCH3, a thick
highly refractive liquid boiling at 224°, and of specific rotation - 114°.
It forms a characteristic benzoic ester, C10H19O . CO . C6H5, melting
at 54°. This is a useful compound for identifying menthol and may be
obtained by heating menthol with the theoretical amount of benzoic
acid, in a sealed tube to 170°; excess of acid is removed by shaking with
a boiling solution of sodium carbonate, and the ester is crystallised from
alcohol. Menthol forms a phenylurethane, melting at 111° to 112°.
Boedtker2 has prepared a number of the homologues of menthol in
1
2
Jour. Amer. Chem. Soc., 39, 1515, through P. and E.O.R.
Bull. Soc. Chim., iv. 17 (1915), 360.
the following manner : Sodamide was allowed to react with menthone
dissolved in ether. The resulting sodium-menthone was treated with
the various alkyl iodides, with the formation of the corresponding alkyl-
menthones. These were reduced with sodium and yielded the corre-
sponding menthol homologues. The alkyl-menthols so prepared had
Specific
Gravity Refractive
Boiling-point. 18° Rotation. Index.
at yo-.
Methylmenthol 129° to 130° (32 mm.) 0-9124 [a]Doi0 - 2° 26' 1-4692

Methylmenthylacetate . 125° (17 mm.) 0-9313 [a]D,20 - 18° 7' 1-4578
! Ethylmenthol 124° (13 „ ) 0-9246 [a] 000 + 4° 55' 1-4769
Ethylmenthylacetate . 131° to 132° (14 mm.) 0-9366 WD,IO - 6° 6' 1-4636
w-Propylmenthol . 141° „ 145° (27 „ ) 0-9075 MD,OO + 29° I1 1-4675
n-Propylmenthylacetate 152° (30 mm.) 0-9515 WD.,,O - 8° 58/ 1 4741 (19°)
Isoamylmenthol . 150° (23 „ ) 0-8985 WD,0o + 33°44' 1-4661
20°
Benzylmenthol 203° to 205° (24 mm.) d-p- 0-9819 WD,OO ~ 43° 19' 1-5257
Standnikowl has prepared several of the esters of menthol by heat-

ing magnesium iodo-mentholate with the esters of ethyl alcohol. For
example, with ethyl acetate, propionate, and benzoate the corresponding
menthyl esters were obtained. These bodies have the following boiling-
points :—
Menthyl acetate 113° at 19 mm.
,, propionate 122° to 123° at 19 mm.
,, benzoate 191° „ 192° „ 18 „
Menthyl benzoate melts at 54*5° to 55°.
Numerous isomeric menthols have been described, many of which
are certainly not chemical individuals.
When menthone is reduced there is found, in addition to menthol, a
certain amount of isomenthol. This body melts at 78° to 81° and is
slightly dextro-rotatory, its specific rotation being + 2°.
The most reliable work on the isomeric menthols is that of Pickard
and Littlebury.2 Starting from the mixture of alcohols which Brunei 3
had obtained by the reduction of thymol, and which he had described
under the name of thymomenthol, they isolated from it about 60 per
cent, of isomeric menthols, 30 per cent, of menthones, and several other
compounds. They prepared the phthalic acid esters and converted them
into their magnesium and zinc salts, which were then fractionally crys-
tallised.
Two distinct bodies were thus obtained, which, on hydrolysis yielded
the corresponding menthols, of which one is inactive menthol (melting-
point 34° C.; boiling-point, 16 mm., 103° to 105° C.; acid phthalic ester,
melting-point 129° to 131° C.), the other, neomenthol crystallising from
petroleum spirit in prismatic tables melting at 51° C.; boiling-point,
l
Jour. Russ.phys. CJiem. Ges., 47 (1915), 1113.
*Jour.
:J
Chem. Soc., 101, 109.
Comptes rendus, 137, 1288; and Roure-Bertrand Fils, Bulletin.
16 mm., 103° to 105° C.; phenylurethane, melting-point 114° C.; acid
guccinic ester, melting-point 67° to 68° C.; acid phthalic ester, melting-
point 175° to 177° C.
The same menthol and neomenthol have also been obtained by the
reduction of inactive menthone by means of hydrogen, in presence of
nickel at 180° C.
The inactive menthol melting at 34° C. just described is probably
identical with the /?-thymomenthol described by Brunei; the inactive
neomenthol is probably identical with the isomenthol described above.
Natural laevo-menthol is clearly a homogeneous compound. On the
other hand, the inactive menthol melting at 34° C. may be split up, by
passing through the form of the brucine salts of the phthalic ester, into
laevo-menthol (melting-point 42° C.; [a]D - 48*76°) and dextro-menthol
(melting-point 40° C.; [a]D '+ 48*15°). Similarly, the inactive neomen-
thol may be decomposed into dextro-neomenthol ([a]D + 19*69°) and
laevo-neomenthol ([a]D - 19*62°). These active modifications are both
liquids; the former having a boiling-point of 98° at a pressure of 16 mm.
and the latter boiling at 105° at 21 mm. Dextro-neomenthol has been
shown to exist in very small quantity in Japanese peppermint oiL
BORNEOL.
Borneol, C10H17OH, the alcohol corresponding to the ketone camphor,,
occurs naturally, in both optically active modifications ; as dextro-borneol
in the wood of Dryobalanops camphor a (Borneo camphor), and as laevo-
borneol in Blumea balsamifera (Ngai camphor). It also occurs in the
optically inactive modification. It is found in numerous essential oils,
such as those of the pine-needle type, in the form of its acetic ester, and
also in spike, rosemary, and numerous other oils. It forms crystalline
masses, or, when recrystallised from petroleum ether, fine tablets which,
when quite pure, melt at 204°. Its boiling-point is only a few degrees
higher, viz. 212°. According to Bouchardat the melting-point is lower
than that given, but this is undoubtedly due to the fact that his speci-
men of borneol probably contained some impurity. Traces of isoborneol,
strangely, raise the melting-point to 206° to 208°. Borneol can be pre-
pared artificially by reducing its ketone (camphor) with sodium. Fifty
grams of pure camphor are dissolved in 500 c.c. of nearly absolute
alcohol, and treated with 60 grams of sodium. After the reaction is
complete the whole is poured into a large volume of water, and the re-
sulting borneol is collected, washed, pressed, and recrystallised from
petroleum ether. This method of preparation, however, yields a mixture
of borneol and isoborneol. The chemically pure body is best prepared
by the saponification of its acetate. On oxidation, the converse reaction
takes place, with the formation of camphor. Borneol forms a series of
esters with the organic acids, of which bornyl acetate is most frequently
found in nature. This body melts at 29°, and has a specific gravity of
*991 at 15°. It is optically active. In common with a large number of
alcoholic bodies borneol forms a crystalline phenylurethane. This can
be prepared by the interaction of phenylisocyanate and borneol. It
melts at 138°. Bornyl chloride, prepared by the action of phosphorus
pentachloride on borneol, melts at 157°.
Borneol forms crystalline compounds with chloral and bromal, the
former melting at 55° and the latter at 104° to 105°.
VOL. II. 10
Bertram and Walbaum give the following as the characters of several
of the borneol esters :—
i
Boiling-point Optical Specific Refractive Index
at 10 mm. Rotation. Gravity. at 15°.
Formate . 90° + 31° 1-013 1-47078

Acetate 98° - 38° 20' 0-991 1-46635
Propioniate 110° + 24° 0-978 1-46435
Butyrate . 121° + 22° 0-966 1-46380
Valerianate 128° to 130° + 20° 0-956 1-46280
It also forms a phthalic acid compound melting at 164°. Pure

borneol has the following characters :—
Melting-point 203° to 204°
Boiling-point 212°
„ rotation (in alcohol) ± 37'6° to 39*5°
Borneol has the following constitution :—
H;
CH,.C.CH,
H,C CH2
CH
1
Henderson and Heilbron recommend the following method for
differentiating between borneol and isoborneol (q*v.). The alcohol is
dissolved in ten to fifteen times its weight of pyridine, and the calculated
amount of âra-nitrobenzoyl chloride added, and the mixture heated on
the water-bath for several hours. The pyridine is removed by extrac-
tion with ice-cold dilute sulphuric acid, and the resulting para-miro-
benzoate of the alcohol, after washing with dilute sulphuric acid again,
is separated, dried, and • recrystallised from alcohol. Bornyl-p-nitro-
benzoate melts at 137°, whilst the corresponding isoborneol derivative
melts at 129°. It is possible that the usually accepted melting-points
of both borneol and isoborneol may require revision, as Henderson and
Heilbron find the borneol regenerated from the crystalline nitrobenzoate
joaelts at 208°, and isoborneol2 obtained in the same way at 217°.
Pickard and Littlebury have carried out a series of investigations
ôn the separation of the optically active borneols and isoborneols, which
is of particular interest, as the method of separation can probably be
âpplied to various other similar bodies. This method depends on the
1
Proc. Chem. Soc., 29 (1913), 381.
'Ibid., 23, 262 ; Jour. Chem. Soc., 91, 1973.
different solubilities of the crystalline compounds of the acid phthalates
of the alcohols, with alkaloids such as cinchonine, or with laevo-menthyl-
amine. The specific rotations which these chemists consider accurate
for borneol are very concordant for the two optical varieties. The values
obtained are:—
Dextro-borneol [a]D = + 37*08° (in alcohol)
Laevo-borneol [a]o = - 37*61° ,, ,,
The corresponding figures for isoborneol are as follows :—
Dextro-isoborneol [a]D = + 34-02° (in alcohol)
Laevo-isoborneol [o]D = - 34*34° „ „
ISOBORNEOL.
Isoborneol, C10H17OH, is an alcohol stereoisomeric with borneol,
which it closely resembles in general characters. It is obtained, together
with borneol, by reducing camphor with sodium, or it may be prepared
by hydrating the terpene camphene by means of acetic and sulphuric
acids. The following 1 is the best method for the preparation of this
alcohol. One hundred grams of camphene are heated with 250 grams
of glacial. acetic acid and 10 grams of 50 per cent, sulphuric acid to 60°
for four hours and the mixture continually shaken. When the reaction
is complete, excess of water is added, and the ester, isobornyl acetate,
separates as an oily mass. Free acid is removed by shaking the oil in
& separator with water until the water is neutral. The ester is then
saponified by boiling with alcoholic potash under a reflux condenser.
The greater part of the alcohol is distilled off, and the residue is poured
into a large quantity of water. Isoborneol is precipitated as a solid mass,
which is filtered off, washed with water, dried on a porous plate and
recrystallised from petroleum ether. Prepared in this manner, isoborneol
melts at 212° (but see Henderson's and Heilbron's results, supra). It is
moreover, so volatile that the determination of its melting-point must be
made in sealed tubes.
Its specific rotation is + 34°.
Isoborneol yields camphor on oxidation, but it yields camphene on
dehydration much more readily than borneol does. If a solution of
isoborneol in benzene be heated with chloride of zinc for an hour, an
almost quantitative yield of camphene is obtained. Pure borneol under
the same conditions is practically unchanged.
Isoborneol forms a phenylurethane, C6H5NH. CO . O . C10H17, melting
at 138° to 139°, which is identical with the melting-point of borneol
phenylurethane.
Isobornyl formate is a liquid of specific gravity 1*017, and boils at
100° at 14 mm.; isobornyl acetate has a specific gravity 0*9905, and
boils at 107° at 13 mm.
The following table exhibits the principal difference between borneol
and isoborneol:—
1
Jour, prakt. Cliem., New Series, 49, 1.
Borneol. Isoborneol.
Crystalline form . . . . — double refraction + double refraction
Melting-point . . . . 204° (208° ?) 212° (217°
Solubility in benzene at 0° Iin7 1 in 3
,, ,, petroleum ether at 0° 1 in 10 to 11 1 in 4 to 4-5
Melting-point of phenylurethane . 138° 138°
„ ,, ,, chloral compound 55° to 56° liquid
„ „ bromal 104° „ 105° 72°
,, ,, ,, acetic ester 29° liquid
With zinc chloride unchanged forms camphene
Specific rotation 37° 34°
PlPEKITOL.
Piperitol is a secondary alcohol, corresponding with the ketone,

piperitone, occurring in several of the so-called peppermint group of
eucalyptus oils.1
It is a liquid of the formula C10H18O, having the following char-
acters :—
Specific gravity a t 2 2 ° . . . 0-923
Its constitution is probably :—
CH . CH
HCl/CHOH
C. C,H7
CAMPHENE HYDKATE.
2
Aschan has recently prepared a new alcohol from camphene, which
is not identical with isoborneol. He obtained it by digesting camphene
monohydrochloride with a solution of calcium hydroxide for about
eighteen hours with continual agitation. The camphene hydrate so
formed is a crystalline compound, highly refractive, and melting at
150° to 151°. It boils at 205°. It differs very markedly from borneol
and isoborneol by yielding camphene on dehydration with the greatest
ease, even when the mildest dehydrating agents are used.
Camphene hydrate is a tertiary alcohol, and a study of its characters
and method of preparation caused Aschan to consider that it is im-
probable that borneol and isoborneol are stereoisomeric, but that they
probably have different constitutional formulae.
MYRTENOL.
Myrtenol, Cj0H16O, is a primary cyclic alcohol, which was isolated
from essential oil of myrtle, in which it 8occurs principally in the form of
its acetic ester, by von Soden and Elze. It is separated from geraniol,
with which it is found, by fractional distillation, and by the crystallisa-
1
Baker and Smith, A Research on the Eucalyptus, 2nd edition, p. 373.
2 3
Berichte, 41, 1092. Chem. Zeit., 29 (1905), 1031.
tionjof its acid phthalate, which melts at 116°. Myrtenol has an odour
of^myrtle, and possesses the following characters :—
,, ,, ,, 9 mm. 102° „ 105°
The above figures are those of Semmler and Bartelt,1 those of
yon Soden and Elze being as follows :—
Boiling-point at 751 mm. 220J to 221°
,, ,, ,, 3-5 mm. 79-5° „ 80°
Optical rotation -f 49° 25'
Myrtenol forms an acetic ester, quantitatively, so that it can be de-
termined by acetylisation.
With phosphorus pentachloride it yields myrtenyl chloride, C10H15C1,
which by reduction with sodium and alcohol yields pinene.
On oxidation with chromic acid in acetic acid solution, myrtenol
yields a corresponding aldehyde, which has been termed myrtenal. This
body has the following characters :—
Formula C10H140
Melting-point of semi-carbazone 230°
., „ .. oxime . 71° to 72°
Myrtenol, according to Semmler and Bartelt, has the following con-
stitution :—
C . CH2OH
CH
SANTELOL.
There exists in East Indian sandalwood oil an alcohol, of the
formula C9H16O, which has been named santelol, or santenone alcohol.
It is closely allied to, and much resembles, the alcohol obtained by the
hydration of the hydrocarbon, santene (q.v.), and is probably stereo-
isomeric with it. There is some difference of opinion as 2to the proper
nomenclature of the two alcohols. According to Charabot, the naturally
occurring alcohol, also obtainable by the reduction of santenone, is
analogous to borneol, and should therefore be termed, if that analogy is
1
Berichte, 40
(1907), 1363.
2
Les Principes Odorants des Vegetaux, p. 100.
to be used in the nomenclature, 7r-nor-borneol, whilst the name ?r-nor-
isoborneol should be reserved for the isosantelol, which results from the
hydra tibn of santene. The two alcohols are probably stereoisomeric,
and the names assigned to them are exactly reversed by Semmler and
Schimmel, who term the alcohol obtained by the hydration of santene,
santelol or 7r-nor-borneol. Both alcohols are probably of the following
constitution : —
CEL
CHOH
HoC
Santelol can be purified by conversion into its phthalic acid ester,

which is liquid, but which forms a silver salt which does not melt even
at 230°.
It is a solid body melting at 58° to 62°, and boiling at 196° to 198°.
7r-Nor-isoborneol, obtained by the hydration of santene, or by boiling
teresantalic acid with formic acid, has the following characters : —
Boiling-point 87° to 88° at C9 mm.
Melting-point 68° to 70
It forms an acetate having the following characters : —
Formula CnH18O.,
Boiling-point 89 to 90-5° at 9 mm.
Molecular refraction 50 '47
The above \ figures are given for the alcohols based on the nomen-
clature advocated by Charabot as mentioned above.
APOPINOL.
Apopinol, C10H18O, is an alcohol, which has been identified in a
Japanese essential oil by Keimaza.1 It yields citral on oxidation, and
it is not certain that it is in fact a chemical individual, being, possibly,
an impure form of linalol.
KESSYL ALCOHOL.
Kessyl alcohol, C14H24O2, has been isolated from Japanese valerian,
or Kesso, oil. It is a solid compound forming fine rhombic crystals and
having the following characters : —
1
Jour. Pharm. Soc., Japan (1903), August.
„ „ 760 „ 300° „ 302°
It forms an acetic ester, which boils at 178° to 179° at 16 mm., and

has an optical rotation - 70° 6'. Its formula is C14H23O2. OC . CH3.
SANTALOL.
There exist in sandalwood oil (from Santalum album) two isomerie
sesquiterpene alcohols, of the formula C15H24O. They are both primary
unsaturated alcohols, one being bicyclic, the other tricyclic. These two
alcohols are termed a-santalol and /3-santalol.
a-santalol has the following characters :—
„ at 8 mm 155°
Specific rotation 4- 1° 6'
The specific gravity, refractive index, and specific rotation given
above are those recorded by Paolini and Divizia1 and are probably ac-
curate since the a-santalol was prepared by regeneration from its strych-
nine phthalate. The values recorded for commercial santalol, prepared
by fractional distillation, are as follows, and are the average values for
the mixed santalols as they occur in sandalwood oil :—
Semmler. v. Sodeu. Schimmel.
Specific gravity . 0'973 at 20° 0-976 to 0'978 0-973 to 0*982
Optical rotation . - 21° - 16° 30' to - 20° - 14° „ - 24°
Refractive index . 1-50974 — 1-5040 „ 1-5090
Schimmel gives the following figures for a-santalol,k but those of
Paolini and Divizia are probably more accurate :—
/2-santalol has the following characters :—
10 168° „ 169°
Specific rotation . - 42°
These values, except the boiling-point at 760°, are those of Paolini

and Divizia. Schimmel gives the following figures :—
„ ,, 14 ,, 170° „ 171°
Specific gravity 0'986S at 0°
Optical rotation . ' - 56°
According to Paolini and Divizia (loc. tit.}, the two santalols can be
separated in the following manner : They are first separated as far as
possible by careful fractional distillation, and the impure fractions con-
verted in the usual manner into the hydrogen phthalate aad this again
1
Atti. R. Accad. Lincei, 1914 (v.), 28, ii. 226.
into the strychnine salt. By repeated recrystallisation the strychnine
salt can be purified until the melting-point and rotatory power are con-
stant. When this point is reached, saponification yields the pure alcohol.
The strychnine phthalate has the following formula :—
C6H4(CO,. C15H23) (CO 2 H.C 21 H 22 O 2 N 2 ).
By oxidation of the santalols, an aldehyde, or mixture of aldehydes,
is obtained, which has been termed santalal. It has the formula C15H220,
and the following are its physical characters :—
Optical rotation + 13° to H- 14°
Melting-point of oxime . 104° to 105°
„ ,, „ semi-carbazone 230°
\Semmler regards the body nor-tricyclo-ecsantalane, C10H1G, as the
parent substance of all the santalol derivatives. It is obtained by de-
composing the ozonide of santalol in vacuo.
The acetic esters of the two santalols have been prepared, but their
absolute purity has not been substantiated.
a-santalyl acetate boils at 308° to 312°, and /?-santalyl acetate at 316°
to 317°.
The formulae i suggested by Semmler for the two santalols are as
follows : —
CH2 CH
. CH : CH . CH2CH2CH2 . OH
H2C CH.,
CH
a-Santalol.
\CH . CH : CH . CH 2 . CH,. CH 2 . OH
CH,
3-Santalol.
AMYEOL.
The alcohols of the so-called West Indian sandalwood oil, which is
distilled from a species of Amyris, are known under the name of amyrol.
It is, in all probability a mixture of two alcohols of the formulas C15H240
and C15H260. Its characters are as follows :-
151° „ 152° ,, 11 „
Amyrol has been partially separated into its constituents —of which
tlie higher boiling is probably of the formula C15H26O, and has a specific
gravity 0*987, optical rotation -f 36°, and boiling-point 299°. The lower
boiling alcohol appears to have the formula C15H24O, and to be optically
inactive,
CEDROL AND PSEUDOCEDROL.
Cedrol, C15H26O, is a true sesquiterpene alcohol occurring in cedar-
wood oil (Juniper us virginiana) and several allied essential oils.
It is a crystalline substance having the following characters : —
Melting-point ......... 86° to 87°
Boiling-point . ....... 291° „ 294°
„ at 8 mm ........ 157° „ 160°
Specific rotation (in chloroform) ..... + 9° 31'
It yields a phenylurethane if it is heated almost to boiling-point

with phenyl-isocyanate. This compound melts, at 106° to 107°. On de-
hydration with phosphoric acid it yields the sesquiterpene cedrene.
The relationship between cedrene and cedrol is probably as follows : —
C=CH
=C C(OH)— CH2
Cedrene. Cedrol.
x
Bernini er and Mayer have isolated a physical isomer of cedrol from
the same oil, which they have named pseudocedrol. This alcohol was
obtained by systematic fractionation of the oil, and was found to accumu-
late in the traction which distils between 147° and 152° at 9 mm. pressure.
Pseudocedrol is a saturated tertiary alcohol having the following char-
acters : —
Specific gravity at 20° ........ 0-9964
Optical rotation ......... + 21° 30'
When pseudocedrol is heated in a sealed tube at 235° it yields a
mixture of dihydrocedrene, C15H26, and cedrene, C15H24.
According to Semmler and Mayer, cedrol and pseudocedrol are of
the same chemical constitution, the two bodies being physical isomer s.
CEDBENOL.
In addition to cedrol and pseudocedrol, cedar- wood oil contains a
third alcohol, of the formula C15H240, which has 2been named cedrenol.
This alcohol was isolated by Semmler and Mayer, who found it to exist
to the extent of about 3 per cent, in the oil. It is a tricyclic unsatur-
ated alcohol, closely related in constitution to the sesquiterpene cedrene,
.as shown by the following formulae : —
J 2
Berichte, 45, 1384. Ibid., 45, 786.
(C12H20) (C12H20)
C=CH C = CH
CH2 GH2—OH
Cedrene. Cedrenol.
Cedrenol has been isolated in a state of purity by means of its phthalic
acid ester. i
It is a viscous, colourless liquid, having the following characters':—
It was, however, probably not quite pure, when obtained in this
manner. It forms an acetic ester, having the following characters :—
When regenerated by saponification of the acetic ester, cedrenol was
found to have the following characters :—
By the action of phosphorus pentachloride, cedrenol yields cedrenyl
chloride, C15H23C1, which, when reduced by sodium and alcohol yields
cedrene.
CADINOL.
Semmler and Jonas l have isolated a sesquiterpene alcohol, C15H260,
from oil of galbanum. It yields a hydrochloride melting at 117° to 118°..
VETIVENOL.
2
Genvresse and Langlois isolated an alcohol of the sesquiterpene
group of the formula C15H94O from oil of vetiver, which they named
vetivenol. This alcohol has been examined by Semmler, Risso, and
Schroeter.3 From the fraction boiling at 260° to 298° at 13 mm. they
obtained an ester of vetivenol, C15H24O, with an acid of th^ formula.
C15H92O2. On hydrolysis the alcohol was obtained, which had the
This alcohol possesses only one double bond, and must be tricyclic.
It is a primary alcohol, yielding a phthalic acid ester. On reduction
1 2
Berichte, 47 (1914), 2068. Comptes rendus, 135, 1059.
" Berichte, 45, 2347.
with hydrogen and spongy platinum, it yields dihydrovetivenol, C15H260,,
' a true sesquiterpene alcohol, having the following characters :—
Dihydrovetivenol forms an acetic ester, whose characters are as
follows:—
Optical rotation + 2^° 48'
There was also obtained from the oil a second alcohol, C15H24Or
which contains two double bonds, and is bicyclic. It is also a primary
alcohol, but its characters have not been ascertained with accuracy.
A mixture of bicyclic and tricyclic vetivenol isolated by means of phthalic
acid had the following characters, from which those of bicyclic vetivenol
may, to some extent, be deduced :—
Boiling-point at 14 mm 168° to 170° .
ZlNGIBEROL.
1
Brooks has isolated from the fraction of oil of ginger boiling at 154°
to 157° at 15 mm. an alcohol which he finds to be a sesquiterpene
alcohol, Cl5H26O, corresponding to the sesquiterpene zingiberene. It has
the fragrant odour of ginger, and probably possesses one of the following
constitutions:—
C(CH3)2OH C(CH3) : CH,
CH,
CH . CH . C(CH3)CH . CH2 H2C CH . CH2. C(CH3)(OH)CH: CH2

CH(CH3) C(CH3)
GUAIOL.
Guaiol, C15H26O, is an odourless sesquiterpene alcohol found in the
essential oil of the wood of Bulnesia Sarmienti, known as guaiac wood
oil.
It is obtained by extracting the wood with ether, and several times
recrystallising the pasty mass so obtained from alcohol.
Guaiol is a tertiary bicyclic alcohol, with one double linkage, having
Melting-point 91°
Boiling-point a t 9 m m . . . . . . . . 147° t o 149°
9O°
Specific gravity — 0-9714
Refractive index . . . . . . . . 1'5100
1
By acting on guaiol with potassium in alcohol, and adding methyl
iodide, guaiol methyl ether is formed, which has the following char-
.acters:—
OKO
Specific gravity at ±*i 0-9332
„ rotation - 31-8°
Refractive index at 18'5° 1-48963
If guaiol be shaken in aqueous acetone with potassium permangan-
ate a glycerol results, which is the first body of its type known in the
sesquiterpene series. This body, guaiol glycerol, C15H28O2, forms
colourless tablets, melting at 210° to 211°, and is suitable for the identi-
fication of guaiol.
CLOVE SBSQUITEBPENE ALCOHOL.
Semmler and Mayer1 have isolated a sesquiterpene alcohol, C15H260,
from the high boiling fractions of oil of cloves. It was probably not
obtained in an absolutely pure condition, but had the following char-
acters, which must be regarded as approximate only:—
Optical dotation -17°
Refractive index f . . . . 1-5070
It yields a chloride, C15H25C1, of specific gravity 0*990 at 20°. It is
a bicyclic sesquiterpene alcohol, with one double bond.
LEDUM CAMPHOR.
Ledum camphor, C15H260, is a solid sesquiterpene alcohol present
in the essential oil of Ledum palustre. It forms long, colourless needles
Melting-point 104°
Boiling-point 281°
9O°
On dehydration it yields the sesquiterpene ledene, which has scarcely
been investigated.
COSTOL.
Semmler and Feldstein2 have isolated a sesquiterpene alcohol,
C15H24O, from the oil of costus root, to which they have given the name
costol. It was purified by conversion into its acid phthalate, which, on
hydrolysis yields the pure alcohol, having the following characters:—
Refractive index . . . . . . . . 1 -5200
Optical rotation 4- 13°
1
Berichte, 45 (1912), 1390. Ibid., 47 (1914), 26S7.
Costol is a diolefinic bicyclic sesquiterpene alcohol, which, on oxida-
tion by chromic acid in acetic acid yields an aldehyde, C15H22O, which
yields a semi-carbazone, melting at 217° to 218°. This aldehyde, wrlich
is triolefinic has the following characters :—
Optical rotation . . +24°
Costol forms an acetic ester, having a specific gravity 0-9889 at 21°

and optical rotation + 19°.
ELEMOL.
Semmler and' Liao1 have examined the solid body isolated from
Manila elemi oil by Schimmel & Co. This was found to be a sesqui-
terpene alcohol, C]5H26O, which has been named elemol. It was
purified by converting it intov its benzoic acid ester, from which the
alcohol was prepared in a pure state by hydrolysis. It has the following
characters:—
Its benzoic ester has the following characters :—

On reduction elemol yields tetrahydroelemol, C15H300. Elemol is

a monocyclic sesquiterpene alcohol, and on dehydration yields the sesqui-
terpene elemene.
According to Semmler and Liao 2 tetrahydroelemol has the following
characters:—
Melting-point . 35-5°
By treatment with formic acid, it yields tetrahydroelemene. The
constitution of this body, which throws some light on that of elemol, is
probably as follows :—
C—CH(CH3)2
.CH.(C5Hn)
CH(CH3)
1
Berichte, 49 (1916), 794. *Ibid., 50 (1917), 1286.
JUNIPEROL.
1
-Eamsay has isolated a crystalline sesquiterpene alcohol from the
essential oil distilled from the bark of the juniper tree. It forms
optically inactive triclinic crystals, melting at 107°, and having the
formula C15H240.
EUDESMOL.
Eudesmol is a sesquiterpene alcohol, isolated from several species of
eucalyptus oil by Baker and Smith, who 2 regarded it as an oxide of the
formula C10H16O. Semmler and Tobias have, however, shown that it
is a tricyclic, unsaturated alcohol. It has the following characters :—
Boiling point at 10 mm. 156°
,, rotation (in chloroform) + 38° to 43°
Molecular refraction . 67-85.
It forms an acetate, which boils at 165° to 170° at 11 mm. By re-
•duction with hydrogen and spongy platinum, it yields dihydroeudesmol,
an alcohol melting at 82°. On dehydration it yields a sesquiterpene,
eudesmene. Eudesmol appears to have a tendency to liquefy by keeping.
Whether the liquid body is an isomer or not is unsettled.
GLOBULOL.
This sesquiterpene alcohol was discovered by Schimmel & Co. in oil
•of Eucalyptus globulus. It is found in the last fractions of the distillate,
separating out in crystalline condition. On recrystallisation from 70
per cent, alcohol, it was obtained in the form of brilliant, almost odour-
less needles, having the following characters :—
Melting-point . . . 88-5°
Boiling-point at 755 mm. . 283°
Specific rotation . . . - 35° 29' (12 per cent, chloroform solution)
Its formula is C15H26O.
Schimmel & Co.a attempted to acetylise the alcohol by means of acetic
anhydride, but the reaction product only showed 5 per cent, of ester,
which was not submitted to further examination. The bulk of the
alcohol had been converted into a hydrocarbon, with loss of water.
Ninety per cent, formic acid is most suitable for splitting off water.
One hundred grams of the sesquiterpene alcohol were heated to boiling-
point with three times the quantity of formic acid, well shaken, and, after
•cooling, mixed with water. The layer of oil removed from the liquid
was freed from resinous impurities by steam-distillation, and then
fractionated at atmospheric pressure. It was then found to consist of a
mixture of dextro-rotatory and laevo-rotatory hydrocarbons. By repeated
fractional distillation, partly in vacuo, partly at ordinary pressure, it was
possible to separate two isomeric sesquiterpenes, which, after treatment
with aqueous alkali, and distillation over metallic sodium, showed the
following physical constants :—
2
iZeit.f. Kristallogr., 46,3 281. Berichte, 46 (1913), 2026.
1. 2.
Boiling-point . . . . 247° t o 248° 266°
Optical rotation - 55° 48' + 58° 40'
Semmler and Tobias l consider that eudesmol and globulol are related
in the same manner as \borneol and isoborneol.
PATCHOULI CAMPHOR.
Patchouli camphor, C15H26O, is a solid alcohol found in oil of
patchouli. It is a crystalline body having the following characters:—
Melting-point 56°
Specific rotation . . . . . . . 118° ( i n fused state)
„ „ - 97° 42' (in chloroform)
On dehydration it yields patchoulene, a sesquiterpene which has not
been i investigated.
CUBEB CAMPHOR.
Cubeb camphor, C16H26O, is a sesquiterpene alcohol which is found in
oil of cubebs, especially in old samples of the oil. It is laevo-rotatory,
melts at 68° to 70°, and boils at 248° with decomposition. Nothing is
known of its constitution.
MATICO CAMPHOR.
This sesquiterpene alcohol is found in old samples of Matico leaf oil.
It is a crystalline body, of the formula, C15H26O, melting at 94°, and of
specific rotation — 28*73°, in chloroform solution.
GONOSTYLOL.
This body, Cl5H26O, exists in the oil of Gonystilus Miquelianus. It

Melting point 82°
Specific rotation + 30° (in alcohol)
On dehydration it yields the sesquiterpene, gonostylene.
BETULOL.
Betulol is a sesquiterpene alcohol of the formula C15H24O, found in
oil of birch buds. It can be isolated as a hydrogen phthalate, by warming
a solution of betulol in benzene, with phthalic anhydride. It has. ac-
cording to Soden and Elze, the following characters:—
4 mm. 138° „ 140°
^Berichte, 46(1913), 2030.

It forms an acetic ester boiling at 142° to 144° at 4 mm. pressure, of
specific gravity 0*986.
This alcohol has, however, been quite recently reinvestigated by
Semmler, Jonas, and Eichter.1 They consider that it is a bicyclic sesqui-
terpene alcohol whose characters are as follows:—
Specific gravity at 16° . . . . . 0-9777
By the action of phosphorus pentachloride it yields betulyl chloride,
a partial molecular rearrangement having apparently taken place, since,
on hydrolysis, it yields a tricyclic betulol which is of particular interest
in that it is the first tricyclic sesquiterpene alcohol of a crystalline char-
acter to be discovered. Its characters are as follows :—
ATKACTYLOL.
Atractylol, C15H26O, is a sesquiterpene alcohol which forms the
principal constituent of the oil of Atractylis ovata. It is a tertiary tri-
cyclic alcohol, having the following characters :—
Melting-point 59°
at 15 mm. 162°
CAPAEKAPIOL.
Caparrapiol, C15H26O, is a sesquiterpene alcohol found in the oil of
Nectandra Caparrapi. It has the following characters :—
GALIPOL.
Galipol is a sesquiterpene alcohol of the formula C15H26O, found in
oil of Angostura. It has the following characters :—
It is a very unstable compound.
MAALI SESQUITERPENE ALCOHOL.
There exists in the essential oil of Maali resin a sesquiterpene
alcohol, C15H26O, corresponding with the sesquiterpene which has al-
ready been described. It has the following characters :—
Melting-point 105°
Boiling-point 260°
Specific rotation + 18° 33'
1
Berichte, 51 (1918), 417.
OPOPONAX SESQUITERPENE ALCOHOL.
A sesquiterpene alcohol, C15H26O, has been extracted by means of
phthalic anhydride from oil of opoponax resin. It distils at 135° to
137° in vacuo (2 imm.), and yields a crystalline phenylurethane. But
as, in spite of repeated crystallisations, it could not be obtained of con-
stant melting-point, it is probable that the substance is a mixture of two
or more alcohols.
4. ESTERS.
It will now be convenient to pass on to that very important group
of compounds, the esters.1 An ester is a combination of an alcohol with
an acid, the combination being associated with the elimination of water.
For example, ordinary ethyl alcohol combines with acetic acid to form
the ester, ethyl acetate, according to the following equation : —
C2H5OH + HOOC . CH3 = C2H5OOC . CH3 + H2O
>-', Alcohol. Acetic Acid. Ethyl Acetate. Water.
The esters play a most important part in the economy of plant life,
and are highly important constituents of numerous essential oils. In-
deed, in many cases they are the dominating constituent, and the oil
may be said to owe its perfume value largely, or in some cases almost
entirely, to the esters it contains.
In dealing with natural perfumes it must be remembered that when
one speaks of, for example, lavender oil containing 35 per cent, of linalyl
acetate, or geranium oil containing 30 per cent, of geranyl tiglate, these
are merely convenient forms of expression, and give a conventional
method of expressing the ester value. For the esters are really merely
calculated from analytical results to a given formula ; whereas, in fact,
in nearly every essential oil containing esters there is a predominating
ester associated with several others in smaller quantities which are im-
possible to separate, and are all expressed in terms of the predominating
ester. The recognition of these subsidiary esters is of the highest im-
portance, since it enables the scientist to prepare the various synthetic
esters and blend them in minute quantities so as to give a long scale of
modified odours. Indeed, the synthetic esters form one of the most
important portions of the price list of the synthetic perfume manu-
facturer. The following are the general methods for the artificial pre-
paration of esters : —
1. By the interaction of the alcohols and acids at an elevated
temperature; the reaction is assisted by the use of some catalytic agent,..
or one which absorbs the water formed, such as dry sodium acetate.
The reaction is rarely complete, however, and may be rendered more
nearly quantitative by 'using the acid anhydride in place of the acid:
itself. The reaction is : —
2R . OH + O = 2E . O . OCE + H2O, when E is an alkyl radicle.
2. By the interaction of the silver salt of the acid with the halogen
derivatives of the alcohol, when the reaction is as follows : —
AgN03 + C.2H6I = C2H6N03 + Agl.
ir
The section on the esters, is, in the main, reproduced from a monograph by the
author in the Perfumery and Essential Oil Record, July, 1913.
VOL. II. 11
3. By acting on the alcohols with acid chlorides, as, for example :—
C2H5OH + C6H5COC1 = C2H5OOC . C6H5 + HC1.
To decide whether an ester is present in a mixture of compounds,
such as a compound synthetic perfume, is a matter of no great difficulty.
A weighed quantity, from 2 to 5 grams, according to the probable amount
of ester present, is dissolved in a very small quantity of alcohol and a
few drops of phenolphthalein solution added. An alcoholic solution of
caustic potash is added drop by drop from a burette until all free acid is
neutralised, as indicated by the liquid assuming an intense red colour.
A measure! quantity of the alcoholic potash solution is then run into the
flask, 25 c.c. of semi-normal alkali usually being sufficient, and an exactly
equal volume run into another flask. The contents of the two flasks
are then boiled for an hour under a reflux condenser, and after an hour
are cooled and the amounts of alkali present determined by means of
semi-normal acid. If the amount of alkali left in the flask containing
the sample is less than that in the " blank " flask, the difference has
been absorbed in saponifying the esters present, breaking them down
into the respective alcohols and acids. So that this consumed alkali is
a measure of the amount of esters present. If an investigation into the
nature of the esters present is necessary, it must be remembered that
after the saponification the alcohol resulting is almost invariably an in-
soluble oil, so that by diluting the reaction mass with water the resulting
alcohol, together with the other compounds of the sample, will float as
an oily layer on the surface of the liquid, and this oily layer must be in-
vestigated in the usual manner. The acid, however, formed by the
decomposition of the ester is usually soluble in the aqueous liquid, which
can be separated from the oil, and the acid distilled off if volatile, or
precipitated as a silver salt if non-volatile.
Some oils consist almost entirely of esters ; for example, those of
<Gaultheria procumbens and Betula lenta contain about 99 per cent, of
methyl salicylate. Bergamot and lavender owe the greater part of their
perfume value to esters of linalol, of which the acetate predominates.
Geranium oil owes its fragrance chiefly to geranyl esters, of which the
tiglate is the chief. On the other hand, oils such as spike lavender,
sandalwood, lemon-grass, and citronella contain but small quantities of
esters, and owe their perfume value to entirely different types of com-
pounds.
ESTERS OF METHYL ALCOHOL.

Methyl alcohol, CH3OH, is the lowest member of the paraffin
alcohols, and although it occurs to a small extent in the free state in a
few essential oils it is not a perfume material at all, and, being very
soluble in water, is entirely washed out of the oil by the distillation
waters. There are, however, a number of highly odorous esters ot
methyl alcohol which are indispensable in synthetic perfumery. These
are as follows :—
Fatty Acid Esters of Methyl Alcohol.—The following esters of methyl
alcohol are commercial products, and all have fruity odours, and are
very suitable for blending with flower oils to impart distinctive secondary
odours to them. They are, generally speaking, very expensive, some
of them costing as much as £12 per lb., but, as only minute quantities
are used, the actual cost is not very material. They may be identified
by the melting-point of the fatty acid yielded on saponification :—
Melting-point of
Fatty Acids.
Methyl caprinate, CH3(CH2)8COoCH« . . 31° to 32°
caprylate, CH3(CH2)6CO2CBU( . 16° „ 17°
heptoate, CH3(CH2)5CO,,CH3 - 10°
laurinate, CH3(CH2)]0Cb2CHn 43° to 44°
nonylate, CH3(CH2)7CCX,CH, " 12° „ 13°
^ Methyl Anisate.—Methyl alcohol forms an ester with anisic acid,

having the formula C6H4(OCH3)(COOCH3). It is a crystalline body
with a fine chervil odour.
Methyl Anthranilate.—This ester is one of extreme importance, and
to it is largely due the possibility of manufacturing artificial neroli oils.
It was discovered as a constituent of neroli oil in 1895 by Walbaum,
and has since been identified in numerous other flower oils, such as
tuberose, ylang-ylang, jasmin, and gardenia. Its value in synthetic per-
fumery is therefore obvious. Its constitution is that of a methyl ester
or ortho-amido-benzoic acid, of the formula here shown :—
CH
1
TTP
HC I r "MTT
^C.NH 2
C . COO . CH,
It is prepared artificially in various ways, most of which depend on the
preliminary synthesis of the acid, which is then converted into its methyl
ester. Anthranilic acid is prepared by the reduction of or£/&0-nitro-benzoic
acid, with tin and hydrochloric acid ; or from phthalimide by treatment
with bromine and caustic potash. The ester is prepared directly from is-
atoicacid (anthranil-carbonic acid), C6H4(CO)(NCO2H), by treatment with
methyl alcohol and hydrochloric acid. Methyl anthranilate is a crystal-
line substance melting at 24° to 25°, whose solutions have a beautiful
blue-violet fluorescence, which is apparent in all oils containing it. It
boils at 132° at 14 mm., and has a specific gravity 1-168. It possesses a
powerful odour similar to that of oil of neroli and similar flower oils,
its identification is easy, since on saponification it yields anthranilic acid,
melting at 144° to 145°. It also yields a picrate, melting.at 104°. It
can be estimated quantitatively by the method proposed by Hesse and
Zeitschel. About 25 to 30 grams of the sample are dissolved in two to
three times its volume of dry ether. It is cooled in a freezing mixture,
and then a mixture of 1 volume of sulphuric acid and 5 volumes of
ether are added slowly, drop by drop, until no further precipitation
takes place. The whole of the methyl anthranilate is thus precipitated
as sulphate. This is collected and washed with ether and weighed, or
it may be titrated with semi-normal potash solution. If p be the weight
of oil employed andw the number of c.c. of semi-normal alkali used, then
the percentage of methyl anthranilate is *
Minute quantities of the ester may be quantitatively determined by
diazotising the ester and observing its colour reaction with either /3-
naphthol or dimethylaniline, against a standard solution of the ester.1
Methyl Benzoate.—This highly odorous ester has the composition
CHgOQC . C6H5. It is present in the oils of ylang-ylang, tuberose, and
cloves, etc., and is also known in commerce as Niobe oil. It is a colour-
less, optically inactive liquid of fragrant odour, and is a necessary con-
stituent of odours of the ylang-ylang type. It is a favourite ingredient
in the perfume known as Peau d'Espagne, and blends well with santal,
musk, geranium, or rose. It can be prepared by passing a current of
dry hydrochloric acid gas into a solution of benzoic acid in methyl
alcohol. The mixture is heated to 100° for several hours, and the re-
sulting ester then precipitated with water. Pure methyl benzoate has
the following characters : It boils at 199° at 760 mm., has a specific
gravity 1*1026, and refractive index 1*5170. It should be free from
chlorine, which may be tested for in the manner described under
benzaldehyde. Methyl benzoate may be characterised by its forming a
crystalline compound with phosphoric acid, which the benzoic esters of
homologous alcohols do not.
Methyl Cinnamate.—This ester, which occurs in various balsamic
products, has the constitution C 6 H 5 . CH : CH . COOCH3. It is an oily
body with a penetrating fruity odour, and is of great value in the pre-
paration of perfumes for such articles as toilet vinegars, smelling salts,
etc. It can be prepared by the condensation of methyl alcohol and
cinnamic acid by means of dry hydrochloric acid in the same way as
methyl benzoate. It forms a low melting crystalline mass having the
Refractive index 1-56816 „ 35°
Boiling-point 256 at 745 mm.
„ 262° to 265° at 760 mm.
Methyl Malonate.—This ester is an artificially prepared body, having
a fruity odour, somewhat similar to the above-described esters of the
fatty acids. It has the formula CH2(CO2CH3)2, and boils at 181°. It
may be prepared by treating potassium cyan-acetate with methyl alcohol
and hydrochloric acid. On saponification with alcoholic potash it yields
malonic acid, which melts at 132°, and serves well for the identification
of the ester.
Methyl Methyl-anthranilate.—This ester is quite similar in all its
characters to methyl anthranilate. It has the constitution—
C6H4(NH . CH3)(CO . OCH3),
that is, one of the hydrogen atoms in the amido group of the anthranilic
acid has been substituted by a methyl group. Its odour and fluorescence
are quite similar to those of methyl anthranilate, and its estimation may
be effected in the manner described for that ester. Its identification is
easy, as it yields methyl-anthranilic acid, melting at 179° on saponifica-
tion. The ester melts at 18*5° to 19*5°, boils at 130° to 131° at 13 mm.,
is optically inactive, and has a specific gravity 1*1238 at 20°, and a re-
fractive index 1*57963.
Methyl Phenyl-acetate. — Phenyl-acetic acid can be prepared by
1
Berichte, 35, 24 (1902); J. Amer. Chem. Soc., 1921, 377.
chlorinating toluene, thus converting it into benzyl chloride, which

is then converted into benzyl cyanide, which, on digestion with sul-
phuric acid, yields phenyl-acetic acid or a-toluic acid. This is con-
densed with methyl alcohol, forming the methyl ester of the formula
C6H5. CH 2 . COOCH3. It has a powerful " honey" odour, and is very
useful in scent bases of this type.
Methyl Phenyl-propionate.—Phenyl-propionic acid, also known as
hydrocinnamic acid, forms a methyl ester of the formula
C,H5. CH 2 . CH2COO . CH3.
The acid is obtained by the reduction of cinnamic acid by means of
sodium amalgam. The acid is then esterified by the condensing action
of a mineral acid in methyl alcohol solution. The ester is an oil of very
sweet oiour, and is very useful for flower bouquets.
Methyl Salicylate.—This ester is practically identical with oil of winter-
green or oil of sweet birch, both of which contain about 99 per cent, of
the ester. It is also present in numerous other plants, and its artificial
production is carried out on a very large scale. The artificial ester is
quite suitable for replacing the natural oil, and is used to a very large
extent for flavouring tooth powders, pastes, and washes, being exceed-
ingly popular in America. The ester has the constitution
CtfH4(OH)(COOCH8).
The best method for producing it artificially is to condense salicylic
acid and methyl alcohol by means of sulphuric acid. It is a colourless
oil, optically inactive, and possessing an intense wintergreen odour. It
Specificgravity at 0° . 1-1969
„ ,, 16° 1-1819
Boiling-point 224°
Melting-point - 8° to - 9°
Solubility . 1 in 6 to 8 volumes of 70 per cent, alcohol
ESTERS OF ETHYL ALCOHOL.

Ethyl Acetate.—This ester does not play a very important role in
synthetic perfumery, but its intensely fruity odour, together with the
fact that it is found naturally in the perfume of the magnolia gives it
certain possibilities, if used in very minute quantities. It is an oil of
the formula CH3COO . C2H5. It boils at 76°, and has a specific gravity
0'908. It is easily soluble in the usual organic solvents, and fairly
soluble in water.
Ethyl Anisate.—Very similar to the methyl ester of anisic acid is its
ethyl ester. This is a crystalline compound of the formula
C6H4(OCH3)(COOC2H,,)
with a fine odour of chervil.
Ethyl Anthranilate.—This ester, of the formula
C 6 H 4 . (NH2)(COOC2H6),
is a liquid boiling at 260°. It can be prepared by the action of hydro-
chloric acid and ethyl alcohol on isatoic acid. It has the characteristic
neroli odour possessed by the methyl ester, but is both sweeter and
softer in perfume, and does not discolour so readily as the methyl ester.
Ethyl Benzoate.—This ester has not been found, so far, to occur
naturally in essential oils. It has, however, been prepared by synthetic
processes, for example, by condensing ethyl alcohol with ben zoic acid
by means of dry hydrochloric acid gas. Its odour is very similar to
that of methyl benzoate (q.v.), but not quite so strong. It is an oil of
specific gravity 1*0510, refractive index 1*5055, and boiling-point 213°
at 745 mm. It is soluble in two volumes of 70 per cent, alcohol.
Ethyl Butyrate.—The butyric ester of ethyl alcohol has the formula
CH3(CH2)2COO. C2H5.
It is a liquid boiling at 121°, and has a very fruity odour, very similar
to that of the pine apple.
Ethyl Valeridnate.—This ester, C4H9COOC2H5, is an oil with a pine-
apple odour. Its specific gravity is 0-894, and" boiling-point about 133°.
Ethyl Heptoate.—This ester, which has the formula
CH8(CH2)5COO . C2H5,
is also known as " oenanthylic ether," and is of a fragrant odour, re-
calling that of the secondary constituents of brandy. It is used and
sold as an artificial oil of cognac. It is an oil boiling at 187° to 188°.
Ethyl Caprylate.—This ester is an oil reminding one of the secondary
products of fermentation. It boils with decomposition at 275° to 290°,
and has the formula CH3(CH2)6COOC2H5.
Ethyl Cinnamate.—The cinnamic ester of ethyl alcohol is a natural
constituent of a few essential oils, including camphor oil and storax. It
is formed synthetically by condensing cinnamic acid and ethyl alcohol
by dry hydrochloric acid gas. It has a soft and sweet odour, and is
particularly suitable for blending in soap perfumes. It is an oil at
ordinary temperatures, melting at 12°, and boiling at 271°. Its specific
gravity is 1*0546, and its refractive index 1*5590.
Ethyl Laurinate.—The laurinic ester of ethyl alcohol has also, quite
recently, come into rogue in synthetic perfumery. It is an oil of
peculiar fruity odour, intensely strong, having the constitution
CH3(CH2)10COOC2H5.
It boils at 269°.
Ethyl Malonate.—Ethyl malonate is not a member of the paraffinoid
acid esters, but is sufficiently nearly related to this series to be included
here as a matter of convenience. It is of considerable value in modify-
ing flower odours, having a more or less characteristic apple odour, but
of a much sweeter type than the valerianic ester perfume. It is an oil
of specific gravity 1*068, and boils at 198°.
Ethyl Myristinate.—This is the highest ester of the series that is of
any practical value in perfumery. It is an intensely odorous oil, melt-
ing at 10° to 11° and boiling at 295°. Its constitution is
CH3(CH2)12COOC2H5.
Ethyl Nonylate.—This ester has, during the past year or two, been
recognised as having a most useful odour for modifying flower bouquets.
It is a fruity oil boiling at 227° to 228°, and having the constitution
CH3(CH2)7COOC2H5.
Ethyl Octylate.—This ester is a fruity oil boiling at 207° to 208°. It
has the formula CH3(C . H2)6COOC2H6.
Ethyl Phenyl-acetate.—This ester has the formula
C 6 H f> . CH 2 . COOC2H5.
It is very similar in odour and use to methyl phenyl-acetate.
Ethyl Salicylate.—The ethyl ester of salicylic acid resembles the
lower homologue, methyl salicylate, in its general characters and per-
fume value. It is an oil of specific gravity 1-1372, refractive index
1*52338, and optically inactive. It boils at 234°. It solidifies at low
temperatures, and melts at + 1-3°.
ESTERS OF AMYL ALCOHOL.
Amyl Acetate.—This is, with the exception of amyl formate, which
is not of practical importance, the simplest possible ester of amyl alcohol,
and has the formula CH 3 . COO . C5H11. It is a fruity oil, with a strong
odour resembling that ot the pear, and is known as art ficial oil of pear.
It is prepared on a very large scale by, for example, treating 100 parts
of dry sodium acetate, 100 parts of amyl alcohol, and 130 parts of
sulphuric acid for twelve hours at ordinary temperature, and then dis-
tilling off the ester. It has a specific gravity 0'876, and boils at 138°.
The alcohol in this ester is not normal amyl alcohol, but isoamyl
alcohol.
Amyl Valerianate.—This ester is an oil of strong apple odour, and is
used for the preparation of cider essence. Its formula is C5HU . C5H9O2.
Amyl Benzoate.—This ester has the formula C5Hn. (O2C)(C6H5). It
is one of the best fixatives known, and has a slight but distinct amber
odour. It is prepared by condensing amyl alcohol and ben zoic acid
with dry hydrochloric acid âs.
Amyl Heptylate.—This ester is one of the newest synthetic odours,
and is also one of the very expensive ones. It has the formula
CH3(CH2)r)COOCr)H11, and is an oil of powerful fruity odour. It can
be identified by saponifying it and examining the resulting fatty acid,
which should melt at - 10° and boil at 223°.
Amyl Salicylate.—All the perfumes of the orchid type, and many of
the Trefie variety, have amyl salicylate as one of their most important
bases. The ester is known under the names orchidee, trefle or trefoil,
and artificial orchid essence. It is used to a considerable extent in
artificial perfumery. It is a colourless liquid of the formula
Q,Hn(02C)(OH)(C6H4),
boiling at 276° to 277° at 760 mm., or at 151° to 152° at 15 mm. Its
specific gravity is about 1*052, and its refractive index is about T5055.
It is dextro-rotatory, about + 2°. It is easily identified as on saponifica-
tion it yields the characteristic odour of amyl alcohol, and salicylic acid,
which can easily be identified by the usual reactions and by its melting-
point.
ESTERS OF HIGHER FATTY ALCOHOLS.
Heptyl Heptoate.—This is one of the most recent introductions to
synthetic perfumery and one of the most expensive. It has the formula
CH3(CH2)5OOC . (CH2)5CH3. It has a fine, powerful, fruity odour.
Hexyl Acetate.—Hexyl acetate, CH3(CH2)5OOC . CH3 is an ester
found naturally in the oil of Heraclwim giganteum. It has a fruity
odour, and boils at 169° to 170°. Its specific gravity is 0'890 at 10°.
Hexyl Butyrate.—This ester is also a powerful fruit oil, and boils

at 205°.
Octyl Acetate.—This ester has the formula CH3(CH2)7. OOC . CH3.
It is an oil boiling at 207°, and has a distinct orange odour. Its specific
gravity is 0*885.
Octyl Butyrate.—This occurs naturally in a few essential oils. It is
an oil boiling at 244°. and having a strong, fruity odour. Its formula
is CH3(CH2)7OO . C . (CH2)2,CH3.
Octyl Heptylate.—This is the highest ester of the series that is found
to be useful as a perfume. It has the formula
CH3(CH2)7OOC(CH2)5CH3.
THE GERANYL ESTEKS.

The esters belonging to the geraniol series of alcohols are absolutely
indispensable in the manufacture of artificial perfumes. When it is
remembered that these esters are present in such oils as bergamot, rose,
geranium, lavender, petit-grain, neroli, and numerous other sweet-
smelling essential oils, it will readily be seen how useful they are in
building up similar perfumes artificially.
Geranyl Formate.—The lowest of the fatty acids, formic acid, forms
an ester with geraniol, having the constitution C10H17. OOC . H. It
has not, apparently, been found in nature, but it is manufactured by
allowing anhydrous formic acid to react with geraniol in the presence
of a little mineral acid to act as a condensing agent. It is an ester of
a sweet rose-geranium type, boiling at 113° to 114° at 15 mm. It is
not possible to manufacture it quite pure on a commercial scale, and
the best samples to bs met with contain about 92 per cent, of true ester.
Such samples have a specific gravity between 0*924 and 0*926 at 15°,
are optically inactive, have a refractive index 1*4640 to 1*4660, and are
soluble in 10 volumes of 70 per cent, alcohol. To decide on the quality
of a given sample, these characters should be determined and a saponifica-
tion performed quantitatively. At least 90 per cent, of geranyl formate
should be indicated. The geraniol obtained in the saponification process
should be separated, washed with water, and examined. It should have
the general characters given under the alcohol geraniol above.
Geranyl Acetate.—The acetic ester of geraniol having the formula
C10H17. OOC . CH3 is probably the most largely employed of the series.
It is found naturally in palmarosa oil, lemon-grass oil, sassafras leaf oil,
geranium oil, petit-grain oil, neroli oil, coriander oil, lavender oil, and
numerous others. It is best prepared artificially by the action of acetic
* anhydride on geraniol in the presence of anhydrous sodium acetate,
which assists the reaction materially. Geranyl acetate has an exceed-
ingly sweet odour of great fragrance. Its delicate and distinctive
perfume makes it invaluable for the preparation of the various rose
odours, and it is also very useful in the perfumes of the ylang-ylang
and orange flower type. In its pure state it has the following char-
acters :—
Specific gravity 0*9388 at 0°, or 0*9174 at 15°
Boiling-point at 14'5 mm. . . . 130° to 130'5°
,, „ 760 „ . . . 242° „ 245°
In the manufacture of geranyl acetate on a commercial scale it would

not pay to make it absolutely pure, so that samples as met with in the
ordinary way are not quite pure geranyl acetate. The acetylisation
process, by which esters are made, is not always a quantitative one,
and in some cases it is impossible to acetylate an alcohol to its full
theoretical extent. Commercial samples, however, contain 95 per cent.
or more of true ester, and should have the following characters :—
Specific gravity at 15° 0*910 to O918
Optical activity . . . . . . . 0°
Eefractive index 1-4617 to 1-4662
it should be soluble in 7 to 10 volumes of 70 per cent, alcohol; it should
contain at least 95 per cent, of true ester.
Geranyl Bitty rate.—This ester of the formula C10H17. OOC(CH2)2CH3
is an oil having a fine rose odour, distinct from the esters of the lower
fatty acids, and is largely employed in perfuming soaps, and in com-
pounding artificial otto of rose. It can be prepared by heating geraniol
with butyryl chloride in the presence of anhydrous pyridine, and is an
oil boiling at 142° to 143° at 13 mm. pressure.
Geranyl Isobutyrate.—This ester is isomeric with the last described,
and is quite similar in character, but with a slightly different odour.
Its formula is C10H17. OOC(CH)(CH3)2, and it is an oil which boils at
135° to 137° at 13 mm. pressure.
Geranyl Isovalerianate.—This ester has the constitution
C10H1702C(CH2)(CH)(CH3)2.
The rose odour is still further modified by the presence of the five carbon
acid radicle, and judicious blending of the various geranyl esters is
•capable of giving numerous characteristic bouquets to the various rose
odours. This ester boils at 135° to 138° at 10 mm. pressure.
LINALYL ESTERS.
Linalyl Formate.—The formic acid ester of linalol, C10H17OOCH3, has
a distinctive odour somewhat resembling that of the acetate. It is an
oil boiling at 189° to 192°, and is prepared by treating linalol with formic
acid, but the reaction is not complete and commercial samples are never
pure esters.
Linalyl Acetate.—Linalyl acetate is an ester of extreme value in the
reproduction of bergamot and lavender odours, since the natural ester
is the characteristic odour bearer of the former, and to a large extent of
the latter. It also occurs in ylang-ylang oil, petit-grain oil, neroli oil,
jasmin oil, gardenia oil, and many others. As the alcohol linalol is very
susceptible to alteration under the influence of heat or chemicals, it is
not practicable to prepare anything like pure linalyl acetate by the usual
process of acetylation. Tiemann has prepared it in a pure condition by
the interaction of linalol sodium and acetic anhydride. Linalyl acetate
is a colourless oil, with a very characteristic odour of bergamot, and is
optically active in the same sense as the linalol from which it has been
prepared. It has the formula C10H17OOC . CH3, and when pure boils
at 96-5° to 97° at a pressure of 10 mm., or 115° to 116° at 25 mm.
pressure. At atmospheric pressure it boils at about 220° with decom-
position. Its specific gravity is 0*913 and optical rotation about + 6° or
- 6°. The preparation yielding these figures contained 97*6 per cent.
of true linalyl acetate. Commercial specimens of the best make have
Refractive index at 20° 1-4500 ,, 1-4550
Ester value 88 to 95 per cent.
This ester is indispensable in the reproduction of numerous flower oils
in addition, of course, to artificial bergamot oil.
Linalyl Propionate.—This ester is also produced by condensing the
free alcohol and the free acid by means of sulphuric acid. It has a
somewhat fruity odour recalling that of bergamot, and is especially suit-
able for perfumes of the lily of the valley type. It is a colourless oil,,
boiling at 115° at 10 mm. pressure.
Linalyl Butyrate.—The butyric ester of linalol has the formula,.
C10H17OOC . CH 2 . CH2CH3. It resembles geranyl butyrate in odour,
but is somewhat heavier. It is most useful for imparting fruity odours
to flower perfumes. It is prepared by condensing the alcohol and the
acid by means of sulphuric acid.
BENZYL ESTERS.
Benzyl Acetate.—This ester is a constituent of the oils of jasmin,
ylang-ylang, and similar flower oils. It has not a very intense odour,
but is essential to the successful production of such perfumes as artificial
jasmin. It has the formula C 6 H 5 . CH 2 . O . OCCH3. It is a colourless
oil, boiling at 206° at ordinary pressure, and has a specific gravity
1-0570 at 16° and a refractive index 1-5034. The propionic ester has
the formula C6H5CH2OOCCH2CH3, and closely resembles the acetate
in odour.
Benzyl Benzoate.—This ester is a constituent of balsam of Peru, and
also occurs in tuberose and ylang-ylang oils. It is prepared on a very
large scale, as it has the extra virtue of beinsf one of the best fixers of
odours, and a remarkably good solvent for artificial musk, so that it
serves a triple purpose of imparting its own delicate odour to the blend,
of acting as a vehicle for the otherwise poorly soluble musk, and acting
as a good fixer. A method of preparing it in an almost pure condition
is to dissolve sodium in benzyl alcohol and then add benzoic aldehyde,
and then heat for a day in a water-bath. The mixture is then acidified
with acetic acid and the benzyl benzoate precipitated with water. It
forms a colourless oil, which, when free from chlorine, does not darken,
having a slight, but sweet, odour. It is, when absolutely pure, a solid,
melting at 21°, and boiling at 323° to 324°, and having a refractive index
1-5681 at 21°, and a specific gravity 1*1224. The best commercial
samples are liquid at the ordinary temperature, and have the following
characters:—
Borling-point at 760° about 310° to 320°
If cooled to a very low temperature crystallisation will take place,
and the ester then melts at 20° to 210.1
1
According to Ellis, the melting-point is 19-5°. The specimen was partially
melted and the liquid poured off three times, and the product was twice recrystallised
from ether. (Private communication from the laboratories of Messrs. A. Boake,
Roberts, & Co., Ltd.).
Benzyl Cinnamate.—The cinnamic acid ester of benzyl alcohol is a
natural constituent of storax, tolu, and Peru balsams. It is a crystalline
substance with a characteristic sweet balsamic odour. It may be
prepared by heating sodium cinnamate, alcohol, and benzyl chloride
together under a reflux conjdenser. It is a useful ester where a sweet
balsamic odour is required to be introduced into a perfume, especially
of the heavy type. It forms white, glistening prisms, which melt at 39°,
and decompose when heated to 350°. The best commercial specimens
• have the following characters :—
Boiling-point at 5 mm 195° „ 200°
or under atmospheric pressure at 335° to 340° with decomposition;
ester value, 96 to 98 per cent.; it is soluble in 1 volume of 95 per cent.
alcohol.
BORNYL ESTERS.
# Bornyl Formate.—This ester occurs naturally. It can be prepared
synthetically by the action of anhydrous formic acid on borneol in the
presence of a small amount of a mineral acid. It has a fragrant odour,
and is useful in blending with borneol itself. Its optical rotation
depends on that of the borneol from which it has been prepared.
Dextro-rotatory bornyl formate has, in the purest state in which it has
been prepared, the following characters :—
at 15 mm. pressure 98° ,, 99°
The purest laevo-bornyl formate examined had a specific gravity
1*016, optical rotation — 48° 56', refractive index 1'47121, and boiling-
point 97° at 15 mm. pressure. The ester has the constitution
C10H17. OOCH.
Bornyl Acetate.—The acetic acid ester is the most important of the
series. It is a constituent of pine-needle and rosemary oils, and has a
most fragrant and refreshing odour. It is prepared artificially by the
action of acetic anhydride on borneol, in the presence of sodium acetate,
or by the condensation of borneol with glacial acetic acid in the presence
of a small amount of a mineral acid. It is absolutely necessary in the
reproduction of any pine odour. It is a crystalline body, crystallising
from petroleum ether in rhombic hemihedric crystals melting at 29°.
The optical activity depends on that of the borneol from which it has
been prepared. It has the following characters :—
Optical rotation + or — abont 40°
Kefractive index 1-4650 to 1-4665
Boiling-point at 10 mm. pressure about 98°
Melting-point . . . . 29°
It is soluble in 3 volumes of 70 per cent, alcohol. The commercial
product is usually a mixture of dextro-rotatory and laevo-rotatory bornyl
acetate. It should contain not less than 98 per cent, of ester, and
should have a specific gravity from O988 to 0*992; and it should melt
at about 29°. Bornyl acetate has the constitution C10H17OOC. CH3.
It can be kept for a long time in a state of superfusion when it has
once been liquefied.
Bornyl Butyrate.—The next higher ester of borneol is the butyrate.
It is a similar camphoraceous ester, having the formula
C10H17OOC. CH2CH2CH3
and the following characters :—
Boiling-point at 10 mm. pressure 120° to 121°
Specific gravity . . . . . . . . . 0 966|
It usually contains 98 to 99 per cent, of true ester.

Bornyl Isovalerianate.—This is the highest ester of borneol met with
in commerce. It has the composition C10H17OOC . CH 2 . CH : (CH3)2.
It occurs naturally in several essential oils, and is prepared artificially
by esterifying borneol with anhydrous isovalerianic acid. It is a colour-
less oil, boiling at 255° to 260°, and has a specific gravity of 0*956. It is
an ester, like terpinyl acetate, that requires two hours' saponification,
and it also requires a large excess of alkali. Good commercial specimens
Optical rotation about - 35°
Refractive index 1-4620 to 1*4635
Boiling-point at 10 mm. pressure . . . . 128° „ 130°
It has a strong camphoraceous odour.
Bornyl Propionate.—The propionic acid ester of borneol closely
resembles the acetic ester, but as is, of course, usual in homologous
series, its odour is slightly different. It has the formula
C10H17OOC. CH2CH3,
and has the following characters:—
Optical rotation . . . . . . . + or - about 25°
Boiling-point at 10 mm. pressure . .' . 109° to 110°
It usually contains 95 to 97 per cent, of true ester.
CITRONELLYL ESTERS.
Citronellyl Formate.—Citronellyl formate, C10H19O . OCH, is an arti-

ficial ester resulting from the action of concentrated formic acid on
'citronellol. It is an easily decomposed ester which is, on a commercial
scale, rarely produced of more than 90 to 93 per cent, strength. Such
commercial specimens have the following characters :—
Boiling-point about 100° at 10 mm.
True ester . 90 to 93 per cent.
Citronellyl Acetate.—The odour of the acetic ester of citronellol
recalls to some extent that of bergamot. It is a natural constituent of
geranium oil, and is useful in small amounts for blending with rose and
geranium odours. It is prepared by the action of acetic anhydride on
citronellol. When pure it has the following characters :—
Optical rotation about + 2° 30' to - 2° 30'
Refractive index . . . . . . 1*4:456
Boiling-point at 15 mm. pressure . . 119° to 121°
The best commercial samples vary in their characters within very
narrow limits, which should be as follows:—
The odour of the ester varies slightly, according as it is made from

the dextro-rotatory or the laevo-rotatory variety of the alcohol. That
of the former is rather fuller and deeper in its rose odour than that
of the latter. Both esters blend excellently with the corresponding
citronellols, and are very useful in preparing synthetic otto of rose.
The formula of this ester is C10H19OOC . CH3.
ClNNAMYL ESTEES.
Cinnamyl Propionate.—The propionic acid ester has a distinct grape-

like odour, and is very useful for fruit and flower blends. It has the
constitution C6H5. CH : CH . CH2OOC . CH 2 . CH3.
Cinnamyl Butyrate.—This ester has the formula
C6H5. CH : CH. CH2OOC(CH2)2CH3.
It has a characteristic fruity odour, and is most useful for imparting a
fruity bouquet to a flower perfume, but must be used in small quantities.
Cinnamyl Cinnamate.—This ester is known as styracin, and is found
in storax and other balsamic products, and possibly also hi oil of hya-
cinths. It has the constitution
C 6 H 5 . CH : CH . COOCH2CH : CH. C6H5.
It has an odour resembling that of benzyl cinnamate. It forms crystals
melting at 44°. It yields a characteristic dibromide, melting at 151°,
which serves to characterise this ester.
HOMOLINALOL ESTER.
Homolinalyl Acetate.—This body has the constitution CUH19OOCCH3,
and is prepared by the action of homolinalol-sodium on acetyl chloride,
or by the action of acetic anhydride on homolinalol. It is an oil with
a marked bergamot odour, similar to that of linalyl acetate, but not
identical with it. It boils at 111° to 117° at 15 mm.
TERPINYL ESTERS.
Terpinyl Formate.—The formic acid ester of terpineol, C10H17OOCH,
occurs naturally in Ceylon cardamom oil. It is prepared artificially by
the action of formic acid on terpineol, but on a commercial scale is pre-
pared most economically by the action, for a week, of anhydrous formic
acid on turpentine oil. It has a fragrant odour, resembling, but superior
to, that of geranyl formate. It has the following characters :—
Specific gravity 0'99S
Specific rotation 4- or - 69°
Terpinyl Acetate.—The acetic acid ester of terpirieol is also a natural
ester. It nas a refreshing odour, and is often described as being a ber-
gamot and lavender substitute. The writer, however, considers this
description unjustifiable, and that it is really due to the fact that it is so
often used and recommended as an adulterant for these two essential
oils. Terpinyl acetate is<a colourless oil, of the formula
C10H17OOC. CH3,
and can be prepared by various methods. If terpineol be heated
with acetic anhydride and sodium acetate it is largely converted into
terpinyl acetate, but the yield never exceeds about 84 per cent. It can
be obtained by heating pinene with excess of acetic acid for sixty-four
hours. It is either dextro- or laevo-rotatory or inactive. A sample pre-
pared by heating limonene with acetic acid gave the following values :—
Boiling-point at 40 mm. pressure 140°
The best commercial samples are optically inactive, and have the
Specific gravity . . 0-955 to 0-965
Optical rotation practically nil
Ester content 86 to 92 per cent.
It is soluble in about 5 volumes of 70 per cent, alcohol. This ester has
the character of being saponified much more slowly than most other
esters, so that in any determination in which it is involved it is necessary
to saponify the sample for two hours before it is safe to consider the re-
action complete. This fact also assists in determining whether terpinyl
acetate is present as an adulterant in natural essential oils, for if the
saponification value as determined by thirty minutes' saponification is
materially lower than that as determined by a two hours' saponification,
it may be fairly safely inferred that terpinyl acetate or some similar ester
is present.
Terpinyl Propionate.—This ester, which has the formula
C10H17OOC . CH 2 . GH3,
is regarded as an excellent lavender substitute—that is, for use in con-
junction with other bodies. By many perfumers it is regarded as the
best lavender odour\existing amongst synthetic perfumes. It is a colour-
less oil of sweet and fragrant odour, and is very lasting in its effects.
Terpinyl Cinnamate.—Cinnamic acid forms an ester with terpineol,
which has an indescribable odour, but which is exceedingly sweet. It
is a useful oil to blend with lilac and similar odours. It is a heavy oil
of the constitution C10H17OOC . CH : CH . C6H,.
PHENYL-ETHYL ESTEKS.
Phenyl-ethyl Acetate.—Phenyl-ethyl alcohol yields a series of highly
aromatic esters. That of acetic acid has the formula
C6H5. C 2 H 4 . OOC . CH3.
Its odour is usually described as such as to give fine " leaf" effects if
used properly. It is a liquid boiling at 232°, of specific gravity 1*038.
Phenyl-ethyl Propionate.—The propionic ester of phenyl-ethyl alcohol
has the formula CQH5. C 2 H 4 . OOC . CH2CH3. It has a pronounced
rose odour, differing slightly from that of the acetic ester. It is very
useful in blending rose odours.
VARIOUS ESTEKS.
Phenyl-propyl Cinnamate.—This ester occurs in storax, and has a
perfume res mbling that balsamic substance. It has the formula
C6H5CH,. CH2CH2OOC. CH : CH . C6H5.
It is a powerful fixative as well as being useful on account of its rich,
heavy odour.
Pinenyl Acetate.—By passing nitrous fumes into well-cooled pinene
and steam-distilling the reaction product, an alcohol, pinenol, is obtained.
It has the formula C10H15OH. It can be acetylated, and the resulting
acetate has the formula C10H15—OOCCH3. It has an odour resembling
that of lavender oil. It boils at 150°. at a pressure of 40 mm.
Pinoglycyl Acetate.—This ester can be prepared by the direct acetyla-
tion of pinoglycol, C10H1(.O(OH)2, an alcohol resulting from the oxida-
.tion of pinol with permanganate of potassium. It can also be prepared
from pinol dibromide and acetate of silver. It is an ester with an ex-
cellent fruity odour, of the formula C10H1GO(C2H3O2)2, melting at 97° to
98°, and boiling at 155° at 20 mm. pressure, or at 127° at 13 mm.
Pinolglycyl Propionate.—This ester, of the formula C10H16O(C3H5O2)2,
is a quite similar ester, prepared in a similar manner. It also has a
fine fruity odour.
Styrolyl Acetate.—Styrolene alcohol, or phenyl-ethyl glycol, is an
alcohol prepared from styrolene dibromide by the action of caustic
potash. It can be esterified, and forms an acetic ester of the formula
€6H5. CH(OH)CH2 . OOC . CH3. It is an ester with a fine flower odour,
which has been described as "fragrant and dreamy". It is generally
stated by those who have used it that it is indispensable in the prepara-
tion of fine flower bouquets with a jasmin odour.
Styrolyl Propionate.—This body, having the formula
C6H5CH(OH)CH2OOC . CH2CH3,
is very similar to the acetate, and also has a fine flower odour which is
very lasting and powerful.
Styrolyl Valerianate.—The valerianic ester of styrolol has the formula
C6H5CH(OH)CH2OOC . CH 2 . CH(CH3)2. It has a most powerful odour
resembling jasmin and narcissus, and is very useful for the preparation
of these odours. It is very powerful in odour, and care is required in
its use, or the effects will be spoiled by a too powerful odour.
MENTHYL ESTERS.
Menthyl Acetate.—This ester, of the formula CH 3 . CO . OC10H19, is
present in oil of peppermint, its odour being an important character-
istic of that oil. It can be prepared by heating menthol with acetic
anhydride and sodium acetate. Its characters are as follows:—
9O°
Specific gravity at ri 0-925
„ 15° 0-9298
Menthyl Isovalerianate.—This ester, having the formula
C4H9COO . C10H19,
exists naturally in American oil of peppermint. It can be prepared
artificially by boiling menthol with isovalerianic acid and sodium
acetate. It is a very stable ester and requires a considerable excess of
alkali, and at least two hours boiling, for complete saponification. It
METHYL METHOXYRESORCYLATE AND METHYL METHOXYSALICYLATE.

Two glucosides have been separated from the roots of Primula
officinalis by Goris, Mascre, and Vischniac,1 which have been termed
primeverin and primulaverin, and which are both hydrolysed, yielding
the two constituents of the essential oil.
Primaverin has the formula C20H28O13 and melts at 206°, and on
hydrolysis yields sugars and the methyl ester of /?-methoxyresorcylic
acid, of the formula
C . CO . O . CH3
H . C/\C . OH
H.C CH
C . O . CH3
This is the solid constituent of the essential oil, melting at 49°. It
has been, described by Mutschler 2 as primula camphor.
Primulaverin, C20H28O13, melts at 163°, and on hydrolysis yields the
liquid portion of the essential oil, which is the methyl ester of w-meth-
oxysalicylic acid, of the formula
C . CO . O . CH
H. . OH
CH,. O. ,CH
.H
1
2
Roure-Bertrand Fils, Bulletin, October, 1912, 3.
Annalen, 185 (1877), 222.
5. ALDEHYDES.
A number of the aldehydes, both of the aliphatic and aromatic series,
are of the highest importance in synthetic perfumery. The relationship
existing between alcohols, aldehydes, and acids is shown by the following
example:—
CH3. CH2OH CH3 . CO . H CH3CO . OH
Ethyl alcohol Ethyl aldehyde Acetic acid
Generally speaking, aldehydes are prepared by the following methodr

inter alia: (1) Oxidation of primary alcohols, (2) by the dry distillation
of a mixture of the calcium or barium salts of two monobasic fatty acids.
For the approximate determination of aldehydes, an absorption process
of shaking with a solution of either neutral or acid sulphite of sodium
is most generally used. Five or 10 c.c. of the oil to be examined are
shaken in a flask holding about 150 c.c. with about 100 c.c. of 30 per
cent, solution of sodium bisulphite, the flask being kept in a water-bath
for one to three hours as may be necessary. The agitation is repeated
frequently, and when absorption is complete, the oil is driven up into
the graduated neck of the flask by adding more of the bisulphite solu-
"tion, and the unabsorbed oil can be measured, the remainder represent-
ing the aldehyde (or ketone). The aldehyde citral in small quantities is
better determined by means of hydroxylamine. The determination of
aldehydes will be dealt with in a subsequent chapter. The following are
the principal synthetic or isolated aldehydes which will require descrip-
tion: (1) The aldehydes of the fatty series. (2) The aldehydes of the
geraniol series. (3) The aldehydes of the aromatic series. The use of
the higher aldehydes of the fatty series has during the past year or two
become a matter of some importance to the synthetic perfumer. These
aldehydes possess intensely powerful odours, and must be used in very
minute quantities lor they will spoil any perfume in which they are used.
The following are the general methods by which the higher fatty
aldehydes may be produced.
1. The corresponding alcohol may be oxidised :—
E . CH2OH + O2 = R . CHO . + H2O.
2. The barium or calcium salt of the corresponding acid may be
distilled with barium formate :—
(K . COO)2Ba + (H . COO)2Ba = 2BaCO3 + 2E . CHO.
Schimmel & Co. 2 have prepared a number of fatty aldehydes by
a modification of this reaction. They distilled mixtures of barium
formate with the barium salt of the corresponding acid, in a vacuum, as
it was well known that this increases the yield when working with the
higher aldehydes, which volatilise with difficulty.
3. Darzens 3 claims a method in which a ketone is condensed with1
chloracetic-ether in the presence of an alkaline condensing agent. For
example, acetone reacts with chloracetic-ether as follows:—
2
iRadcliffe, P. and E.O.R.,
8
1917, 65. D.R.P., 126, 736 of 1902.
Ibid., 174, 239, and 174, 279.
VOL. II. 12
Cl . CH2 . COOG,H,
" =
C— CH . COOC2H5 + HCI
o
^/
The resulting product is then hydrolysed, giving—
O
and, finally, this compound on heating evolves carbon dioxide and
undergoes a slight molecular change, yielding a butyric aldehyde of the
formula:—
CH,\r/H
CH3/U\CHO + CO,
4. Aldehydes are also formed by the action of nascent hydrogen
(sodium amalgam) upon the chlorides of acid radicles or their oxides
(the acid anhydrides):—
(1) CH3COC1 + 2H = CH 3 . CHO + HCI
(2) (CH 3 . CO),O + 4H = 2CH 3 . CHO + H 2 O
5. Aldehydes are formed by the reduction of the ester of the corre-
sponding acid to the alcohol, and then oxidising the alcohol with heated
copper as catalyst. It is well known that when primary alcohols in the
gaseous state are passed over finely-divided copper dust, obtained by
reduction of copper oxide, at 250° to 400°, they yield hydrogen, and
aldehydes or ketones respectively.
Aldehydes are usually most easily separated from the essential oils
in which they occur, by means of acid sodium sulphite. The oil—or
the suitable fraction thereof—is well shaken for a time varying accord-
ing to the nature of the aldehyde, with an equal volume of a saturated
solution of sodium bisulphite, with a little ether added, in order to hinder
the non-aldehydic portion of the oil from becoming occluded in the
crystals of the bisulphite compound of the aldehyde. These crystals are
separated and washed well with ether They are then decomposed by
warming with a solution of sodium carbonate, and the regenerated
aldehyde is extracted by means of ether.
Neuberg and Tiemann l propose the following method, depending
on the fact that most aldehydes form a compound with thiosemi-car-
bazide. The oil containing aldehyde is heated in alcoholic solution on
a water-bath, with thiosemi-carbazide. Various salts of the heavy
metals will form insoluble precipitates with the thiosemi-carbazone
formed, and such precipitate is dissolved in alcohol, and a current of
hydrogen sulphide passed through until the metal is precipitated, leaving
the thiosemi-carbazone dissolved in the alcohol.
The following are the most effective compounds to prepare for the
identification of an aldehyde.
Semi-carbazones.—Most aldehydes react with semi-carbazide, forming
l
Berichte (1902), xxxv., 2049.
condensation products known as semi-carbazones, which are usually oi:

a well-defined crystalline character with a sharp melting-point, the
reaction taking place is as follows :—
B.CHO + NH 2 . NH . CO . NH2 = E . CH : N . NH . CO . NH2 + H2O.
Aldehyde. Semi-carbazide. ~ Semi-carbazone.
They are usually best obtained by dissolving the aldehyde in alcohol,
and adding excess of an equimolecular mixture of semi-carbazide hydro-
chloride, and acetate of sodium. The mixture is allowed to stand for
some time and the semi-carbazone then precipitated by the addition of
water. Some semi-carbazones are more easily prepared by substituting
free acetic acid (glacial) for the acetate of sodium. Semi-carbazones are
best recrystallised from hot methyl alcohol.
Oximes.—Most aldehydes yield a condensation product with hydroxyl-
amine, according to the equation :—
E . CHO + NH 2 . OH - E . CH : NOH + H2O.
Aldehyde. Hydroxylamine. Oxime.
To obtain the oximes, equimolecular quantities of the aldehyde and
hydroxylamine are heated in alcoholic solution on the water-bath for
thirty to sixty minutes. The hydroxylamine is best added in the form
of hydroxylamine hydrochloride, and the necessary amount of alcoholic
solution of potash added to liberate the hydroxylamine. Most, but not
all, the oximes are crystalline.
Phenylhydrazones.—Nearly all aldehydes form condensation pro-
ducts with phenylhydrazine, known as phenylhydrazones, according to
the following equation :—
E. CHO + NH 2 . NH . C6H5 = E . CH : N . NH . C6H5 + H2O.
Aldehyde. Phenylhydrazine. Phenylliydrazone.
They are best prepared by heating the aldehyde in alcoholic solution,

on the water-bath, under a reflux condenser, with slightly more than
the equimolecular quantity of phenylhydrazine hydrochloride, with
acetate of sodium added. Thirty to sixty minutes is usually sufficient
for the reaction.
Pyruvic Acid Compounds.—Lubrzynska and Smedley l have recently
shown that a number of aldehydes such as heliotropin, anisic aldehyde,
benzaldehyde, and cinnamic aldehyde, condense with pyruvic acid in
slightly alkaline solution, with the formation of /2-unsaturated-a-ketonic
acids. For example, if heliotropin and pyruvic acid in alkaline solution
be left standing for about eight days at ordinary temperature, dihydroxy-
methylene-benzal-pyruvic acid is formed. This body forms yellow
needles, melting at 163° Similarly, anisic aldehyde yields methoxy-
benzal-pyruvic acid, melting at 130°; and cinnamic aldehyde yields
cinnamal-pyruvic acid, melting at 73°.
Doebner2 showed that certain aldehydes, citral, for example, form
condensation products with pyruvic acid and /2-naphthylamine, known
as naphthocinchoninic acids. The reaction takes place as follows :—
1 2
Ghem. Zentral. (1914), 561. Berichte, 27 (1894); 354 and 2026.
E . CHO + CH3CO . COOH + C10H7NH2

Aldehyde. Pyruvic acid. j8-Naphthylamine.
N = C—E
= CH + 2H90 + H9
COOH
Naphthocinchoninic acid.
Schlogll has shown that para-aminophenylglycine, para-amino-
phenyloxamic acid, and para-aminoacetanilide form compounds with
aldehydes, which have sharp melting-points and are suitable for the
characterisation of aldehydes. With ^-aminophenylglycine condensa-
tion takes place when the glycine, mixed with alcohol and the alde-
hyde in question, is warmed. For the purpose of condensing with
j9-aminophenyloxamic acid and with £>-aminoacetaldehyde the alcoholic
suspension of the amino-body is acidulated slightly with hydrochloric
acid and the solution is warmed after the aldehyde has been added.
This method yields the hydrochloride of the condensation products.
Condensation Product
M.p. Designation
of with
Cinnamic 2>-Aminophenylglycine 120° Cinnamic aldehyde anilglycine

aldehyde .
Furfurol »» 135° Furfurol anilglycine
Benzaldehyde p-Aminophenyloxamic acid 180° Benzaldehyde aniloxamic acid ."
Vanillin
Cinnamic 5» >»
170° Vanillin aniloxamic acid
125° Cinnamic aldehyde aniloxamic acid &
'9
aldehyde . 8
Furfurol 130° Furfurol aniloxamic acid *&
Benzaldehyde ^-Aminoacetanilide . !
. 165° Benzaldehyde acetaminoanile b'
Vanillin » 208° Vanillin acetaminonile . 0<
Cinnamic » 195° Cinnamic aldehyde acetaminoanile; •
aldehyde .
THE ALIPHATIC ALDEHYDES.

The following are the principal members of the fatty series of
aldehydes which either occur in essential oils, or are used in synthetic
perfumery :—
Formic Aldehyde.—This aldehyde, H . CHO, is the lowest member
of the aliphatic series. It has been found, but rarely, in the distillation
waters of a few essential oils. It can be identified by evaporation on
a watsr-bath with ammonia when crystals of hexamethylene-tetramine
are formed.
Acetic Aldehyde.—Acetic aldehyde, CH3 . COH, ocours in a number
of essential oils, or their distillation waters. It is a liquid boiling at 21°.
Butyric Aldehyde.—This body, C3H7COH, has been found in the oils
of Eucalyptus globulus and Cajuput. It boils at 75° and forms a para-
nitro-phenylhydrazone, melting at 91° to 92°.
Isovalerianic Aldehyde.—This aldehyde, which has the constitution
CH3 . CH(CH3) . CH2 . CHO, exists in American peppermint oil. L
l
Jour.$rakL Ghent., ii. 88 (1913), 251.
boils at 92*5°, and forms a thiosemi-carbazone, melting at 52° to 53°.

Its specific gravity is 0-804.
Vdlerianic Aldehyde.—The normal valerianic aldehyde,
CH3(CH2)3.CHO,
, is a liquid boiling at 102°, of specific gravity 0*816.
Hexylic Aldehyde.—Hexylic or caproic aldehyde, C5H11CHO, has
been identified in oil of Eucalyptus globulus. It is a liquid boiling at
128° at 740 mm., and having a specific gravity 0-837.
Heptylic Aldehyde.—This aldehyde, also known as oenanthylic alde-
hyde, is formed by distilling castor oil under reduced pressure. It is an
Oil of powerful fruity odour, boiling at 155°, or at 45° at 10 mm. pressure,
and having a specific gravity 0*820, and refractive index 1'4150. It
forms an oxime melting at 50°.
Octyl Aldehyde.—The eight-carbon aldehyde has the formula
CH3(CH2)6CHO.
It is a natural constituent of neroli and rose oils. It is described as
hiving a deep honey-like odour, and is usetul in rounding off perfumes
with a heavy odour. It is a liquid boiling at 82° at 13 mm., and has a
specific gravity about 0*826, and refractive index 1*41955. It' absolutely
pure its specific gravity is only 0*821. It melts at - 13° to - 16°. It
yields an oxime melting at 60°, a semi-carbazone melting at 101°, and a
naphthocinchoninic acid compound melting at 234°.
Nonyl Aldehyde.—The nine-carbon aldehyde has the formula
CH3(CH2)7CHO.
This aldehyde belongs to the rose and orange types of odour. It is
present naturally in both these essential oils. It can be used success-
fully, in very small quantity, in all perfumes of the rose, geranium,
orange, and neroli types. It is an oil having a specific gravity 0*8277,
refractive index 1*4245, and boils at 92° at a pressure of 13 mm. Its
melting-point is + 5° to + 7°. It yields an oxime melting at 69°, and
a semi-carbazone melting at 100°, which serve to identify it.
Decyl Aldehyde.—This body, which has the formula CH3(CH2)8CHO,
is also a constituent of rose, orange, and other essential oils. It is most
useful in minute quantities in reproducing the odours of orris, neroli,
cassie flowers, rose, and orange. It is probably the most generally
useful of the whole of this series of aldehydes. It is an oil boiling at
207° to 209° at 755 mm. pressure, and at 80° to 81° at 6 mm. The specific
gravity is 0*828 and refractive index 1-42977. Its melting-point is
+ 2° to + 5°. It yields a naphthocinchoninic acid compound, melting
at 237°, an oxime melting at 69°, and a semi-carbazone melting at 102°.
On oxidation it yields capric acid melting at 30° to 31°.
Undecylic Aldehyde.—This 'has recently been prepared, and is now
being used in the blending of flower bouquets. It has the formula
CH3(CH2)9CHO.
It melts at - 4°.
Duodecylic Aldehyde.—The twelve-carbon aldehyde, also known as
lauric aldehyde, has the constitution CH3(CH2)10CHO. It was origin-
ally introduced for blending with violet perfumes, but it is not very
suitable for this purpose. It is, however, of considerable value in mixed
flower perfumes and fancy bouquets. It is a solid body and rapidly
oxidises to lauric acid, melting at 23° to 24° and boiling at 128° at 13 mm.
It should therefore be kept in solution in alcohol. It yield sTa semi-
carbazone melting at 102°.
Tredecyl Aldehyde. — This aldehyde has the constitution
CH3(CH2)11CHO.
American perfumers go so far as to state that it has created quite a
furore amongst progressive perfumers. It has no distinct flower per-
fume, and can be used to modify the odour of almost any combination.
It is stated that it is so characteristic that nothing can replace it. It is
very expensive, but must only be used in minute quantities.
Tetradecyl Aldehyde. — This is the highest of this series of aldehydes,
and has the formula CH3(CH2)12CHO. It resembles the thirteen-carbon
aldehyde somewhat, and is very useful for blending in flower combina-
tions.
Hexylenic Aldehyde. — This aldehyde, of the constitution
CH3 . CH2 . CH2 . CH = CH . CHO,
is an unsatuiated compound, and exists in a number of plants, for
example in the leaves of the vine and strawberry. It forms a hydrazone
melting at 167°.
Undecylenic Aldehyde. — This aldehyde is closely related to those just
described, but belongs to the unsaturated series. It has the formula
CH2 : CH(CH2)8CHO. It is very similar to the aldehydes just de-
scribed, and is used in exactly the same way, namely, for modifying the
odour of flower combinations. It melts at + 5° to + 7° and boils at
118° at 13 mm.
Oleic Aldehyde. — Oleic aldehyde, C17H33 . CHO, is 'found in oil of
orris root. It has the following characters : —
Specific gravity ......... O8513
It forms a semi-carbazone melting at 87° to 89°.
The aldehydes of the geraniol series are of very great commercial
importance. The only two which are of common occurrence are citral
and citronellal.
CITRAL AND NERAL.
Citral, or geranaldehyde, and neral or neraldehyde, are, as indicated
under geraniol, the two stereoisomeric forms of the aldehydes derived
from geraniol and nerol. Citral is best described as a-citral, and neral
corresponds with /?-citral. The constitution of the two aldehydes is
either that indicated under geraniol, namely,
,
>C : CH . CH.," . CH.,' . C(CH3) : CH . CHO
CH t
or
2
V). CH,. CH,. CH,. C(CH3) : CH . CHO
CH X
The former is the more probable constitution. Citral as found in
commerce, is probably almost invariably a mixture of the two isomers,
which are very similar in their general characters. It occurs to a con-
siderable extent in various essential oils, being the principal constituent
of lemon-grass oil, and of the oil of Backhousia citriodora, and occurring
to the extent of about 4 to 6 per cent, in lemon oil, which owes its
characteristic flavour to this aldehyde.
It can be obtained artificially by the oxidation of the alcohols geraniol,
nerol, and linalol, by means of chromic acid. To prepare it from these
sources, the following process may be used. Ten grams of potassium
bichromate are dissolved in a mixtuie of 12*5 grams of sulphuric acid
and 100 c.c. of water. To this mixture, 15 grams of geraniol are gradu-
ally added, care being taken thatr the mixture is kept cold at first, and
then allowed to get warm, the w hole being well shaken for about half an
hour. It is then rendered slightly alkaline and a current of steam passed
through it. To separate the citral from other products and from un-
changed geraniol, the distillate is shaken with a saturated solution of
sodium bisulphite, and shaken from time to time, for about twenty-four
hours in the cold, or for an hour or so at water-bath temperature. In
the cold, crystals of the compound of citral with bisulphite separate,
which are dried, washed with ether, mixed with sodium carbonate and
steam distilled, when citral passes over. By careful manipulation about
35 per cent, of the theoretical amount is obtained.
Citral can also be obtained in a pure state by distilling a mixture of
the calcium salt of geranic acid with calcium formate, according to the
usual method for the production of aldehydes.
Citral can also be obtained from essential oils, such as lemon-grass
oil, by means of the bisulphite process, but care should be taken that the
temperature be kept low, as otherwise a considerable loss occurs, due to
the conversion of part of the citral into sulphonic acid compounds.
Citral combines with 4 atoms of bromine, and, under the influence of
dehydrating agents, such as potassium hydrogen sulphate, yields cymene,
C10H14. Under the influence of alkalis, citral condenses with acetone,
with the splitting off of water to form pseudo-ionone, C13H20O, which is
converted into isomeric ionones by means of acids. These bodies are
the characteristic artificial violet perfume, which will be mentioned later.
Keduction with sodium and alcohol produces the alcohol, geraniol.
Various derivatives of citral have been prepared, such as the oxime,
anilide, and phenylhydrazone, which are oily liquids, and the semi-
carbazone, which appears to exist in several isomeric forms of different
melting-points. Most characteristic, however, is the citryl-/3-naphtho-
cinchoninic acid, discovered by Doebner. This can be prepared by warm-
ing together in alcoholic solution 20 parts of citral, 20 parts of
/^naphthylamine, and 12 parts of pyruvic acid. This acid, C23H23NOo,
melts sharply at 197°, and is the most useful compound for characteris-
ing citral. Indeed, Doebner has applied its preparation to the quantita-
tive estimation of citral in oils containing it. The determination of this
body in essential oils is by no means an easy matter, and will be men-
tioned later. A siîdy of citral and its derivatives has caused the most
recent investigators to assign one or other of the formulae given 011
p. 53 to the stereoisomeric varieties of citral.
According to Tiemann the following are the characters of a-citral and
/?-citral, but as these were determined before the exact relationships of
geraniol and nerol and the stereoisomeric aldehydes were as well under-
stood as they now are, they must be accepted with some reserve.
a-Citral.
ft-Citral.
The purest specimens which have been prepared of natural citral,
either from lemon-grass oil, lemon oil, or the oil of Tetranthera citrata,
Refractive index . 1-4880 to 1-4900
Boiling-point at 12 mm. 110° ,, 112°
» 760 „ 228° „ 229°
Several years ago Tiemann 1 carried out a great deal of work on the
chemistry of citral, in connection with which the following points are
•especially noteworthy. He has shown that in addition to the normal
bisulphite of sodium compound of citral, three hydrosulphonic acid
•derivatives are formed, according to the conditions under which the ex-
periment is performed (acidity, alkalinity, temperature, etc.). He con-
sidered that the explanation of the existence of two well-defined isomeric
semi-carbazones (melting at 164° and 171°) was the existence of two
stereoisomeric forms of citral in lemon-grass oil. To support this, he
mixed the normal bisulphite compound with water and added sodium
carbonate. The liquid was then shaken with ether, and about half the
citral set free and dissolved in the ether (fraction a) ; the remainder was
set free by the addition of caustic alkali and extracted with ether (fraction
b). Whilst both fractions have exactly the same physical properties, it
is found that fraction a gives only one semi-carbazone, melting at 164°,
whilst fraction b gives both, melting at 164° and 171° respectively. The
same was found to be the case with the cyanacetic compound fraction a
yielding only one citralidene cyanacetic acid, melting at 122°, whilst
fraction b gave this, and also one melting at 80°, which is now known
to be impure, the pure compound melting at 94° to 95°. This view has
been confirmed by the discovery of the alcohol nerol, as mentioned above
(and see also under ionone).
Further important work on the pure chemistry of citral by Semmler
and by 2Skita has been published during the past few years. Semmler has
shown that aldehydes which possess one or more labile hydrogen atoms
adjoining the CHO group, possess the property of forming enolic acetates,
that is, acetates in which a double bond has migrated into the conjugated
position. He draws the following general conclusions in regard to this
property of this type of aldehyde :—
1. All the aldehydes hitherto studied, which contain next to !the
functional aldehydic group one or more labile hydrogen atoms are cap-
Berichte, 42 (1909), 1161, 2014; 44 (1911), 991.
-Ibid., xxxi. 3278, 3324; xxxii. 107.
able of reacting with the organic anhydrides and acids in their enolic
forms giving unsaturated esters.
2. These unsaturated esters, by oxidation, permit of the elimination
of the CHO group and the preparation of aldehydes or acids with fewer
carbon atoms.
3. This reaction shows that the estimation of alcohols in essential
oils containing aldehydes may lead to numbers which are too high.
4. The enolic esters, on saponification, regenerate the aldehydes.
With sodium and alcohol, the saturated alcohol corresponding to the
aldehyde is obtained.
This migration has been described under geraniol (p. 17).
Bnklaar1 has shown that when citral is reduced by metals in a
stream of hydrogen, it yields not only reduced aliphatic compounds, but
that the ring is also closed, and a series of cyclic compounds is also
formed.
Cyclo-citral thus formed appears to have the following constitution :—
CH3 CH,
.CHO
H,C C . CH,
CH2
According to Skita, the reaction proceeds in a different manner if
the reduction be effected with palladium chloride and hydrogen. In
this case the citral in alcoholic solution is mixed with an aqueous solu-
tion of palladium chloride and the whole thickened with gum-arabic.
Hydrogen gas is then forced into this solution under pressure. The
products of the reduction include citronellal and citronellol and a di-
molecular aldehyde, C20H34O2, which probably has the following con-
stitution :—
CH
\C : CH. CH,. CH.2. C(CH3)CH.,. CHO
CH,
iH. /
CH3-
: CH . CH2 . CH2 C(CH3)CH2 . CHO
CH/
Schossberger has recently isolated the isomeric form of citral which
is known as isocitral, corresponding to the isogeraniol resulting from
enolised citral acetate.
Isocitral is left as a residue when reduced enolised citral is freed
from isogeraniol by means of phthalic anhydride, and has the following
characters :—
1
Chem. Weekblad, 4 (1907), 322.
It yields a /2-naphthocinchoninic acid compound melting at 206°.
Citral is used on a very large scale for the manufacture of ionone,,
the base of the artificial violet perfumes (q.v.)
The identification of citral is a matter of considerable importance,
and may be effected by the preparation of several well-defined crystal-
line derivatives.
The semi-carbazones, C10H1(}: N . NH . CO . NH2, are well defined.
That of a-citral melts at 164° and that of /2-citral at 171°, a mixture of
the two in equal amounts melting at 135°. If it is desired to obtain
mainly the semi-carbazone of a-citral, 5 parts of citral should be dis-
solved in 30 parts of glacial acetic acid. Four parts of semi-carbazide
hydrochloride are dissolved in a little water and added \ to the citral
solution. After standing for a short time, a considerable quantity o(
crystals separate in fine needles. These are recrystallised several times
from methyl alcohol, when 60 to 70 per cent, of the theoretical yield
can be obtained of the a-citral semi-carbazone, melting at 164°. The
mother liquors yield /3-citral semi-carbazone, melting at 171°. If the
reaction be allowed to take place in a neutral, instead of an acid, solu-
tion, about 10 per cent, of /?-citral semi-carbazone can be obtained,
leaving a mixture of the two isomers, melting at 135° as the main yield.
The isomeric semi-carbazones may be separated in the following manner::
The dry mixture of semi-carbazones is finely powdered, and repeatedly
exhausted with boiling ether. The liquid is filtered and deposits crystals
melting at 135°. The ethereal mother liquor on concentration yields
only the same product, but the insoluble residue has a higher melting-
point and can be washed with ether until this rises to 160°. This pro-
duct can now be recrystallised from alcohol, when the pure /3-citral
semi-carbazone melting at 171° is obtained, the alcoholic mother liquors
yielding the a-citral compound, which on a second recrystallisation is
obtained pure, melting at 164°.
In order to resolve the mixture melting at 135°, it should be dis-
solved in cold acetic ether to saturation, and allowed to stand so that
the solvent evaporates very slowly. Two distinctly different forms of
crystals separate which can be picked out and recrystallised separately,
when the two semi-carbazones are obtained in a state of purity.
Very characteristic of citral is the compound which it forms with
/2-naphthocinchoninic acid. It is obtained in the following manner:
Twenty grams of citral and 20 grams of pyruvic acid are dissolved in
absolute alcohol, and 20 grams of /?-naphthylamine are added. The
whole is heated for three hours on the water-bath under a reflux con-
denser.
On cooling a-citryl-/3-naphthocinchoninic, acid separates in fine
needles, melting at 199° to 200°, which are filtered off and washed with
ether, and recrystallised from alcohol. If too little citral is present
a-methyl-^-naphthocinchoninic acid is formed as well, but this is less
soluble than the citral compound, and is separated from it by dissolving
the latter in hot alcohol and recrystallising it. The reaction taking
place is as follows :—
C9H15. CHO + CH 3 . CO . COOH + C10H7NH2 =

Citral. Pyruvic acid. j8-naphthylamine.
/N:C.C 9 H 15
C10H / | + 2H.O + H.,
\C : CH " "
COOH
a-citryl-j8-naphthocinchoninic acid.
Citral also forms a crystalline derivative with cyanacetic acid,
citrylidene-cyanacetic acid of the formula—
,CN
C9H15CH: C/<f
N3OOH
It is obtained by mixing 1 molecule of cyanacetic acid, 1 molecule
oi\ citral, and 2 molecules of caustic soda. The reaction liquid is
extracted with ether, in order to remove non-aldehydes, and the clear
liquid acidified with acetic acid. The separated acid is dissolved in
benzene and precipitated by petroleum ether when it forms yellow
crystals, melting at 122° in the case of a-citral, and at 94° to 95° in the
case of /3-citral.
In a similar manner citrylidene-malonic acid can be prepared, melt-
ing at 191°.
The oxime and phenylhydrazone are liquid, and not suitable for
identification purposes.
On oxidation by weak oxidising agents, citral yields geranic acid,
C10Hj602; on reduction it yields geraniol.
Citral forms condensation compounds with sulphites and \acid
sulphites which are exceedingly useful in the estimation of the alde-
hyde. Tiemann has isolated three separate hydrosulphonic acid com-
pounds. The normal bisulphite compound is best prepared by shaking
citral with a hot solution of sodium bisulphite containing free sulphur-
ous acid.
When the normal sodium bisulphite compound is dissolved in water
and submitted to steam distillation, half of the citral passes over, the
remainder being converted into the sodium salt of the so-called " stable "
citraldihydrodisulfonic acid :—
/OH
2C9H15. CH< = C9H15COH + C9H17(SO3Na)9COH.
\SO3Na
This compound is readily soluble in water without regeneration of the
citral from the solution either by sodium carbonate or hydrate.
When citral is agitated with an aqueous solution of neutral sodium
sulphite, the sodium salt of the " labile " citraldihydrodisulfonic acid
results according to the following equation :—
C9H15COH + 2Na 2 SO 3 + 2H2O = C9H17(SO3Na)2COH + 2NaOH.
This differs from the isomeric " stable" compound in being quan-
titatively decomposed by the action of sodium hydrate into citral and
neutral sodium sulphite.
A thiosemi-carbazone, melting at 107° to 108°, and a semi-oxamazone,

melting at 190° to 191°, have been prepared.
ClTBONELLAL AND EHODINAL.
These aldehydes, of the formula C10H18O, are those corresponding to

the alcohols citronellol and rhodinol (assuming, as is apparently true,
that they are distinct compounds as indicated under citronellol. Their
constitutions would therefore be as follows : —
C . CH9 . CH9 . CH9 . CH(CH3)CH, . CHO.

Citronellal.
C : CH . CH2 .iCHo . CH(CH3)CH2 . CHO.

GIL
Bhodinal.
Citronellal which was originally termed citronellone, is one of the
characteristic constituents of citronella oil, in which it occurs to a con-
siderable extent. It can be prepared by shaking the essential oil with
a hot solution of sodium bisulphite, and decomposing the resulting
bisulphite compound by means of sodium carbonate and distilling the
citronellal in a current of steam. Citronellal is optically active, and it
is probable that the specimens isolated from natural sources are mixtures
of the two optically active isomers, so that the actual theoretical rotation
is not known with certainty.
It can be prepared artificially by the reduction of cjtronellol, C10H200,
and the isomeric rhodinal can, according to Bouveault, be prepared by
the reduction of rhodinal from oil of rose.
According to Tiemann and Schmidt, citronellal has the following
characters : —
,, ,, at 25 mm. 103° „ 105°
Commercial specimens of a high degree of purity have the follow

ing characters :—
Specific gravity 0'855 ,, 0-858
Citronellal prepared from Java citronella oil is laevo-rotatory to the
extent of about - 3°.
For the identification of citronellal, the semi-carbazone is the easiest
crystalline compound to prepare. It results if an alcoholic solution of
citronellal be well-shaken with a solution of semi-carbazide hydrochloride
and acetate of sodium. It is purified by recrystallisation from a mixture
of chloroform and petroleum ether, and then melts at 84°. It also
forms a well-defined naphthocinchoninic acid, which is prepared in the
same manner as the corresponding citral compound. It melts at 225°.
It also forms eitronellylidene-cyanacetic acid, melting at 137° to 138°.
It forms additive compounds with sodium bisulphite, which are similar
in characters to the corresponding citral compounds.
On oxidation it yields citronellic acid, C10H18O2. On acetylation,
catronellal is converted into the alcohol isopulegol, which is acetylated,
forming isopulegyl acetate, so that this aldehyde is included in the re-
sults of determinations of geraniol in oils in which both constituents are
present. For example, the total acetylisable constituents of citronella
oil, which are usually returned as " geraniol/' really include the citronellal
present as well. According to Tiemann,1 citronellal, under the influence
of acetic anhydride forms an enolic ester which is gradually converted,
by heating with the anhydride, into isopulegol acetate—the relationships
being shown as follows :—
CH3—C=CH2 CHo—C=CH9 CH3—C=CH.,"
CIH2 CEL n
i
CHO, (CH 3 )CO.OCH \CH2 OH.CH/\CIL
CH ,CH
H . CH3 CH . CH, CH . CH
Citronellal. Enolic acetate. Isopulegol.
Ehodinal, under similar circumstances, appears to give rise to men-
thone, the relationships being shown as follows :—
CH3—C— CH3 CH3—C—CH3 CH3—CH—CH3
CH CH CH
CHO (CH3)CO . OCH,
CH2 CH CH, CH2v ,CH2

'"^H. 01 CH . CH3 CH. CH3
Rhodinal. Enolic acetate. Menthone.
The work of Harries and Himmelmann 2 provides considerable con-
firmation of the individuality of the aldehydes citronellal and rhodinal.
By the action of ozone on the aldehyde, results differ materially accord-
ing to the source of the " citronellal," and those chemists are of opinion
that the two complexes—
CH3
. CH2 and \C : CH
CH9' CH,
are present, which is in accordance with the assumption stated pre-
viously. They consider that the first complex becomes less stable as the
acid-carrying group in the molecule increases.
This view would explain the observation made by Tiemann and
Schmidt, that citronellal when heated with acetic anhydride, only
yields about 50 per cent, isopulegol; or the fact noted by Harries and
1
Berichte, 42, 2014. ., 41 (1908), 2187.
Schauwecker, that when citronellal acetal is oxidised by permanganate,
there is formed the acetal of the semi-aldehyde of /3-methyladipic acid
and a glycol. The indistinct melting-points observed in citronellal
derivatives (for example in the semi-carbazone) can also thereby be ex-
plained. It would appear that commercial citronellal contains the two
isomeric forms in varying proportions.
H. J. Prins L has isolated two isomerides of citronellal by repeated
fractionation. The first boils at 203° to 204°, has a specific gravity of
0*888 at 14°, and forms a semi-carbazone, melting-point 85° to 86°.
The second boils at 198° to 199°, has a specific gravity of 0*8745 at 14°,
and yields a semi-carbazone, melting-point 83° to 84°. It is suggested
that the formula of the first is—
CH 2 : CMe . CH2 . CH 2 . CH2CHMe . CH 2 . CHO,
whilst that of the second is—
CMe,: CH . CH 2 . GIL,. CHMe . CH2. CHO.
These results would suggest that ordinary " citronellal" is a mixture of
citronellal and rhodinal.
The aldehydes of the cyclic series include a number of compounds
which are of common occurrence in essential oils, and a certain number
which are prepared synthetically for perfumery purposes.
The simplest of these, in reference to chemical constitution, is:—
BENZALDEHYDE.
Benzaldehyde, C6H5COH, is the main constituent of oil of bitter
almonds and other oils of the same family. It-can be formed in various
ways, including the oxidation of benzyl alcohol, or, as is usually done, by
acting on benzal chloride, C6H5CHC12, with sulphuric acid or with milk
of lime, or by heating benzyl chloride, C6H5CH2C1, with water and lead
nitrate. Artificial benzaldehyde is manufactured and sold largely as
" artificial oil of almonds ". It is almost identical with the natural oil,
but possesses a rather harsher odour, probably due to the presence of
traces of impurities, which generally consist of chlorinated compounds.
A very pure variety, however, is now produced, which is free from these
impurities. The natural benzaldehyde results from the decomposition of
a glucoside, amygdalin, under the influence of the ferment emulsin in the
presence of water (vide oil of bitter almonds).
The starting-point in the synthesis of benzaldehyde,2 which requires
a good deal of skill for its successful manufacture, is the hydrocarbon
toluene, and this must first be separated from the benzene and other
hydrocarbons accompanying it in its crude form by suitable fractional
distillation. The initial reaction of the toluene is with chlorine, and this
reaction takes place far better in sunlight than away from it. The toluene
is heated to boiling in as strong a light as possible, and a current of
perfectly dry chlorine is passed through it until 100 parts has increased
in weight to 140 parts. The weather and light will determine the time
which is taken to complete this reaction; during the winter the whole
day may be necessary, whereas on a fine summer day the reaction may
be finished in two to three hours. The chlorinated compound so formed
1
2
Chem. Weekblad, 14 (1917), 692-95.
Badcliffe, P. and E.O.R. (1917), 298.
is benzalchloride, C6H5. CH. C12, which has now to be converted into
benzaldehyde.
The crude benzalchloride obtained by the above-described chlorination
of toluene is mixed with three times its weight of water and its own
weight of finely precipitated calcium carbonate, and the mixture is heated
for four hours in a bath of oil or similar material to a temperature of
130°. After the expiration of this time steam is passed through the
Contents of the reaction vessel, which is maintained at the temperature
of 130° until no more oil distils over. The resulting crude benzaldehyde
<sontains a fair amount of benzoic acid which must be removed. The
bulk of the benzoic acid, however, is left in the reaction vessel, and may
be recovered by filtering the hot liquid and adding hydrochloric acid, by
which means the benzoic acid separates out and may be filtered off,
washed, and dried. If recrystallised from hot water it can be obtained
in a state of purity. The crude benzaldehyde which has been steam
distilled, together with the watery distillation liquid, is now treated with
a concentrated solution of acid sulphite of sodium and the whole well
shaken until almost the whole of the oily liquid has gone into solution.
If crystals of the double compound of benzaldehyde and sodium sulphite
separate, more water must be added and the liquid well shaken until the
crystals are dissolved again. The aqueous solution is now filtered from
any small quantity of oil which remains undissolved, and the filtrate
treated with anhydrous sodium carbonate until it acquires a decided
alkaline reaction. The alkaline liquid is now subjected to distillation
with steam, when the benzaldehyde distils over.
There is, of course, always the risk of the purified benzaldehyde con-
taining traces of chlorine—in fact, samples manufactured with merely
ordinary care may be found to contain up to 2'5 per cent, of this im-
purity. It is very objectionable when the benzaldehyde is to be used, as,
for example, a soap perfume in pale-coloured soaps, since the presence
of chlorine compounds invariably causes the product to change colour,
which renders the soap more or less unsaleable. One of the causes of
the presence of chlorine in tha finished product is that chlorine reacts
with toluene, especially if the temperature is a little too low when
the current of chlorine starts, in such a way that one atom enters
the nucleus, forming chlorotoluene, C6H4C1CH3. Chlorine reacts with
toluene in such a manner, at higher temperatures, as to replace the atoms
of hydrogen in the methyl side chain, so as to form benzal chloride,
C6H5CHC12. But the reaction of chlorine on chlorotoluene is quite
similar, and the result is the presence of a certain amount of chloro-
benzal-dichloride, C6H4C1. CHClg. In the subsequent reaction with
water and calcium carbonate, it is only the chlorine in the side chain
which is eliminated, so that we shall, under the above conditions, have
a certain amount of chlorobenzaldehyde formed, C6H4C1. COH. It is
obvious, therefore, that the greatest care must be exercised in carrying
out the synthesis of benzaldehyde if a product free from chlorine is to be
obtained. In the actual course of the reaction in practice, the mixture
contains several chlorinated compounds, including benzal chloride, which
is the principal constituent of the mixture, and which is eventually con-
verted into benzaldehyde, benzyl chloride, chlorotoluene, and benzo-
trichloride. If the mixture is boiled with water, with the addition of
•calcium carbonate, the resulting reaction-mass consists essentially of
benzaldehyde, benzyl alcohol, and traces of the chlorinated products
which do nob enter into the hydrolytic reaction, and also a considerable
quantity of benzoic acid which remains behind in the still as calcium
benzoate, when the volatile bodies are steam distilled. By rendering the
distillation residue acid with dilute sulphuric acid, or preferably dilute
hydrochloric acid, the free benzoic acid is obtained. A large proportion
of the so-called " benzoic acid ex toluol " is obtained in this manner as a
by-product in the manufacture of benzaldehyde.
The process of Lauth and Grimaux is also very largely employed ;
a mixture of benzyl chloride 5 kilos, nitrate of lead or copper 7 kilos,
and water 10 litres, is boiled for seven or eight hours in an apparatus
provided with a reflux cooler ; the reaction being as follows : —
C0H5CH2C1 + O = C6H5CHO + HC1.
When the reaction is complete the oil is distilled, or more nsually
decanted off, and the benzaldehyde thoroughly agitated with fifteen
times its weight of bisulphite of soda. This results in the formation of
the solid sodium bisulphite compound. This is washed with alcohol
and then decomposed by a solution of sodium carbonate, and finally the
benzaldehyde is distilled in a current of steam.
A process giving a chlorine free product is as follows : —l
A mixture of 300 kilos of toluene and 700 kilos of 65 per cent, sul-
phuric acid is thoroughly agitated, and 90 kilos of finely powdered
manganese dioxide added little by little. The temperature is maintained
about 40°. The process is a very slow one, and finally a mixture of
unchanged toluene and benzaldehyde is obtained, and from this the
sulphite compound is prepared, purified, and the pure benzaldehyde
isolated as usual.
Benzaldehyde has the following constitution : —
CH
HC, .CH
C.CHO
„ ,, 5 mm ........ 45°
Specific gravity ......... 1'052
Optical rotation ....... . +0°
It forms a semi-carbazone melting at 214°, and a phenylhydrazone
melting at 156°.
On oxidation it readily yields benzoic acid, melting at 121°. Ex-
posure to the air is sufficient to effect this oxidation.
For the examination of benzaldehyde for chlorine, see p. 352.
SALICYLIC ALDEHYDE.
Salicylic aldehyde, C7H6O2, is the simplest representative of the
ortho-hydroxy aldehydes, which are, generally speaking, strongly odorous
1
D.R.P., 101221 of 1897.
compounds. It occurs naturally in the essential oil of several varieties
of Spiraea, and can be manufactured artificially with considerable ease
if the following details be followed :—
One hundred grams of caustic soda are dissolved in 100 c.c. of water
and placed in a round-bottomed flask. To this are added 30 grams of
phenol. The mixture should be warmed to 60° to 65° and then attached
to a reflux condenser. Seventy-five grams of chloroform are then added
gradually in the following manner: One-third is first to be added
through the condenser, and as the temperature rises the mixture must
be cooled to 65° by immersion in cold water. In ten minutes, a second
third of the chloroform is added with the same precautions, and after
another twenty minutes the remainder is added. After allowing the
whole to remain for two hours at 65°, with constant shaking, the chloro-
form in excess is distilled off in a current of steam, and the alkaline
liquid then acidified with dilute sulphuric acid, and steam passed through
until no more oily drops pass over. The distillate is extracted with
ether, and the ether evaporated. The residue now consists of salicylic
aldehyde with unchanged phenol. It is treated with strong solution of
sodium bisulphite, and the resulting crystalline compound is washed
with alcohol to remove phenol, and finally once with ether. The
crystals are decomposed by dilute sulphuric acid, and the liberated
salicylic aldehyde extracted with ether, and, on evaporation of the ether,
purified by distillation.
Salicylic aldehyde is an almost colourless oil with a fragrant odour
of meadowsweet. Its constitution is as follows :—
CH
HC/VJH
HC..COH
C.CHO
Solidify ing-point - 20°
It yields an oxime, melting at 57°, and a phenylhydrazone, melting
at 96°.
On oxidation it yields salicylic acid, melting at 155° to 156°.
CINNAMIC ALDEHYDE.
Cinnamic aldehyde, C9H8O, is the principal odorous constituent of:
cinnamon and cassia oils, and is manufactured to a considerable extent.
artificially. It can be extracted from the oils in which it occurs by
means of sodium bisulphite, the sodium bisulphite compound being
decomposed with dilute sulphuric acid, and distilled in a current of
steam. The preparation of artificial cinnamic aldehyde, which is used
in perfumery as a substitute for the natural oils, is usually carried out;
by a condensation of benzaldehyde and acetaldehyde, according to the
following reaction:—
C 6 H 5 . CHO + CH3CHO = C 6 H 5 . CH : CH . CHO + H2O.
VOL. II. 13
A mixture of 10 parts of benzaldehyde, 15 parts of acetaldehyde,

900 parks of water, and 10 parts of 10 per cent, solution of caustic soda
are allowed to stand for ten days at 30° with constant stirring. The
cinnamic aldehyde formed is extracted with ether and purified by
fractional distillation.
Cinnamic aldehyde is a sweet, odorous liquid, resembling cinnamon
oil, but without its delicacy of odour. It has the following consti-
tution : —
CH
^ .CH
C . CH : CH . CHO
at 20 mm. 128° „ 130°
Specific gravity 1-0540 „ 1*0570
Melting-point - 7-5°
Its phenylhydrazone melts at 168°, and its semi-carbazone at 208°.
PHENYLACETIC ALDEHYDE.
Phenylacetic aldehyde, C8H8O, is one of the most important of
modern synthetic perfumes. It has not been found naturally in essential
oils. It possesses a powerful odour of hyacinths, and is extremely
useful for the reproduction of all odours of this and the narcissus type.
Phenylacetic aldehyde can be prepared by various methods, of which
the following are the principal:—
Methyl cinnamate l (16 parts) is dissolved in methyl alcohol (20 parts)
and treated with bromine (20 parts). The mixture solidifies in the cold.
It is shaken with a solution of caustic soda (12 parts) in water (24 parts),
the temperature being kept down to 40°. After two hours the mixture
is neutralised with dilute sulphuric acid, and an oily layer separates.
This is mixed with water (to 250 parts) and sodium carbonate (5'5 parts)
added, and the aldehyde distilled in a current of steam, and extracted
with ether, and the ether evaporated. The yield is about 75 per cent, of
the theoretical.
By allowing phenylmagnesium bromide to react with ethoxyacetal,
Spath 2 has shown that the following reaction takes place :—
C6H5. MgBr. + (OC2H5). CH 2 . CH(OC2H5)2
= C2H5O . MgBr . + C6H5. CH(OC2H5). CH2(OC2H5).
The ether thus formed reacts with a second molecule of magnesium
phenylbromide, thus:—
C6H5CH(OC2H5). CH2(OC2H5) + MgC6H5Br
= C2H5OMgBr + C6H6 + C6H5. CH : CH(OC2H5).
1 2
Bull. Soc Ind. Mulhouse, 83 (1913), 805. Moiiatshefte, 36, (1915), 1.
On saponification this last compound yields vinyl alcohol and phenyl-
acetaldehyde and alcohol, thus :—
C6H6. CH : CH(OC2H5) + H20 = C 6 H 5 . CH 2 . CHO + C2H5OH.
Phenylacetaldehyde can also be prepared by treating sodium cinna-
mate with bromine, and then adding oxalic acid. The sodium salt of
phenylbromolactic acid results. On steam distillation this gives off CO2,
and yields phenylacetaldehyde (the reaction is probably more complicated
than the equation indicates):—
C6H5. CHBr . CHOH . COONa = C 6 H 5 . CH 2 . CHO + KBr + CO2.
It also results by reducing phenylethyl alcohol in vapour with copper
dust at 250°, when hydrogen is evolved:—
C 6 H 5 . CH2CH2OH = C^H5. CH 2 . CHO . + H2.
Phenylacetaldehyde is very apt to polymerise, especially in the pres-
ence of acid or alkali, so that its preparation in the pure state is a matter
of some difficulty. It has the following constitution :—
CH
HC/VJH
HC, .CH
C . CH 2 . CHO
„ „ at 11 mm 78°
CUMIC ALDEHYDE.
Cumic aldehyde, or isopropyl-benzaldehyde, is present in cummin oil
and in the oils of boldo leaf, cassie flower oil, and, probably, in certain
eucalyptus oils. It is an oil of powerful odour, having the formula
C10H120. Its characters are as follows :—
„ at 14 mm 116°
It yields a semi-carbazone melting at 210° to 211°, oxime melting at
58° to 59°, and phenylhydrazone melting at 126° to 127°.
C—CHO
HC
V/CH
C . CH(CH3)
It can be prepared by extraction from the oils in which it occurs by .
means of sodium bisulphite in the usual manner.
On oxidation it yields cuminic acid, melting at 114° to 115°.
METHOXY-CINNAMIC ALDEHYDES.
Ortho-methoxy-cinnamic aldehyde is present in small amount in
cassia oil. It has the composition C10H10O2, and its physical characters
are as follows:—
Melting-point 45°
Boiling-point 295°
Melting-point o f phenylhydrazone . . . . . . 116°
Para-methoxy-cinnamic aldehyde has been isolated from tarrago . oil.
Melting-point of oxime 138°
„ ' ,, „ semi-carbazone 220° (?)
,, , , , , phenylhydrazone . . . . . . 138°
The constitution of these aldehydes is as follows:—
CH C . O . CH
HCl /C.O.CH, HCV /CH

C . CH : CH . CHO C . CH : CH . CHO
o-methoxy-cinnamic aldehyde. £>-methoxy-cmnamic aldehyde.
The or tho-compound yields, on oxidation by permanganate of potas-
sium, methyl-salicylic acid melting at 99°, whilst the para-compound
yields anisic acid melting at 184°.
An aldehyde was isolated from the oil of the root of a variety of
Chlorocodon, by Goulding and Pelly,1 which Friedlander 2 has shown to
be _p-methoxy-cinnamic aldehyde. This aldehyde has been obtained
artificially by Tiemann and Parrisius3 by acting with chloroform on an
alkaline'Solution of methylresorcinol.
HYDKOCINNAMIC ALDEHYDE.
Hydrocinnamic aldehyde, C9H10O, exists in cinnamon bark oil. It
has the constitution—
CH
•Rr/V'TT
±±Oi| |UJti
HC| /CH
C . CH 2 . CH 2 . CHO
It forms a semi-carbazone melting at 130° to 131°.
PARA-METHYL-HYDROCINNAMIC ALDEHYDE.
This aldehyde is a homologue of hydrocinnamic aldehyde, having the
following constitution :—
1 2
Proc. Chem. Soc. 24'(1908),
s
62. Monatshefte, 30 (1909), 879.
Berichte,R (1880), 2366.
C.CH
HCl CH
C . CH2CH . CHO
It is prepared synthetically and has an intensely powerful odour of
the lily or lilac type.
ANISIC ALDEHYDE.
Anisic aldehyde, C8H8O2, is a methyl ether of para-oxy-benzaldehyde,
which is found to a small extent in the oils of fennel and aniseed. It is
manufactured on an extensive scale artificially, and is the basis of
all the perfumes of the hawthorn or "May blossom" type. It is
known commercially as " aubepine ". A certain amount of anisic alde-
hyde is obtained as a by-product in the manufacture of coumarin, but
the greater, part of it is obtained by very careful oxidation of anethol, the
characteristic constituent of aniseed oil, which has the constitution —
= CH . CH8
CH3
The aldehyde is obtained by gently warming the oil for about an hour
with three times its volume of nitric acid (specific gravity I'l), and separ-
ating the heavy oil so formed, and washing it with potash solution. The
crude oil is agitated with a warm concentrated solution of sodium bisul-
phite, with which the aldehyde combines, and the resulting crystalline
magma is washed with alcohol and pressed in blotting-paper, and dis-
solved in warm water. Excess of sodium carbonate is added, when the
aldehyde is liberated and floats on the surface of the liquid. It can be
further purified by distillation. It can also be prepared from phenol,
which is treated in ethereal solution, with a mixture of hydrochloric and
hydrocyanic acid gases, using zinc chloride as the condensing reagent.
An imide hydrochloride is formed according to the following equation : —
/OH
C6HrOH + HCN + HC1 = C6H4<
X
CH : NH . HC1
which on reaction with water forms ^>-oxy-benzaldehyde —
C0H4< + H20 = C6H4< + NH4C1

X
CH : NH . HC1 \OH
This on methylation in the usual manner yields anisic aldehyde.
Anisic aldehyde has the following constitution : —
C . GHO
HC/NCH
HC CH
C . OCH3
Its physical characters are as follows;—
,, , , at 4 m m . . . . . . . . 91°
It readily oxidises to anisic acid, melting at 184°, so that it should be
kept in amber glass, well-stoppered bottles, in order to prevent oxidation.
It forms a semi-carbazone melting at 203° to 204°, and two oximes, one
melting at 63° and the other at 132°.
There is a solid " aubepine" met with in commerce, which appears
usually to be the sodium bisulphite compound of anisic aldehyde.
VANILLIN.
Vanillin, C8H8O3, is one of the most important synthetic perfumes.
It is the active odorous ingredient of the vanilla pod, in which it occurs
to the extent of about 2 per cent., appearing on the surface of the bean
as a fine white crystalline efflorescence. It occurs naturally also in
Sumatra benzoin (about 1 per cent.), Siam benzoin (-15 per cent.), and
the balsams of Tolu and Peru (traces). Numerous other bodies have
been recorded as containing it, such as asafoetida, beetroot and as-
paragus, the seeds of Lupinus albus, the seeds of Rosa canina, etc.
It was first artificially prepared by Tiemann from the glucoside coni-
ferin, which occurs in the cambium of various coniferous woods. The
constitution of vanillin is that of methyl protocatechuic aldehyde—
C.CHO
HG C . O . O H3
V
C.OH
Vanillin.
and coniferin, C16H22O8 + 2H2O, which is a glucoside melting at 185°,
was the substance which Tiemann first used for preparing vanillin from,
and for whose process Haarmann and Eeimer took out a patent. Coni-
ferin was decomposed, either by emulsin or by boiling with dilute acids,
into glucose and coniferyl alcohol, C6H3(OH)(OCH3)C3H4OH, and this
body on oxidation yields vanillin ; or the oxidation may take place first
and the hydrolysis afterwards. The process then consisted of the follow-
ing reactions. When coniferin is oxidised with an aqueous solution of
chromic acid it is converted into gluco-vanillin.
C6H3(0. CH3)(0. C6HU05)(CHO),
the glucoside of vanillin, a crystalline body melting at 170°. For this
purpose a solution of 10 parts of coniferin in 200 parts ot water is treated
at the ordinary temperature with a solution of 8 parts of chromic acid
dissolved in a small quantity of water, and the mixture allowed to stand
for several days. Barium carbonate is then added to precipitate the
chromium. The solution is evaporated to a small bulk, treated with
alcohol and filtered. The filtrate on evaporation yields crystals of gluco-
vanillin, melting at 170°. On treating this body with the ferment emulsin,
or by boiling it with dilute mineral acids, it is decomposed into glucose
and vanillin. The latter may be extracted with ether. This process,
however, has only an historical interest to-day.
The most important method, however, by which vanillin is now pre-
pared is by the oxidation of eugenol, the chief constituent of oil of cloves.
This process proved the subject-matter of a patent taken out in England
in 1876 by Tiemann, and an almost simultaneous one in France by De
Laire. The eugenol was instructed to be separated by diluting the oil
with three times its volume of ether and agitating the ethereal solution
with a dilute solution of ,potash or soda. The aqueous liquid is separated
and acidified, and the eugenol separated by extraction with ether. The
eugenol is first acetylated by means of acetic anhydride, and the resulting
acet-eugenol is dissolved in acetic acid and oxidised with permanganate
of potassium. The liquid is then filtered, and rendered alkaline, and the
whole is then evaporated, and the residue treated with moderately dilute
acid, and extracted with ether. The ethereal solution is extracted with
a solution of sodium bisulphite, which combines with the vanillin. The
double sulphite compound is decomposed with dilute sulphuric acid, and
the vanillin is extracted with ether, from which solvent it is obtained in
fine white crystals.
The best yield, however, is obtained by first converting the eugenol
into iso-eugenol, OH . OCH3 . C6H3 . CH : CH . CH3, bv treating it with
solution of potassium hydrate. The acetylation product is oxidised, by
which a cetyl- vanillin is chiefly formed, which yields vanillin by splitting
off the acetyl group.
By direct oxidation by means of ozone, isoeugenol is converted into
vanillin.
OH . OCH3 . C0H3 i CH : CH . CH3 + 2O3 =
isoeugenol
CH3COH + C8H803
vanillin.
Vanillin is also obtained by starting from meta-amido-benzaldehyde,
which is converted into its diazo compound, which yields meta-oxy-
benzaldehyde, on treatment with water. These reactions may be repre-
sented as follows : —
xNH./1) N 2 . NO3
CGH4< " +NOHO + HN08 = C 0 H/ +2H 0 O
\COH
Meta-amido-benzaldehyde. Diazo nitrate.
X N 2 '.NO 3 /OHd)
C0H / + H90 = C0H / + N 2 + HN03
\COH \COH<8>
Meta-oxybenzaldehyde.
The weta-oxybenzaldehyde is then nitrated and methylated, by which
means para-nitrome£a-methoxy-benzaldehyde
C6H3 . NO 2 (4) . OCH3 ( 3 ) . COH11)
is formed. By reduction this is altered to the corresponding amido-
aldehyde, which is again diazotised and the amido-group replaced by
hydroxyl in the usual wray, when j9ara-oxywe£a-methoxy-benzaldehyde
results, which is, of course, identical writh vanillin, or protocatechuic

aldehyde methyl ether, C6H3 . COH1 . OCH33 . OH4. Another compli-
cated method, which is the subject of a patent, is to nitrate meta-
methoxy-cinnamic acid methyl ester, by which means the corresponding
m<3ta-methoxy-jt96&ra-nitro-cinnamic methyl ester is formed. This body,
C6H3 . OCH/) . NO2(4) . (G.2H2C02G'Hs)(l) is hydrolysed and the free acid
is converted into its ammonium salt, which is dissolved in water and
reduced to the corresponding meâ-methoxy-âra-amido-cinnamic acid.
This is diazotised in the usual way, and the amido-group is replaced by
hydroxyl, by which means an acid termed ferulic acid is formed. This
is meta-mekhoxy-para-oxyeinudbmic acid, C6H3(OCH3)OH . (C2H2COOH).
This acid is oxidised (best as an acetyl compound) with potassium per-
manganate, and thus converted into vanillin. The two methods last
described, viz. those starting from weto-oxybenzaldehyde and methoxy-
cinnamic acid are only of theoretical interest.
Vanillin is also produced in several ways from guaiacol. A recent
patent (D.R.P. 189,307 — German patent) for this is as follows : Guaia-
col is treated with hydrocyanic acid in the presence of hydrochloric acid
and zinc chloride. The reaction mass, after forty-eight hours, is treated
with hot water and filtered; the unaltered guaiacol is removed by ex-
tracting the vanillin from ethereal solution by means of sodium bi-
sulphite and recovering it in the usual manner. Care must be taken to
remove all traces of guaiacol, as the slightest taint with this phenol
entirely spoils the odour and flavour of the vanillin.
Tiemann and Reimer have prepared vanillin by the action of chloro-
form on guaiacol in an alkaline medium. The mixture is boiled under
a reflux condenser for six hours. A mixture of vanillin and meta-
methoxysalicylic aldehyde results. The mixed aldehydes are separated
from the reaction mass by means of bisulphite in the usual manner,
and the liberated aldehydes are separated in a current of steam. The
vanillin is formed according to the following reaction —
CH C . CHO
+ CHC1,' + 3KOH = 3KC1 + 2H,O

~ +
GEl,v C . O . CH
s\J . W . V^-L-Lg J.-LVAN IJC.O.CH,
xV
C\OH C.OH
(Guaiacol). (Vanillin).
Another method of obtaining vanillin from guaiacol is as follows:
Formic aldehyde is allowed to react with guaiacol in the presence of
phenylhydroxyJamine sulphonate:—
OTT TT ^tO TT
CflH4/ + H . COH + \N . CBH /
\CH3 OH/ \CH3
OH\ /OH
\CGH3. CH,. N< + H20
OCH/ XH3(HS03)(OH)
This body gives up another molecule of water, yielding
OHV xHS03
>C 6 H 3 . CH : N . C(.H,<
3
OCH/ \OH
'which, on hydrolysis by means of sodium acetate, yields vanillin and a
methyl-amido-sulphonic acid.
Guyot and Gey have prepared vanillin by a synthesis depending on
the property possessed by compounds containing two carbonyl groups in
juxtaposition, of condensing with guaiacol giving products from which
it is easy to pass to vanillin.
Acetylglyoxylic acid
CH,— CO— CO— COOH
for example, yields with guaiacol the compound
OH
.CO-CH,
COOH
which is converted by oxidation into vanilloyl carboxylic acid
(CH3O)(OH)C6H3— CO— COOH.
This latter, when heated at 150° to 160° C. with dimethyl-p-toluidine is
decomposed with the production of vanillin.
Gattefosse and Morel (La Parfumerie Moderne, 1919, 114) describe a
method for the production of vanillin by reducing nitrobenzene-sul-
phonic acid with iron filings and hydrochloric acid in the presence of
guaiacol and formic aldehyde. The first-named body is reduced to
phenyl-hydroxylamine-sulphonic acid, which reacts with the guaiacol
as follows : —
/S03H X)CH.,
€6H4< + C6H4< ' + HCOH
\NHOH X)H
Guaiacol. Formic aldehyde.
/SO3H /OCH3
= CtiH / + H20 + C(iH3f OH
\NH3 \CHO
Vanillin.
Vanillin yields a number of well-defined crystalline derivatives, of
which the following are the principal : Bromo vanillin,
C6H2Br (CHO) (OCH3) (OH) ,
melts at 160° to 161° and results when an aqueous solution of vanillin is
treated with bromine. lodo-vanillin melts at 174°. Vanillin methyl
ether melts at 42° to 43°, and the ethyl ether at 64° to 65°. The oxime
Vanillin forms fine white' needles melting at 81° to 82°, or when
.absolutely pure at 82° to 84°, and possessing an intense vanilla odour.
Some of the cheaper commercial samples are heavily adulterated with
the quite odourless compound, acetanilide. The effect of this body is to
lower the melting-point even if present in large quantity, but it is very
easily detected, as by boiling with solution of potash, aniline is formed,
which is easily detected by any of the usual reactions. A quantitative
separation may be effected as follows : The substance is dissolved in
ether and the liquid repeatedly shaken with concentrated solution of
sodium bisulphite. The vanillin is thus extracted, and the ether, after
being washed twice with water, is allowed to evaporate, when the acet-
anilide remains. This will then be found1 to have a melting-point close-
to 113°. A little isovanillin, C6H3(CHO) (OH)3(OCH3)4, is occasionally
present, but this is due to the fact thar, it is generally formed in small
quantity with vanillin, in many reactions.
Acet-iso-eugenol, one of the intermediate bodies in the manufacture of
vanillin, is sometimes found in commercial samples; it lowers the melt-
ing-point of the sample, yields acetic acid in hydrolysis, and gives a fine
red colour with strong sulphuric acid, whereas pure vanillin only gives a
lemon-yellow colour. Benzole acid is also found as an adulterant. This
is easily detected by the high acid value of the substance (vanillin is-
neutral), and by dissolving the sample in ether, extracting the vanillin by
means of sodium bisulphite solution, and neutralising the residue from the
ethereal solution with potash, dissolving it in water, and testing it with a
neutral solution of ferric chloride, when red ferric benzoate is precipi-
tated.
In examining vanilla beans the determination of the vanillin is a
matter of importance. Busse recommends the following process for the
determination: 20 grams of the pods, crushed with sand, are exhausted
with ether in a Soxhlet tube, and the ethereal extract is shaken out with
20 per cent, sodium bisulphite solution. From the latter, vanillin is re-
moved by treatment with dilute H2SO4, the SO2 generated removed by a
current of CO2, and the vanillin extracted by shaking out with ether,
evaporating the solvent and weighing the residue. In East African vanilla
the author found 2*16 per cent, of vanillin, in that from Ceylon 1*48 per
cent., and in Tahiti vanilla from 1-55 to 2'02 per cent. Tiemann and
Haarman found in the best Bourbon vanilla 1*94 to 2*90 per cent., in the
best Java vanilla 2*75 per cent., and in Mexican vanilla from 1*7 to 1*9
per cent. Tahiti vanilla sometimes contains less than 1 per cent, of
vanilla.
In suspected cases the crystals on the beans should be carefully
separated and examined for benzoic acid as above described.
Hanus l recommends that /2-naphthyl hydrazine hydrochloride should
be added to the solution of vanillin in such proportion that from two to
three parts are present for each part of vanillin. After standing for five
hours the precipitate is transferred to a tared filter, washed with hot
water until the washings no longer precipitate silver nitrate, dried at 90°
and weighed. The weight of the hydrazine formed, divided by 1*92 gives,
that of the vanillin present. This method is available in all cases where
an aqueous solution of the vanillin can be prepared.
Hanus has more recently recommended the following method for the
determination of vanillin in vanilla beans and in preparations thereof.2
Three grams of the crushed pods are extracted for three hours in a Soxhlet
tube with ether, the solvent distilled off cautiously, and the residue dis-
solved in a little ether, the solution filtered and the filtrate evaporated
cautiously. The residue is treated with 50 c.c. of water at 60° on a
water-bath ; 0'25 gram of wetfa-nitrobenzhydrazide is then added to the
aqueous solution in a stoppered flask, which is kept for two to three hours
* Analyst, xxv. 318. * PJiarm. Zeit., 50, 1022, 157.
at 60°, and then set aside with occasional shaking for twenty-four hours.
"The vanillin is precipitated quantitatively as vanillin-meto-nitrobenzhydra-
zone, N0 2 . C6H4 . NH 4 . N : CH . C6H3(OCH3). OH. The precipitate
is washed with three successive quantities of petroleum ether to remove
fat, then washed with water, and then again with petroleum ether, and
then dried at 100° for two hours. The weight, multiplied by 0 4829
gives the amount of vanillin present. Preparations of vanillin are
treated similarly, alcohol being removed by evaporation. The presence
of other aldehydes, suc]^ as heliotropin, of course, will vitiate the results
Essence of Vanilla.—The substance sold under this name is, properly,
a spirituous extract of the vanilla bean. Many samples, however, are
little more than alcoholic solutions of artificial vanillin, coloured with
caramel. Some samples, which cannot be described as adulterated, con-
tain a little coumarin or other odorous substance, added to vary the
characteristic vanillin odour and flavour somewhat.
A genuine extract can bs recognised by the fact that it contains some
dark red or red-brown resin, soluble in 50 per cent, alcohol, but pre-
cipitated on further dilution.
Coumarin, or extract of Tonka beans, which contain coumarin, may
be detected as follows : A small quantity of the essence is evaporated to
dryness, the residue fused with caustic potash, saturated with hydro-
chloric acid and treated with a drop of ferric chloride solution. If
coumarin be present, a violet colour due to the formation of salicylic acid,
will be produced.
Winton and Silverman l recommend the following methods for ex-
amining essence of vanilla :—
De-alcoholise 25 grams of the extract in an evaporating dish upon a
water-bath, at a temperature of about 80° C., adding water from time to
time to retain the original volume. After removal of the alcohol, add
normal lead acetate solution, drop by drop, until no more precipitate
forms. Stir to facilitate flocculation of the precipitate, filter through a
moistened filter, and wash three times with a few c.c. of hot water.
Cool the filtrate and extract with ether by shaking out in a separator.
Use 15 c.c. to 20 c.c. of ether at each separation, repeating the process
three or four times, or until a few drops of the ether, evaporated upon a
watch glass, leaves no residue. Place the combined ether extracts con-
taining all of the vanillin and coumarin in a clean separator, and shake
out four or five times with 2 per cent, ammonia, using 10 c.c. for the
first, and 5 c.c, for each subsequent shaking.
Set aside the combined ammoniacal solutions for the determination
of vanillin.
Wash the ether solution into a weighed dish, and allow it to evapor-
ate at the room temperature. Dry in a desiccator and weigh. Usually
the dried residue is pure coumarin. Treat the residue with 5 c.c. to 10
c.c. of cold petroleum ether, boiling between 30° C. and 40° C., and decant
off the clear liquid into a beaker. Kepeat the extraction with petroleum
ether until a drop evaporated on a watch glass, leaves no residue. Dry
the dish for a few moments in a water oven, cool and weigh. Subtract
the weight of the dish and the residue (if any) from the weight previously
obtained after evaporation with ether, thus obtaining the weight of pure
coumarin. Allow the petroleum ether to evaporate at the room tempera-
ture, and dry, if necessary, in a desiccator. The residue should be
l
Jour. Amer. Chem. 8oc.t 24, 1128.
crystalline and have a melting-point of 67° C. This, with the character-
istic odour of coumarin, is sufficient for its identification.
Slightly acidulate the reserved ammoniacal solution of vanillin with
10 per cent, hydrochloric acid. Cool and shake out in a separatory
funnel with four portions of ether of about 15 c.c. to 20 c.c. each.
Evaporate the ether at room temperature in a weighed platinum dish,
dry over sulphuric acid, and weigh. Treat the residue with boiling
petroleum ether (boiling-point 80°) decanting into a dry beaker. Eepeat
the treatment until all vanillin is removed. Dry the dish and .residue (if
any) for a few moments at 100° C. and weigh ; deduct the weight from
the weight of the ether residue. The difference is the weight of the
vanillin. Evaporate the petroleum ether at ordinary temperatures, and
dry in a desiccator. The residue should be crystalline, and melt at 80° C.
to 81° C.
Tests for Caramel.—Valuable indications of the nature of an extract
are obtained in the process of determination of vanillin and coumarin.
Pure extracts of vanilla beans give, with lead acetate, a bulky, more or
less glutinous, brown-grey precipitate, and a yellow or straw-coloured
filtrate, whereas purely artificial extracts coloured with caramel give a
slight dark brown precipitate and a dark brown filtrate. If both vanilla
bean extract and -caramel are present the precipitate is more or less bulky
and dark coloured, and the filtrate is more or less brown. The solution
remaining after extraction of the vanillin and coumarin with ether, if
dark coloured, should be tested for caramel.
The most satisfactory test for caramel is to shake with Fuller's earth,
as recommended - by Crampton and Simons. If the colour is due to
caramel and a grade of Fuller's earth is used, which experience has
proved suitable, the solution, after filtering, is yellow or colourless. This
test does not positively identify the colour, as some other brown sub-
stances may give similar reactions, but no such substance is liable to be
present in vanilla extract.
Winton and Bailey determine vanillin, coumarin, and acetanilide
(which is sometimes found as an adulterant of artificial vanillin, and
therefore indicates its presence) in the following manner, 1which is a
modification of the method devised by Hess and Prescott : -
Twenty-five grams of the essence are weighed into a 200 c.c. beaker,
marked to indicate volumes of 25 c.c. and 50 c.c. The essence is diluted
with water to 50 c.c. and evaporated on a water-bath to 25 c.c. at a
temperature not exceeding 70°. It is now again diluted to 50 c.c. and
evaporated to 25 c.c. Solution of acetate of lead is then added until no
further precipitation takes place. The liquid is then, after being well
stirred, filtered through a moistened filter paper, and washed three times
with hot water, so that the total filtrate does not exceed 50 c.c. The
filtrate, when cold, is shaken with 20 c.c. of ether in a separator. The
ether is separated, and the liquid extracted with three further portions of
15 c.c. of ether. The combined ether extracts are then shaken with 10 c.c.
of 2 per cent, ammonia solution and with three subsequent portions of 5
c.c. The ethereal solution is reserved (B) and the combined ammoniacal
solutions are rendered slightly acid with 10 per cent, hydrochloric acid.
The liquid is then extracted four times with ether, and the ether evapor-
ated and the residue dried at room temperature, and finally in a desic-
cator and weighed (A). If acstanilide is absent, this may be taken as
1
Jour. Amer. Cliem. Soc. (1899-), 256.
pure vanillin, which should melt at 79° to 81°. If acetanilide has been
detected (vide infra), the residue should be dissolved in 15 c.c. of 10 per
cent, ammonia, and the liquid shaken twice with ether. The ether, on
evaporation, will- leave a residue of acetanilide, which is dried at room
temperature and then in a desiccator and the weight deducted from the
"vanillin" (A) previously weighed. The total amount of acetanilide is
the amount thus obtained, together with that present in the ethereal
solution (B) reserved above. The latter is transferred to a tared dish and
the ether allowed to evaporate at room temperature. The residue is dried
in a desiccator and weighed. It is then extracted several times by stir-
ring well with petroleum ether, which is decanted each time. If the
residue is thus completely dissolved, it may be taken to be entirely
coumarin. Any undissolved residue is probably acetanilide (melting-point
112° to 113°) and its weight deducted from the total residue gives the
coumarin.
The acetanilide here found is added to the amount extracted with the
yanillin to give the total amount present.
The presence of acetanilide in these residues may be confirmed by
boiling the residue for two to three minutes with HC1, and when cool,
adding a few drops of 0'5 per cent, of chlorinated lime solution, in such a
manner that the liquids do not mix. A fine blue colour results if acetani-
lide be present.
Commercial essence of vanilla is usually made with about 5 per cent,
of vanillas, the menstruum varying in strength from 40 to 50 per cent.
alcohol in the best varieties. Sugar is sometimes added, but not always.
The average vanillin content is 0*1 to 0*2. Much higher values than
these indicate the presence of synthetic vanillin.
Dox and Plaisancex have described the following method for the
determination of vanillin in extracts of vanilla. In depends on the use
of thiobarbituric acid in the presence of 12 per cent, hydrochloric acid
as a precipitating agent. The precipitate consists of a condensation
product 3-methoxy-4-hydroxy-benzal-malonyl-thiourea. The method
of procedure is as follows: 25 c.c. of the extract is freed from alcohol,
transferred to a 50 c.c. standard flask, and filled up with lead acetate
solution. After standing for several hours at about 37° C., the contents
of the flask are filtered through a dry filter. The filtrate should be a
straw colour, indicating absence of caramel. Forty c.c. of the filtrate is
transferred to another 50 c.c. flask, and sufficient concentrated hydro-
chloric acid is added to make the volume 50 c.c. After standing a few
minutes the lead chloride is removed by filtration and 40 c.c. of the
filtrata is taken for the determination. On adding thiobarbituric acid in
12 per cent, hydrochloric acid solution, an orange-coloured precipitate
results, which, after standing overnight, is filtered on a Good} filter,
washed with 12 per cent, hydrochloric acid, and dried at 98°. A correc-
tion is made tor the solubility of the condensation product which amounts
to 2*6 milligrammes. The conversion factor for the vanillin equivalent
to the weight of condensation product obtained is 0*5462, or T6T, after
correcting for the solubility and the aliquot part taken. Thus, the weight
of precipitate obtained from 64 per cent, of 25 c.c. of extract was 0*450,
and corrected for solubility 0*476, equivalent to 0*026 gramme of vanillin,
or 016 per cent, of the original extract.
The method is not applicable to artificial extracts where caramel is
1
Amer. Jour. Chem. (1916), 481.
added, since caramel contains furfural derivatives which react with thio-
barbituric acid. A delicate test for caramel is the reaction with phloro-
glucinol. After clarification and removing excess of lead as chloride, on
the addition of a solution of phloroglucinol a brown precipitate is formed.
If caramel is absent a delicate rose-pink colour or a slight pink precipitate
may be obtained.
HELIOTROPIN.
This body, also known as piperonal, is a white crystalline compound
possessing a powerful odour of heliotrope. It is the methylene ether of
protocatechuic aldehyde, of the constitution—
/CHOW
The source from which it was originally made is the base piperine,
C17H19NO3. Ground pepper, preferably white Singapore pepper (which
contains up to 9 per cent, of the alkaloid), is mixed with slaked lime
and water, and the whole evaporated to dry ness on a water-bath. The
dry mass is then extracted with ether, which deposits the piperine on
evaporation; or the pepper may be exhausted with alcohol, and the
alcohol recovered. The semi-solid residue is mixed with potash solution,
and the insoluble powder left is washed with water and recrystallised
from alcohol, when the piperine is obtained nearly pure. When boiled
with solution of caustic potash in alcohol, the base is converted into
potassium piperate, which on oxidation with potassium permanganate
yields heliotropin. The heliotropin of commerce, however, is manu-
factured by the oxidation of safrol. This body (q.v.) and its isomer
isosafrol yield large quantities of heliotropin on oxidation with potassium
permanganate or chromic acid.
To prepare heliotropin from isosafrol (which results from the isomerisa-
tion of safrol with alkalis), 5 parts of isosafrol are treated with a solu-
tion of 25 parts of potassium bichromate, 38 parts of concentrated
sulphuric acid, and 80 parts of water. The reaction product is steam
distilled and the distillate is extracted with ether, and the heliotropin
obtained is purified by means of alkaline bisulphite in the usual manner.
Heliotropin melts at 37°, but its perfume is injured by exposure to a
temperature several degrees below this, and it should always be stored in
cool dark places. In very hot weather the stock may with advantage be
kept dissolved in alcohol, ready for use. Its perfume is a powerful helio-
trope odour, and is improved by blending it with a little coumarin or
vanillin, or with bergamot, lemon, or neroli oil. Attention should be
drawn to the fact that the fancy perfumes whose names resemble helio-
trope are usually mixtures of heliotropin—the cheaper ones being chiefly
acetanilide, the more expensive ones containing vanillin or coumarin.
Heliotropine forms a number of well-defined crystalline compounds,
which are suitable for its identification. Bromopiperonal
C 6 H 2 Br. (CHO)(02CH2)
is prepared by treating heliotropine dissolved in carbon bisulphide, with
a slight excess of bromine. It forms crystalline needles melting at 129°.
The oxime of heliotropine exists in two isomeric forms, one melting at
110° to 112°, and the other at 146°. The semi-carbazone melts at 146°.
It also yields a mononitro-derivative which melts at 94'5°, and on oxida-
tion yields piperonylic acid melting at 228°, which on reduction yields
piperonyl alcohol melting at 51°.
ASARYLIC ALDEHYDE.
Asarylic aldehyde, C]0H12O4, is present in calamus oil, and also re-
sults from the oxidation of asarone. It has the constitution—
G . CHO
He"JC.OCH 3
C . OCH.
Asarylic aldehyde is a crystalline body melting at 114°, and yields
asaric acid on oxidation,1 which melts at 144°.
Fabinyi and Szeki give the following details of the compounds
yielded by this aldehyde, which are serviceabler for identification purposes.
When the aldehyde is heated on the w ater-bath with 25 per cent,
hydrochloric acid, it yields a triphenylmethane derivative, nonamethoxy-
triphenylmethane, a body consisting of snow-white crystals, melting at
184*5°. The action of concentrated nitric acid upon the solution in
glacial acetic acid of this triphenylmethane derivative gives rise to
1, 2, 5-trimethoxy-4-nitrobenzene (melting at 130C). With bromine,
nonamethoxytriphenylmethane combines, with separation of a molecule
of trimethoxy bromobenzene, into a tribromo additive compound of
hexamethoxy diphenylmethane, a deep violet-blue body. The 1, 2, 5-tri-
methoxy-4-bromobenzene (melting at 54-5°) may be obtained more readily
from asaronic acid.
PEEILLIC ALDEHYDE.
Perillic aldehyde, C10H14O, is present in the essential oil of Per ilia,
nankinensis. It has been examined by Semmler and Zaar,2 who isolated
it from the oil by means of its sodium sulphite compound. Perillic
aldehyde has the following characters :—
,CH,
CH—C
,CH
J.CHO
1 2
Berichte, 43 (1910), 2676. Ibid., 44, 52 and 815.
By reduction with zinc-dust and acetic acid it yields the acetic ester
of perillic alcohol, from which the alcohol itself is separated by saponi-
fication.
The oxime of perillic aldehyde melts at 102°, and when heated with
acetic anhydride in presence of sodium acetate, is converted into the-
nitrile of perillic acid, a liquid having the following characters :—
On saponification the nitrile yields perillic acid, C10H14O.j, a solid
body having the following characters :—
Boiling-point at 10 mm. pressure 164° ,, 165°
Furukawa and Tomizawa l state that perillic aldehyde has the follow-
ing characters:—
Boiling-point 237°
and that it yields two oximes. Of these the a-anti-aldoxime melts at

102° and is 2000 times as sweet as sugar. The /?-syn-aldoxime melts at
129° and is not sweet. The phenylhydrazone melts at 107'5° and the
semicarbazone at 190° to 199°. The nitrile, according to these chemists
boils at 123° at 15 mm., and has a specific gravity 0'949 at 15°. They
give 132° to 133° as the melting-point of perillic acid, which yields an
amide C9H13. CO . NH 2 melting at 164° to 165°. Perillic alcohol has
a specific gravity 0'969 and boils at 118° to 121° at 11 mm.
Dibromoperillic acid melts at 166° to 167°.
These results show that the structure of perillic aldehyde is similar to
that of limonene, and that, consequently, the reducible double bond is
next to the aldehydic group.
When perillic acid is dissolved in five times its weight of amyl
alcohol and is reduced by sodium at the boiling temperature, dihydro-
perillic acid, C10H16O2, is obtained. This acid melts at 107° to 109° C.
By the reduction of its methyl ester by means of sodium, dihydroperillic
alcohol is formed, which is a liquid with a rose odour and having the
MYRTENAL.
Myrtenal, C10H14O, is an aldehyde found in the oil of Per ilia nankin-
ensis, associated with perillic aldehyde. It is also formed by the reduc-
tion of myrtenol, an alcohol of the formula C10H16O, occurring in oil of
myrtle leaves. Myrtenal has the following characters :—
L
Jour. Chem. Ind. Tokyo, 23 (1920), 342.
Eefractive index . 1-5042
Melting-point of semi-carbazone 230°
„ „ ,, oxime 71° to 72°
Its constitution is—
•CH,
HO
AROMADENDRAL.
This aldehyde has been isolated from various Eucalyptus oils by
Baker and Smith. It has a pleasant odour resembling that of cumic
aldehyde, with which Schimmel & Co. have considered it to be identical.
This, however, is improbable, and Baker and Smith l consider it to have
the formula C9H12O, which would make it to be a lower hornologue of
the terpenic aldehydes. Its physical characters, however, are somewhat
doubtful, as specimens isolated from the oils of Eucalyptus hemiphloia
and Eucalyptus salubris show. These are as follows:—
From E. From E.
Hemiphloia. Salubris.
Boiling-point 210° 218° to 219°
,, rotation . - 49° 12' - 90° 25'
It forms an oxime melting at 85°, and a phenylhydrazone melting at
104° to 105°, or possibly a few degrees higher. It also forms a naphtho-
cinchoninic acid melting at 247°, and on oxidation yields aromadendric
acid melting at 137° to 138°, when dried at 110°. These figures are
to be accepted with reserve, as it is not certain that aromadendral has
yet been separated free from cumic aldehyde.
CRYPTAL.
2
Baker and Smith have isolated an aldehyde from the oils of
Eucalyptus hemiphloia and Eucalyptus bractata, of the formula C10H16O,
which they have named cryptal. Two specimens prepared from the
former oil had the following characters :—
Specific gravity at 20° 0-9431 0'9426
Optical rotation - 76-02° - 76-2°
Eefractive index at 20° 1-4830 1-4830
Boiling-point at 10 mm. . 98° to 100° 99° to 100°
Melting-point of semi-carbazone 176° „ 177° 176° „ 177°
1
2
Jour.
Proc. Roy. Soc., N.S.W. (1900), xxxiv.
A Research on the Eucalypts, 2nd edition, 383.
VOL. II. 14
When prepared from the latter oil, two specimens had the following
characters :—
Specific gravity at 20° . . . . . . 0-9443 0-9446
Optical rotation - 49*7° - 50-2°
Melting-point of semi-carbazone . . . 180° 180°
All these specimens may be mixtures of the two optically active
varieties of the aldehyde.
PHELLANDRAL.
Phellandral, C10H16O, is a hydroaromatic aldehyde of the consti-
tution—
C.CHO
H0C CH,
OH
CH(CH3)2
It occurs in oil of water-fennel, from which it can be extracted by
means of its bisulphite of sodium compound. It also results from the
oxidation of /2-phellandrene.
Phellandral has the following characters :—
Boiling-point a t 5 m m . . . . . . . . . 89°
It is a liquid with an odour of cummin oil. It forms a semi-car-
bazone melting at 204° to 205°, and an oxime melting at 87° to 88°. Its
phenylhydrazone, which melts at 122° to 123°, is not very serviceable for
identification purposes, as it very rapidly resinilies.
On oxidation with moist silver oxide or even by exposure to the air
it yields an acid, tetrahydrocuminic acid (of which it is the corresponding
aldehyde) melting at 144° to 145°. This body is very useful for the
identification of the aldehyde, and is easily prepared in the following
manner. A few grams are exposed in a watch glass to the air for three
or four days, when a crystalline mass results, which is purified by com-
bination with sodium hydroxide in aqueous solution, extracting the
solution with ether, and precipitating the free acid by means of sulphuric
acid. If the aldehyde be oxidised by means of potassium permanganate,
it yields a dibasic acid of the formula C9H16O4, melting at 70° to 72°.
NOR-THICYCLOEKSANT ALAL.
This aldehyde, which has the formula CnH16O, appears to be the

only aldehyde with eleven atoms of carbon yet found in essential oils.
It was isolated from santal oil by Schimmel & Co.,1 who gave the follow-
1
Report, October (1910), 122.
ing details in regard to it: It was separated by means of its bisulphite
compound, and was found to have the following characters :—
„ » 761 „ 222° „ 224°
It forms a semi-carbazone melting at 223° to 224° and an oxime,

which is liquid, and boils at 135° to 137° at 7 mm. It isl probable
that this aldehyde is identical with that obtained by Semmler as a de-
composition product of tricycloeksantalal. To substantiate this belief,
Schimmel & Co. transformed the aldehyde into teresantalic acid. Twelve
c.c. of the aldehyde were heated for ninety minutes with 24 c.c. of acetic
anhydride and 2'5 grams of sodium acetate to boiling under a reflux
condenser. The reaction mixture was washed with water, and fraction-
ated, the resulting product being found to be a mixture of mono- and di-
acetates. By oxidation by means of permanganate of potassium, in
acetone solution, teresantalic a<jid, melting at 148° to 152°, was obtained.
The identity of this acid with the teresantalic acid occurring naturally in
santal oil was established, and the following figures indicate the differ-
ences—doubtless due to want of purification between natural nor-tricyclo-
eksantalal, and that obtained from santalol :—
From E.I. Sandalwood Oil From Santalol
(Schimmel & Co.). (Semmler).
Boiling-point 86° to 87° (6 mm.) 92° to 94° (11 mm.)
Specific gravity . 0-9938 0-9964
Optical rotation . - 38° 48' - 30-8°
Befractive index 1-48393 1-48301
Molecular refraction . 47-20 47-00
Semi-carbazone . melting-point 223° to 224° 224°
Nor-tricycZoeksantalic acid „ 91° „ 93° 93°
Teresantalic acid „ 148° „ 152° 156°
This aldehyde has the following constitution :-

H
*O
H2C c—CH2—(X
CH,
HC —C—CH,
SANTALAL.
This aldehyde, C15H22O, was isolated from santal oil by Guerbet 2
who considered it to have the formula C15H240. It has the following
characters:—
1 2
Berichte, 43 (1910), 1890. Comptes rendus (1900), cxxx. 417.
Boiling-point at 10 mm. 152° to 155°-
Specific gravity at 20° . 0-^95
Melting-point of semi-carbazone about 230°
oxime 104° to 105°
It yields santalic acid, C15H2202, on oxidation.
FAKNESAL.
Farnesol, C15H26O, yields, on oxidation, the aldehyde farnesal,
C15H24O. It forms a semi-carbazone melting at 133° to 135°. Its char-
acters are as follows :—
Specific gravity at 18° . . . 0'893
Its constitution is probably as follows :—
(CH3)2C : CH . CH 2 . CH 2 . C(CH3): CH. CH 2 . CH 2 . C(CH3)CH . CHO,
6. KETONES.
Ketones are bodies of the type K . CO . K', where K and B' may be
identical or different radicles. Ketones are prepared either by the oxida-
tion of secondary alcohols or by the distillation of the calcium salts of the
corresponding acids. Like the aldehydes, the ketones, in general, give
condensation products with hydroxylamine and with phenylhydrazine.
They also, as a general rule, form semi-carbazones. The following is a
useful method for determining whether a ketone is present in a given
mixture. By acetylating the oil, with a consequent saponification the
amount of alcohols present is indicated. The specimen is then treated
with sodium and alcohol, which will reduce most ketones to their cor-
responding alcohols. The reduced oil is now acetylated and saponified.
If it now shows a greater alcohol value this is probably due to the
presence of ketones. Ketones may frequently be determined by absorp-
tion by acid or neutral sodium sulphite, but the generally most useful
method is that based on the reduction of the ketones to alcohols. To
carry out this process 15 c.c. of the mixture is dissolved in 60 c.c. of
absolute alcohol in a flask attached to a reflux condenser. From 5 to 6
grams of sodium in small pieces are then added, and the mixture kept at
the boiling-point. When the metal is dissolved the mixture is cooled,
and the oil is washed with water until quite neutral, after having been
washed first with acetic acid. The amount of alcohols present is then
estimated by the usual acetylation process, and compared with that found
in the unreduced sample. The difference is accounted for by the amount
of ketone present.
Only a few of the ketones of the fatty series are found as natural con-
stituents of essential oils, the majority of them belonging to the aromatic
or hydroaromatic series. The following members of the open-chain
series are found in essential oils :—
ACETONE.
Acetone, CH 3 . CO . CH3, is found in the distillation waters of a few
essential oils such as that of the Atlas cedar. It is a mobile and very
volatile liquid, miscible with water and with oils, and having the follow-
ing characters :—
It forms an oxime melting at 59° to 60°, and a £>ara-bromphenyl-
hydrazone melting at 94°.
METHYL-AMYL KETONE.
This ketone, of the constitution CH3. CO . CH 2 . CH 2 . CH 2 . CH 2 . CH3,
is found in oils of clove and cinnamon. It can be isolated by means of
its sodium bisulphite compound. Its characters are as follows :—
Boiling-point " 151° to 152°
Melting-point of semi-carbazone 122° ,, 123U
ETHYL-AMYL KETONE.
Ethyl-amyl ketone, CH3 . CH2 . CO . CH 2 . CH 2 . CH 2 . CH 2 . CH3, has
been isolated from French lavender oil. Its characters are as follows :—
Melting-point of semi-carbazone . 117-5°
It does not form a crystalline compound with sodium bisulphite.
METHYL-HEPTYL KETONE.
This ketone has been isolated from oil of rose, and in traces, from oil
of cloves. It has the following constitution :—
CH63 . CO. CH&2 . CH2A CHL2 . CH2.2 . CH£2 . CH10 . CH3o.
Boiling-point 196°
„ at 15 mm 80° to 82°
Melting-point - 17°
It forms a crystalline semi-carbazone melting at 118° to 119°. Its
oxime is liquid. On oxidation with hypobromite of sodium it yields caprylic
acid.
METHYL-NONYL KETONE.
Methyl-nonyl ketone,
CH 3 . CO. CH 2 . CH 2 . CH 2 . CH 2 . CH 2 . CH 2 . CH 2 . CH 2 . CH3,
is the principal constituent of French oil of rue. It is a solid compound
of low melting-point, having a characteristic odour of rue. Its characters
are as follows :—
Boiling-point 233°
Melting-point +13°
It yields an oxime melting at 46° to 47°, and a semi-carbazone melt-
ing at 123° to 124°.
METHYL-HEPTENONE.
Methyl-heptenone, C8HUO, occurs in various essential oils, especially
lemon-grass oil, in which it is associated with, and difficult to separate
from, the aldehyde citral.
It is a liquid of strong odour, recalling that of amyl acetate, and has
the constitution:—
CH3X
)C : CH . CH,. CH,. CO. CHS.
CH/
Methyl-heptenone has the following characters :—
From Lemon- From Decornposi-
grass Oil. tion of Citral.
Boiling-point 173° 173° to 174°
Refractive index at 15° 1-4380 —
Optical rotation ±0° ±0°
It forms a semi-carhazone melting at 136° to 138°, which can be ob-

tained as follows : Ten c.c. of methyl-heptenone are dissolved in 20 c.c. of
glacial acetic acid, and a mixture of 10 grams of semi-carbazide hydro-
chloride and 15 grams of sodium acetate dissolved in 20 c.c. of water is
added. After half an hour the semi-carbazone is precipitated by the
addition of water, and recrystallised from dilute alcohol.
Methyl-heptenone also forms a bromine derivative which is well suited
for the identification of the ketone. This body, which has the formula
C8H12Br30 . OH, melts at 98° to 99°, and is obtained as follows : Three
grams of methyl-heptenone are mixed with a solution containing 3 grams
of caustic soda, 12 grams of bromine, and 100 c c. of water. After a
time an oily substance is deposited, which is extracted with ether. The
solvent is evaporated, and the residue, redissolved in ether, is treated with
animal charcoal and filtered. On slow evaporation the product is ob-
tained in well-defined crystals.
Methyl-heptenone combines with sodium bisulphite. On reduction
by means of sodium and alcohol, it forms the corresponding alcohol,
methyl-heptenol, C8H15OH, which has the following characters:—
This alcohol has been identified in oil of linaloe.

Ciamician and Silber1 have found that .light has a marked effect on
methyl-heptenone. The ketone was kept in a glass flask, exposed to
the light for five months, the flask being exhausted of air, which was
replaced by oxygen. When the seal was broken, the contents of the
flask were found to be at reduced pressure, and the oxygen was mainly
converted into carbon dioxide.
The methyl-heptenone was decomposed, with the formation of acetone,
a ketonic glycol, C8H16O3, and a hydroxydiketone, C8HUO2.
1
Berichte, 46 (1913), 3077.
DlACETYL.
Diacetyl, CH3. CO . CO . CH3, is a diketone found in the distillation

waters of santal, caraway, orris, savin, pine, and other essential oils.
Melting-point o f osazone . . . . . . . 243°
„ „ „ phenylhydrazone 133° to 134°
PUMILONE.
Pumilone, C8H14O, has been isolated from the oil of Pinus pumilio.
It is a ketone having the characteristic odour of the oil, and whose
characters are as follows :—
Optical rotation . . . . . . . . . . 15°
lONONE.
The ketone, ionone, is one of the most important of all the synthetic
perfumes, and one most valued by perfumers as being indispensable for
the preparation of violet odours.
In 1893, after many years of patient research, Tiemann and Kriiger l
succeeded in preparing this artificial violet perfume which they termed
ionone. The chemical relationships of this body are so interesting and
important that Tiemann's work is here dealt with fairly fully.
The characteristic fragrance of the violet is also possessed to a con-
siderable extent by dried orris root (iris root), and believing, although
apparently erroneously, that both substances owed their perfume to the
same body, Tiemann and Kriiger used oil of orris for their experiments,
instead of oil of violets, of which it was impossible to obtain & sufficient
quantity. The root was extracted with ether, the ether recovered, and
the residue steam distilled. The non-volatile portion consists chiefly of
resin, irigenin, iridic acid, and myristic acid, whilst the volatile portion
consists of myristic acid and its methyl ester, oleic acid, oleic anhydride,
oleic esters, and the characteristic fragrant body which they termed
irone. Irone (q.v.) has the formula C13H20O, and is an oil scarcely
soluble in water. The smell of this oil is quite unlike violets when in
concentrated form, but if diluted, resembles them to some extent. Irone
is clearly a methyl ketone of the constitution—
CH3 CH3
C
. CH : CH . CO . CH,
HC CH . CH,3
CH2
[
Berichte,2G (1893), 2675.
In order to attempt to synthesise irone, experiments were made
which finally led to the condensation of citral with acetone, in the
presence of alkalis. Irone was not obtained, but an isomer, which
Tiemann called pseudo-ionone, as follows : —
C10H160 + (CH3)2CO - C13H300 + H20.
Pseudo-ionone is an oil, having the following characters : —
If pseudo-ionone be heated with dilute sulphuric acid and a little
glycerine, it is converted into another isomeric ketone, and now well-
known ionone, C13H20O.
This body is now recognised to be a mixture of two isomeric ketones,
known as a-ionone and /?-ionone. The commercial article, which is a
mixture of the two ketones has approximately the following char-
acters : —
It has a characteristic violet odour, and at the same time recalls the
vine blossom. Tiemann originally assigned to this body the formula—
CH3 CH3
C
H2C/\CH . CH : CH . CO . CH3
i
HCs\ JCH. OH3
CH
But further researches on the chemistry of citral caused him later to
support the formula—
CH
C
H2C . CH : CH . CO . CH,
H2C C.CH 3
CH
which is now accepted as representing a-ionone.
Barbier and Bouveault,1 however, assigned to it the unlikely
formula —
CH2-C(CH3) .
CH2< >C . CH : CH . CO . CH3
\CH2— C(CH3)/
Tiemann later 2 succeeded in resolving ionone into the two isomeric
1 2
Comptes rendus (1897), 1308. Berichte, 31 (1898), 808, 867.
compounds, which he terms a-ionone and /3-ionone. Tiemann and
Kriiger obtained ionone by heating pseudo-ionone with dilute sulphuric
acid. De Laire, using strong acid, obtained a quite similar body, but
one which yielded different derivatives. This body is the original iso-
ionone, or, as it is now called, /2-ionone. a-Ionone is prepared from the
commercial product by converting it into the crystalline oxime, which
is recrystallised from petroleum, and regenerating the ketone by means
of dilute sulphuric acid, when a-ionone results. It has the constitution
given above, and its characters are as follows ;—
C
Boiling-point . . . . 127 to 128° at 12 mm.
Melting-point of oxime 89° to 90°
,, ,, ,, semi-carbazone 107°
,, ,, ,, bromphenylhydrazone 142° to 143°
j8-ionone is obtained from the commercial mixture by means of the
aemi-carbazone, which crystallises more readily than the corresponding
derivative of the a-ketone, and can thus be separated.
The constitution of /3-ionone is—
C
H2C/Nc . CH : CH . CO . CH,
H0C X3 . CH,
CH9
Specific gravity . . . . . 0-949
Boiling-point 134C to 135° at 12 mm.
Melting-point of semi-carbazone 148° to 149°
,, „ ,, bromphenylhydrazone 116° „ 118°
Some of the most important modern work, which has led to good
practical results, on the ionone question, is that of Dr. Philippe Chuit.
Eecognising the distinct differences between a-ionone and /3-ionone from
a perfumer's point of view, Chuit has devoted considerable time to de-
vising practicable methods for their separation. The chief constituent
of the ionone of commerce is a-ionone. By the use of concentrated
sulphuric acid in the cold, the principal isomerisation product of pseudo-
ionone appears to be /2-ionone, and under the name violettone this pro-
duct was put on the market. Numerous patents have been taken out
for the preparation of the separate ionones, which need not be here dis-
cussed. Although ionone does not readily combine with alkaline bi-
sulphite, yet it does so by prolonged boiling with the solution of bisulphite,
a discovery made by Tiemann and utilised by him to remove impurities
from crude ionone. Further, it was shown that the hydrosulphonic
compound of a-ionone crystallised more readily than that of /3-ionone,
whilst the corresponding compound of /3-ionone was the more easily
decomposed by a current of steam. These facts constituted a step
towards the effectual separation of the isomeric ionones.
It has been proved that whilst concentrated sulphuric acid at a low
temperature caused isomerisation of pseudo-ionone, so that the resulting
product consists chiefly of /?-ionone, the use of phosphoric, hydro-
chloric, and hydrobromic acids at low temperatures yields chiefly a-ionone.
In conjunction with Bachofen, Chuit has devised a method for
separating the isomeric ionones depending on the following facts. The
method is based on the insolubility of the sodium salt of the hydrosul-
phonic compound of a-ionone in the presence of sodium chloride, whilst
the corresponding /^-compound remains in solution. If sodium chloride-
be added to a hot solution of the hydrosulphonic compounds, separation
of the a-salt takes place slowly as the solution cools, and the salt
crystallises in fine white scales, which can be recrystallised from hot
water. The /^-compound remains in solution.
As an example of the efficacy of this separation the following is given :
5 grams of a-ionone and 5 grams of /2-ionone were boiled with bisulphite
solution for four and a halt hours. To the solution, measuring 165 c.c.,
40 grams of sodium chloride were added. On cooling and standing, 11
grams of moist crystals were obtained, which on decomposing in the
usual manner, by caustic soda solution, yielded on steam distillation 5-
grams of a-ionone. The /3-ionone was recovered from the mother liquor
with a trifling loss.
The composition of the ordinary hydrosulphonic sodium compound
of a-ionone is, according to Chuit,
(C13H21O . SO3Na . )2 + 3H2O,
whilst that of £-ionone is C13H21O . SO3Na + 2H2O.
From the point of view of practical perfumery, Chuit points out that
the possession of the two pure isomers enables perfumers to produce
numerous shades of violet perfume, with characteristic and distinct
odours, a-ionone has a sweeter and more penetrating odour, rather re-
sembling orris than violets, whilst /2-ionone is said to more closely
resemble the true fresh violet flower.
Patents covering the separation of the ionones are numerous.
The following is a copy of the provisional and complete specifications-
provided by the original patentee. The patent has now expired. Further
examination of the bodies in question has shown that a few unimportant
details require correction :—
Provisional Specification.—I, Johann Carl Wilhelm Ferdinand Tiemann, member
of the firm of Haarmann and Reimer, of Holzminden, residing at Berlin, Germany, do-
hereby declare the nature of this invention to be as follows:—
I have found that a mixture of citral and acetone, if it is subjected, in the
presence of water, for a sufficiently long time to the action of hydrates of alkaline
earths or of hydrates of alkali metals, or of other alkaline agents, is condensed to a
ketone of the formula C13H200. This substance, which I term " Pseudo-ionone,"'
may be produced lor instance in shaking together for several days equal parts of citral
and acetone with a solution of hydrate of barium, and in dissolving the products of
this reaction in ether.
The residue of the ether solution is fractionally distilled under a reduced pressure
and the fraction is collected, which boils under a pressure of 12 mm. at a tempera-
ture of from 138° to 155° C., and from it the unattacked citral and unchanged acetone
and volatile products of condensation are separated in a current of steam, which
readily carries off these bodies.
The product of condensation remaining in the distilling apparatus is purified by
the fractional distillation in vactco. Under a pressure of 12 mm. a liquid distils off
at a temperature of from 143° to 145° C. This product of condensation which I term
" Pseudo-ionone," is a ketone readily decomposable by the action of alkalis. Its.
formula is C13H200, its index of refraction is nD = 1*527, and its specific weight
0-904.
The pseudo-ionone has a peculiar but not very pronounced odour; it does not
combine with bisulphite of sodium as most of the ketones of the higher series, but,
in other respects, it possesses the ordinary characteristic properties of the ketones,
forming, in particular, products of condensation with phenylhydrazine, hydroxyl-
amine and other substituted ammonias.
Although the odour of the pseudo-ionone does not appear to render it of great
importance for its direct use in perfumery, it is capable of serving as raw material
for the production of perfumes, the pseudo-ionone being converted by the action of
dilute acids into an isomeric ketone, which I term " lonone," and which has most
valuable properties for perfumery purposes. This conversion may be effected, for
example, by heating for several hours in an oil bath 20 parts of "pseudo-ionone"
with 100 parts of water, 2-5 parts of sulphuric acid, and 100 parts of glycerine, to the
boiling-point of the mixture. The product resulting from this reaction is dissolved
in ether, the latter is evaporated, and the residue subjected to the fractional distilla-
tion in vacuo. The fraction distilling under a pressure of 12 mm. at a temperature
of from 125° to 135° G. is collected. This product may be still further purified by
converting it by means of phenylhydrazine or other substituted ammonias into a
ketone condensation product decomposable under the action of dilute acids.
The ketone derivatives of the pseudo-ionone are converted under similar condi-
tions into ketone-derivatives of the ionone. The pure ionone corresponds to the
formula C13H200, it boils under a pressure of 12 mm. at a temperature of about 128°
0., its specific weight is 0-935, and its index of refraction nD = 1'507.
The ionone has a fresh flower-perfume recalling that of violets and vines, and is
peculiarly suitable for being used in perfumery, confectionery, and distillery.
The ionone, when subjected at a higher temperature to the action of hydroiodic
acid, splits off water and gives a hydrocarbon corresponding to the formula C13H18,
boiling under a pressure of 12 mm. at a temperature of from 106° to 112° C. This
hydrocarbon is converted by strong oxidising agents into an acid of the formula
C12H,«>06, melting at a temperature of 214° C.
Complete Specification.—I, Johann Carl Wilhelm Ferdinand Tiemann, member
of the firm of Haarmann & Reimer, of Holzminden, residing at Berlin, Germany, do
hereby declare the nature of this invention, and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:—
I have found that a mixture of citral and acetone, if it is subjected in the
presence of water for a sufficiently long time to the action of hydrates of alkaline
earths or of hydrates of alkali metals, or of other alkaline agents, is condensed to a5>
ketone of the formula C13H20O. This substance, which I term ** Pseudo-ionone,
may be produced, for instance, in shaking together for several days equal parts of
citral and acetone with a solution of hydrate of barium, and in dissolving the pro-
ducts of this reaction in ether.
The residue of the ether solution is fractionally distilled under a reduced pressure
tnd the fraction is collected, which boils under a pressure of 12 mm. at a temperature
of from 138° to 155° C. and from it the unattacked citral and unchanged acetone and
volatile products of condensation of acetone by itself are separated in a current of
steam, which readily carries off these bodies.
The product of condensation remaining in the distilling apparatus is purified by
the fractional distillation in vacuo. Under a pressure of 12 mm. a liquid distils off
at a temperature of from 143° to 145° C. This product of condensation of citral with
acetone, which I term " Pseudo-ionone," is a ketone readily decomposable by the
action of alkalis. Its formula is C13H200, its index of refraction nD = 1*527, and
its specific weight 0-904.
The pseudo-ionone has a peculiar, but not very pronounced odour; it does not
combine with bisulphite of sodium as most of the ketones of the higher series, but
in other respects it possesses the ordinary characteristic properties of the ketones,
forming, in particular, products of condensation with phenylhydrazine, hydroxyl-
amine, and other substituted ammonias.
Although the odour of the pseudo-ionone does not appear to render it of great
importance for its direct use in perfumery, it is capable of serving as raw material for
the production of perfumes, the pseudo-ionone being converted by the action of dilute
acids into an isomeric ketone, which I term " lonone," and which has most valuable
properties for perfumery purposes. This conversion may be effected, for example,
by heating for several hours in an oil-bath 20 parts of "pseudo-ionone" with 100
parts of water, 2'5 parts of sulphuric acid, and 100 parts of glycerine, to the boiling-
point of the mixture.
The product resulting from this reaction is dissolved in ether, the latter is
evaporated and the residue subjected to the fractional distillation in vacua. The
fraction distilling under a pressure of 12 mm. at a temperature of from 125° to 135°
C. is collected. This product may be still further purified by converting it by means
of phenylhydrazine or other substituted ammonias into a ketone condensation pro-
duct decomposable under the action of dilute acids.
The ketone derivatives of the pseudo-ionone are converted under similar condi-
tions into ketone derivatives of the ionone. The pure ionone corresponds to the
formula C13H200, it boils under a pressure of 12 mm. at a temperature of about 128°
C., its specific weight is 0*935, and its index of refraction nD = 1*507.
The ionone has a fresh flower-perfume recalling that of violets and vines, and is
peculiarly suitable for being used in perfumery, confectionery, and distillery.
The ionone, when subjected at a temperature surpassing 100° C. to the action of
hydroiodic acid, splits off water and gives a hydrocarbon corresponding to the
formula C13Hlg, boiling under a pressure of 12 mm. at a temperature from 106° to
112° C. This hydrocarbon is converted by strong oxidising agents into an acid of the
formula C12H12O6 melting at a temperature of 214° C.
Having now particularly described and ascertained the nature of this invention,
and in what manner the same is to be performed, I declare that what I claim is:—
1. A new chemical product termed pseudo-ionone obtained by the reaction of
citral upon acetone in the presence of alkaline agents and subsequent treatment of
the products, substantially as described.
2. A new article of manufacture termed ionone suitable for perfumery and the like
and having the characteristics hereinbefore set forth, obtained from pseudo-ionone
referred to in the preceding claim, substantially as described.
3. The process for the production of the pseudo-ionone referred to in the first
claim, consisting in the subjection of a mixture of citral and acetone to the action of
an alkaline agent, and in purifying the product of this reaction, extracted by means
of ether, by fractional distillation, substantially as described.
4. The process for the production of the ionone referred to in the second claim,
consisting in treating the pseudo-ionone referred to in the first claim or its ketone
condensation products with phenylhydrazine or other ammonia derivatives, finally
with acids, substantially as described.
The commercial product, as put on to the market, was originally a
10 per cent, solution of ionone in alcohol. This was due not only to
the expensive nature of the product, but also to the fact that its odour is
very intense, and when pure, not like that of violets. Ten grams of
this solution are sufficient to produce 1 kilo of triple extract of violets
when diluted with pure spirit. But to-day 100 per cent, violet perfumes,
such as the violettone, above mentioned, are regular commercial articles.
The perfume is improved both lor extracts and soaps by the addition of
a little orris oil, but in the author's opinion the odour of ionone is not
nearly so delicate as that of the natural violet, although far more powerful.
With regard to the practical use of ionone, which sometimes presents
a difficulty to perfumers, Schimmel & Co. have published the following
remarks:—
" This beautiful article maintains its position in the front rank of
preparations for perfumery, and will probably remain without a rival
among artificial perfumes for some time to come. Although the violet
scent has long been a favourite perfume, its popularity has doubled
through the invention of ionone, and it is not too much to say that the
introduction of that body alone has made it possible to produce a perfect
extract. Some of the leading European perfumers produce violet extracts
which may be recommended as examples of excellence, and which have
•deservedly become commercial articles of the first importance. The
inventors of ionone have earned the gratitude of the entire perfumery
industry, and may be congratulated in turn upon the remarkable success
of their invention.
" As we have already pointed out on a previous occasion, the pre-
paration of a violet extract in which ionone is made to occupy its due
position is not such an easy task as is often assumed; on the contrary,
it requires a long and thorough application.
" To obtain a perfect result with ionone is an art in the true meaning
of the word, and on that account no inexperienced hand should attempt
it. We again and again lay stress upon this fact, because in our business
we are constantly brought face to face with people who think that they
can make a suitable violet extract by simply mixing alcohol with ionone
solution. This view is quite wrong. The employment of ionone pre-
supposes above everything else that the user is acquainted with the
peculiarities of the article and knows how to deal with them. Again
and again the uninitiated come to us with the complaint that ionone
has no odour at all, or that it smells disagreeably, although, as a matter
of fact, these objections are usually withdrawn upon closer acquaintance
with the article. The assumptions in question are only due to a blunting
of the olfactory nerves, or, more correctly, to a nasal delusion, which
also occurs sometimes in the case of other flower odours and to which
people are known to be particularly liable when smelling freshly
gathered violets.
"The principal thing in connection with the employment of ionone
is to discover its proper degree of dilution. In its natural state the
body is so highly concentrated as scarcely to remind one of violets.
This is the reason why it was placed in trade in the form of a 10 per
cent, solution, and not in its pure state. This form has proved an ex-
ceedingly useful one. In using it for extracts, powders, sachets, etc.,
the solution must be further diluted and fixed with some orris oil, civet,
and musk."
By using acetone homologues, homologous or reduced ionones are
produced which have intense odours of a similar character.
The above remarks apply to the commercial product known as ionone.
There are, however, numerous other patents in existence for the pre-
paration of artificial violet oil. The complete specification of one of
these reads as follows :—
I, Alfred Julius Boult, of 111 Hatton Garden, in the County of Middlesex,.
Chartered Patent Agent, do hereby declare the nature of this invention and in what
manner the same is to be performed, to be particularly described and ascertained in
and by the following statement :—
This invention relates to a process for manufacturing hitherto unknown oils
having a violet scent.
Patents No. 8,736 of 1 May, 1893, and No. 17,539 of 18 September, 1893, describe
the manufacture of ionone, which is an essential oil, boiling at 128° under 12 mm.
pressure, and of specific gravity of 0-935. This oil is optically inactive.
The final product of the process according to the present invention is an oil
boiling at 142° to 150° C. under 12 mm. pressure and of specific gravity of from 0'94 to
0*95. It differs from ionone by having when concentrated a very strong scent similar
to that of sandalwood by producing a left-handed rotation of a polarised ray and by
having when diluted a scent more closely approaching that of natural violets than
does that of ionone.
Analysis shows that this oil consists of several ketones of the groups G13H20O of
higher boiling-points and greater density than those of ionone. These ketones are
optically active, and both their existence and their artificial production have been
hitherto unknown.
The process employed in carrying out this invention is as follows : A mixture of
1 to 1J parts acetone (45 kg.), 1 part of lemon-grass oil (38 kg.), 1£ to 2 parts of
alcohol (75 kg.), 1 to 2 parts of a concentrated lime-free solution of chloride of lime
(75 kg.), to which is added a little cobaltous nitrate (30 gr.) dissolved in water, is
boiled during six to eighteen hours at a temperature of 70° to 80° C. in a reflux cooling
apparatus.
The alcohol and the excess of acetone are first distilled off and then an essential
oil is obtained, which, after the first distilled portion (about 4 kg.) of specific gravity
0*88 has been removed, represents the stuff for producing artificial oil of violets. It
is an essential oil with a boiling-point of 155° to 175° at 12 mm. pressure (about 25 kg.).
This oil is heated at 110° C. with a solution of bisulphate of sodium of 11° Beaume
(42 kg. for 360 litres of water) in a vessel with a mixing device until the samples
distilled every day show that the first running, which has an unpleasant smell, has
reached the density of 0*936. This happens after about eight days (the first running
being about 8 kg.).
The crude product (about 17 kg.) in the vessel is then purified by fractional dis-
tillation, all the bad-smelling parts being removed, so that finally there remains an
oil of a density of 0*948 to 0*952 (15° C.) boiling at 142° to 150° under 12 mm. pres-
sure.
The lightest portion of this oil has a specific gravity of 0*945 and boils at 142° C.
under 12 mm. pressure; the largest portion of it, which has the pleasantest and
strongest smell, boils at 149° C. and has a specific gravity of 0*953. Analysis has
shown that both substances belong to the group of ketones C13H20O.
By using other ketones instead of acetone homologous substances may be obtained.
The product obtained by the above-described process contains BO ionone, for it
contains no ingredient boiling at 128° C. under the pressure of 12 mm. and having
a specific gravity 0*935. The violet-like smell of the product obtained according to
the present invention is the result of the presence of substances which are different
from ionone, as their specific gravity and their boiling-point are higher than those of
ionone. The new product has the advantage that it can be manufactured in a very
simple and economical manner, and as its smell is much more like that of real
violets than is the smell of ionone, and as it is more constant and less volatile than
ionone, it is much more suitable for artificial violet scent than the " ionone " which
has hitherto been the only artificially made substance known for this purpose, and
which is much more difficult to manufacture.
Having now particularly described and ascertained the nature of the said inven-
tion as communicated to me by my foreign correspondents and in what manner the
same is to be performed, I wish it to be understood that I do not claim anything
described and claimed in the Specifications of Letters Patent Nos. 8,736 and 17,539,
A.D. 1893, granted to Johann Carl Wilhelm Ferdinand Tiemann, but I declare that
what I claim is :—
1. As an article of manufacture an essential oil having the smell of violets,
boiling at 142° to 150° C. under a pressure of 12 mm. and of a specific gravity of 0*948
to 0*952 (15° C.).
2. A process for the manufacture of hitherto unknown oils having the smell of
violets, which oils have a higher boiling-point and higher specific gravity than
ionone.
3. A process for the manufacture of hitherto unknown oils boiling at 155° to
175° C. under the pressure of 12 mm., which can be converted into violet-smelling
oils of higher specific gravity and higher boiling-point than those of ionone by being
boiled with different substances, such, for instance, as bisulphate of sodium.
4. The manufacture of homologous substances by using other ketones instead of
acetone.
5. A process for the manufacture of artificial essence of violets consisting in
causing lemon-grass oil, alcohol, acetone, and concentrated solutions of salts of
hypochlorous acid to react on one another at the boiling temperature.
6. Process for manufacture of artificial essence of violets consisting in causing
lemon-grass oil, alcohol, acetone, and concentrated solutions of salts of hypochlprous
acid to react on one another at a boiling temperature, cobaltous nitrate being added
if desired.
The patentees state that their invention relates to the preparation

of cyclic ketones of the same group as ionone, but with higher boiling-
points and higher specific gravity. They claim to have proved that,
corresponding to the pseudo-ionone of the patent No. 8,736 of 1893,
which distils at 143° to 145° (12 mm.), and which finally gives the ketone
ionone of boiling-point 126° to 128° (12 mm.), and specific gravity
0*935 (20 C.), there exists also an iso-pseudo-ionone which distils at
149° to 151° (12 mm.), and which gives iso-ionone of boiling-point 133°
to 135° (12 mm.), and specific gravity 0'943 (20 C.), and further that
there exists still another isopseudo-ionone which distils at 157° to 160°
(12 mm.), and which gives a cyclic ketone of boiling-point 142° to 146°
and specific gravity 0-960 (20 C.).
They also claim that large quantities of iso-pseudo-ionone are formed
in the process of Tiemann's patent, and which can be separated by dis-
tillation, coming over at a higher temperature than the ordinary pseudo-
ionone.
According to Hanriot ionone can be detected in very minute amount
by the following reaction: If traces of it be dissolved in concentrated
hydrochloric acid, the liquid becomes of an intense golden colour, and
if the solution be warmed with chloral hydrate, a dirty violet colour
results. The violet colouring matter is extracted by ether, and if the
ether be evaporated a water-soluble violet-coloured residue is left.
This test will detect 1 part of ionone in 2000.
Skita 1 has studied the reduction of ionone by means of palladium
chloride. The reduction-product, dihydroionone, boils at 121° and 122°
(14 mm.); it possessed a faint odour of cedarwood. By the same
method, ^-ionone yields a dihydroionone boiling at 126° to 129° (12 mm.).
When the reduction is continued until hydrogen ceases to be absorbed,
both a- and /3-ionone yield tetrahydroionone, boiling at 126° to J27°
at 13 mm.
The fact that the reduction of a- and /3-ionone affords two different
dihydroionones indicates that the double linkage in the side chain is
the first to be saturated. This agrees with the fact that continued re-
duction leads to the same tetrahydroionone.
C
. CH 2 . CH 2 . CO . CH3
H,CV ^C.CH 3
Dihydroionone from a-ionoce.
C
. CH2 . CH2 . CO . CH3 H 2 C C H . CH2 . CH2 . CO . CH
. CH3 H2C 'CH . CH

CH2 CH2
Dihydroionone from j8-ionone. Tetrahydroionone.
2
Kishner has prepared the hydrocarbons corresponding to the iso-
meric ionones, in which the oxygen atom is replaced by two hydrogen
atoms. These two hydocarbons, C13H22, are a-ionane and /2-ionane.
Their characters are as follows : —
a-ionane. j8-ionane.
Boiling-point ...... 220° to 221° 224° to 225°
00°
Specific gravity at ^ • . . . 0-853 0-815
Refractive index ..... 1'4784 1-4725
1 2
Berichte, 45 (1912), 3312. Jour. Phys. Chim. Russe., 43, 1398.
Their constitutions are as follows : —
CH3— CH2— CH =CH—CH

C
CH3
CH
CH
2
CH/
OH :=CH — — 2^ //.CH
CH
Knoerenagel * has studied the products of condensation of citral

with ethyl-acetoacetate, and has obtained the following bodies : /?-
pseudoionone C13H20O,
CH— CH2— CH— CO— CH3
CH3— C — CH2 — CH — CH = C(CH3)2
and a-isoionone, and /2-isoionone, two other closely related isomers.
IRONE.
Irone is the odorous ketone present in oil of orris. It is isomerift
with ionone, having the formula C13H20O and the constitution —
CH2
H,C . OC . HC : HC . HCV JCH
It has also4 been prepared synthetically by Merling and Welde,2 by

condensing ^d -cyclocitral with acetone.
Irone is a colourless oil, having an odour resembling that of violets.
Boiling-point a t 1 6 m m . . . . . . . . 144°
Optical rotation . . . . . . . . . about + 4 0 °
It forms an oxime, C 13 H 20 : NOH, melting at 12i'5°. If a 10 per cent,
solution of irone in glacial acetic acid be allowed to stand with j?-brom-
phenylhydrazone, crystals of irone j9-bromphenylhydrazone separate,
1 2
J . prakt. Chem. [2], 97, 288. Ann. Chem. (1909), 119.
which melt, after repeated recrystallisation from methyl alcohol, at
174° to 175°. Irone also forms a thiosemi-carbazone melting at 181°.
A ketone isomeric with irone has been isolated from oil of cassie
'flowers. It is possible that this is /3-ionone, but its identity has not yet
been established.
METHYL-HEXANONE.
Methyl-l-hexanone-3, C7H12O, is found naturally in pennyroyal oil,
and is obtained by the decomposition of pulegone. It is an aromatic
Specific gravity at -5° 0-911
Its semi-carbazone melts at 182° to 183°, and its oxime at 43° to 44°.
CH . CBL
BLC CH,
H, .CO
tfng
SANTENONE.
Santenone, C9H14O, is a lower homologue of the regular " terpenic "
ketones of the formula C10H1GO. It occurs naturally in sandal wood oil,
and may be obtained by the oxidation of isosantenol, the alcohol resulting
from the hydration of santene. Santenone has the following char-
acters :—
Melting-point 58° to 61°J
Specific rotation (in alcohol) . . . . . - 4° 40'
It forms a semi-carbazone melting at 222° to 224°. The constitution

of santenone is as follows :—
CH3
H2a —c co
H—C—CH,
C CH,
H
SABINA KETONE.
Sabina ketone, C10H14O, is not a natural constituent of essential
oils, but is of considerable interest on account of its utility in the
synthesis of other ketones.
1
The melting-point 48° to 52° given in Vol. I. was apparently determined on an
impure specimen.
VOL. II. 15
It results from the oxidation of sabinenic acid with peroxide of lead,
sabinenic acid itself being an oxidation product of the terpene sabinene.
It is a liquid having the following characters :—
Optical rotation . . . . . . . . . . 2 4 ° 41'
It forms a semi-carbazone melting at 141° to 142°. Its constitution
is probably as follows :—
CO
HC/
. CH(CH3)2
l
Wallach prepares sabina ketone in the following manner: Twenty-
iive grams of sabinene are treated with 60 grams of potassium per-
manganate, 13 grams of caustic soda, 400 c.c. of water, and 400 grams
of ice. The mixture is well shaken and the unchanged hydrocarbon is
distilled off in a current of steam. Manganese dioxide is then filtered
off, and the sodium sabinenate separated by concentrating the filtrate,
when the salt crystallises out. This is then oxidised by potassium
permanganate in sulphuric acid solution.
Kotz and Lemien 2 have recently converted sabina ketone into its
.homologue methyl-sabina ketone, C10H16O, by first converting it into
hydroxymethylene sabina ketone by Claisen's method, and then reducing
this0 ketone, when the homologue results. It is a heavy oil, boiling at
:221 and having the following formula :—
CO
CH,
C . CH(CH3)2
VEBBENONE.
This ketone, C10H14O, is found naturally in oil of vervain, the true
verbena oil. It has, when isolated from this oil, the following char-
acters :—
.Specific gravity 0-974 at 17°
The natural ketone is, however, probably contaminated with traces of
terpenes.
Verbenone results from the auto-oxidation of turpentine oil, d-
1 2
Annalen, 359 (1908), 265. /. prakt. Chem., 1914 [ii.], 90, 314.
terbenone resulting from the oxidation of American, and Z-verbenone
from that of French, oil of turpentine. When purified by decomposition
t0f its semi-carbazone, the characters of d-verbenone are as follows :—
,, ,, at 16 mm. 100°
Melting-point + 6*5°
Verbenone has the following constitution :—

CH-
The constitution of verbenone has been established l by its reduction

to the corresponding saturated secondary alcohol, dihydroverbenol, and
into the corresponding saturated ketone, or dihydroverbenone.
CH
'
HOHC/
HX-C-CH
CH
CH—CH3 CH—CH3
Dihydroverbenol. Dihydroverbenone.
Dextro-dihydroverbenol melts at 58° C. and boils at 218° C.; it yields
an acetic ester, the odour of which recalls that of bornyl acetate. Dextro-
dihydroverbenone is produced by the oxidation of the above alcohol by
means of chromic acid, or by the reduction of verbenone by means of
hydrogen in presence of colloidal palladium. It boils at 222° C. (D15
0'9685; [a]D + 52-1 9°; wD201-47535; molecular refraction 44-45) and gives
a semi-carbazone melting at 220° to 221° C.; its oxime melts at 77° to 78°
C. On applying Grignard's reaction to d-verbenone, a hydrocarbon is
obtained which appears to be methylverbenene, C11H16 (boiling-point
8 mm., 49° C. ; boiling-point 771 mm., 175° to 176° C.; D15 0-876; D20
G'872; aD ± 0°; HD201-4969; molecular refraction 49-64). This inactive
hydrocarbon is probably composed of a mixture of isomerides; it fixes
oxygen with avidity, rapidly becoming resinified.
1
Roure-Bertrand Fils, Bulletin, October, 1913, 134.
When submitted to oxidation by a 2 per cent, solution of permangan-
ate, d-verbenone yields pinononic acid, C9H14O3, melting at 128° to 129°
C., the semi-carbazone of which melts at 204° C. Lastly the constitution
of verbenone, as expressed by the above formula, is further confirmed by
the fact that the bicyclic system is convertible into a monocyclic system
by boiling with 25 per cent, sulphuric acid, with the formation of acetone
and 3-methylcyclohexene-(2)-one-(l). This cyclohexenone has been char-
acterised by its semi-carbazone (melting-point 198° C.) and by its conver-
sion into y-acetobutyric acid (melting-point 36° C). The oily liquid,
which did not react with sulphite, was submitted to benzoylation after
dilution with pyridine. It thus gave rise to a benzoate from which was
CH
C—CH,
Verbenol.
isolated d-verbenol.20 This alcohol boils at 216° to 218° C. (Dr 0-9742 ;

[a]D + 132-30°; nD 1-4890; molecular refraction 45*25). When oxidised
by chromic acid it yields verbenone ; with permanganate it gives pinon-
onic acid. By the action of acetic anhydride it is converted into l-
verbenene (boiling-point 758 mm., 159° to 160° C.; D15 0-8852;
aD - 74-90°; ?^D 1-49855; molecular refraction 44-61). Verbenene,
CH9
CH
C—CH3
Verbenene.
when treated with powerful dehydrating agents, such as zinc chloride
or phosphoric anhydride, is converted into jp-cymene.
PIPERITONE.
This ketone occurs in eucalyptus oils derived from a particular
group of trees, the leaves of which have the venation characteristic of
species yielding phellandrene-bearing oils. It follows the general rule
for all constituents in eucalyptus oils, increasing in amount until the
maximum is reached in one or more species. It occurs in greatest
quantity in the oils of these eucalyptus trees known vernacularly as
"Peppermints," such as E. piperita, E. dives, etc., and consequently
is found more frequently in the oils from species growing on the eastern
part of Australia.
Piperitone can be most easily obtained from the higher boiling por-
tions of the oil of E. dives. It combines slowly with sodium-bisulphite,
and by repeated agitation for two or three weeks eventually forms
crystals in some quantity. A proportion of alcohol assists the combina-
tion. The pure ketone prepared from the purified crystals is colourless
at first, but on long standing becomes slightly yellowish in tint. It has
a burning peppermint-like taste andl odour. The formula is C10H16O.
According to Eead and Smith piperitone is, under natural condi-
tions, optically inactive. By fractional distillation under reduced pres-
sure, it is prepared, by means of its sodium bisulphite compound, in a
laevo-rotatory form. The slight laevo-rotation is probably due to the
presence of traces of cryptal. By fractional distillation alone, it is
usually obtained in a laevo-rotatory form ; whether this is due to decom-
position products or not is unknown. Piperitone has a considerable
-prospective economic value, as it forms thymol by treatment with
formic chloride, inactive menthone by reduction when a nickel cata-
lyst is employed, and inactive menthol by further reduction. Its char-
Optical rotation Laevo-rotatory — 50° or more
Boiling-point 229° to 230° (uncorrected)
at 10 mm. 106° to 107°
With hydroxylamine, piperitone yields a normal oxime melting at

110° to 111°, and an oxamino-oxime melting at 169° to 170°. The semi-
carbazone prepared from piperitone which had been regenerated from
its bisulphite compound melts at 219° to 220°. But piperitone prepared
by repeated fractionation under reduced pressure yields two semi-carba-
zones, melting at 175° to 176° and 182° to 183° respectively. On
reduction in alcoholic solution by sodium amalgam, piperitone yields a
dimolecular ketone, C20H34O2, melting at 149° to 150°. According to
Smith the probable constitution of piperitone is
CH . CH
HCv .CO
. C3H7
Givaudan & Co., however,2 compare the properties of piperitone with
those of the ketone prepared synthetically4 by Wallach,3 and discovered
in Japanese peppermint oil by Schimmel and later in camphor oil by
Bchimmel, and finally in the oil of Cymbopogon sennaarensis by Eoberts,5
1 2
Jour. Chem. Soc., 1921, 781. P. and E.O.R., 1921, 80.
*Annaten,t 362 (1908), 271.
4
8
Semi annual Report, French edition 1910, II., 87.
Jour. Chem. Soc., 107 (1915), 1465.
and consider that it is identical with this body, The constitution would
then be
C.CEL
H2C CH
H. CO
CH(C3H7)
Eead and Smith (ioc. cit.) have prepared benzylidene-piperitone, of
the formula C10H14O: CH. C6H5, by the interaction of piperitone and
benzaldehyde in the presence of alcoholic sodium ethoxide. This body
melts at 61°, and the discoverers claim that it is sufficiently character-
istic to definitely differentiate piperitone from any of the hitherto
described menthenones.
CABVONE.
Carvone, C10H14O, is the ketone characteristic of dill and caraway
oils. It occurs in the dextro-rotatory form in these oils, and as laevo-
carvone in kuromoji oil.
Carvone has the following constitution :—
C.CH,
HO CO
•*"*-2 \ / 2
H3OC . C : CH2A
It is a colourless oil, solidifying at low temperatures and having a
characteristic odour of caraway. Its characters are as follows :—
Optical rotation ± 59° 30'
Boiling-point 224°
Inactive carvone can be obtained by mixing equal quantities of tht

optically active isomers. Carvone yields all the usual ketonic compounds
such as the crystalline oxime and phenylhydrazone. The former com-
pound is interesting on account of the fact that it is identical with nitroso-
limonene (vide limonene). Carvone also forms a crystalline compound
with sulphuretted hydrogen, C10H14(OH)(SH). This results by passing,
the gas through an alcoholic solution of caraway oil saturated with
ammonia gas. The resulting crystals can be purified by recrystallisation,
and decomposed by alcoholic potash, when nearly pure carvone results,
The following table gives the optical rotations of the purest specimens of
dextro- and laevo-carvone derivatives that have been prepared :—
Derivatives of
Dextro-carvone. Laevo-carvone.
Carvone . . . . 62° - 62°
„ sulphydrate + 5-53° - 5-55°
Carvoxime . . . . + 39-71° - 39-84°
Benzoyl carvoxime + 26-47° - 26-97°
,, hydrochlor-carvoxime - 10-58° + 9-92°
The principal derivative for the identification of carvone is the oxime,
which can be obtained by dissolving 5 grams of carvone in 25 c.c. of
alcohol and adding a warm solution of 5 grams of hydroxylamine hydro-
chloride in 5 c.c. of water, and then rendering the solution alkaline by
the addition of 5 grams of caustic potash in 40 c.c. of water. The car-
voxime is precipitated by pouring the liquid into water, and recrystallised
from alcohol. Optically active carvoxime melts at 72°, but ^'-carvoxime,
which is obtained by mixing equal quantities of the two optically active
isomers, melts at 93°.
The phenylhydrazone melts at 109° to 110°, and the semi-carbazone-
at 162° to 163° (active varieties) or 154° to 155° (inactive form). The
sulphuretted hydrogen compound mentioned above melts at 210° to 211°.
By reduction carvone fixes 2 atoms of hydrogen on to the ketonic
group, and 2 atoms in the nucleus, with the formation of dihydrocarveol,.
C10H180, whose corresponding ketone, dihydrocarvone, C10H16O, exists in
small quantities in caraway oil.
G. Vavon l has examined the hydrogenation of carvone, in presenc
of platinum black as a catalyst, and shown that it takes place in three
entirely distinct phases. Carvone fixes successively three molecules of
hydrogen, giving dextro-carvotanacetone, then tetrahydrocarvone, and
finally carvomenthol.
By stopping the hydrogenation at a suitable moment, it is possible to-
obtain any one of these three bodies.
Carvotanacetone thus prepared has the following constants :—
Boiling-point . . . . . . . 227° t o 228° C .
0-937
18 1-4817
'*D
Molecular rotation 46-20
[OJ578 + 59-8°
Its oxime and its semi-carbazone melt respectively at 75° C. and 173° C.
Tetrahydrocarvone boils at 218° to 219° C.
Df° ............ 0-904
V° . . . . . . . . . . . . 1-4555
Molecular rotation ......... 46-25
[a]678 ............ - 27°
Carvomenthol, obtained by the fixation of 3H9 by carvone, is a thick

liquid boiling at 217° to 218° C.
D*° ............ 0-908
wD2° ..... ....... 1*4648
Msw . . . . . . . , . . . . _ 24-7°
Its acetate is a liquid with pleasant odour, boiling at 230° to 231° C,

D*0 ............ 0-928
™D20 ............ 1-4477
[«l678 ........ . . . . . . 27-6°
1
The benzoate is a thick liquid.
Boiling-point (15 mm.) . 185° to 186° C.
1-006
1-509
Molecular rotation 77-19
M578 12-9°
DlHYDROCARVONE.
Dihydrocarvone, C10H16O, is found to a small extent in oil of caraway,
and can be prepared by the oxidation of dihydrocarveol by chromic acid
in acetic acid solution. The ketone has the constitution :—
CH . CH
CH . a<
It is an oil having an odour resembling those of carvone and menthone.
It forms a characteristic dibromide, C1QH16Br2O, by the action of bromine
in acetic acid, melting at 69° to 70° (optically active form) or 96° to 97°
(racemic variety). Dihydrocarvoxime melts at 89° (active variety) or 115°
to 116° (racemic variety).
UMBELLULONE.
Umbellulone, C10H14O, is a ketone which was isolated from the oil of
Umbellularia calif ornica, by Power and Lees. It has been examined by
Tutin l who assigned to it one of the following alternative constitutions : —
H,C -- -HC - CO H,C -- HC - CO
CH, —CH, CH,—C—CH,
HC- =CH
CH3 CH3
Semmler,'2 however, has carried out a very exhaustive examination of
the ketone, and considers that its constitution is that of a bicyclic ketone
of the thujone series, as follows :—
C—CH,
/Y
HC
H9C CO
C—CH(CH3)2
1
Jour. Chem. Soc., 89 (1906), 1104. *Berichte, 40 (1907), 5017.
Umbellulone is a colourless liquid of irritating odour, recalling that of

peppermint. It has the following characters :—
93° at 10 mm.
He tractive index 1-48325
The normal semi-carbazone melts at 240° to 243°. By reduction it
yields dihydroumbellulol, C10H18O, a liquid of specific gravity 0*931 at 20°
and optical rotation — 27° 30'.
This body, on oxidation, yields /3-dihydroumbellulone, C10H16O, a
ketone which yields a semi-carbazone melting at 150°. These two bodies
have, according to Semmler, the following constitutions :—
HO.HC
H
'°\CH. CH . CH,
H,
H2C CH
Dihydroumbellulol C10H180.
OC CH
>CH. CH . CH,
H3C/
H2C CH
/8-Dihydroumbellulone, C10H16O.
PlNOCAMPHONE.
Pinocamphone, C10H16O, is the principal constituent of oil of hyssop,
in which it occurs in its laevo-rotatory variety. It is a saturated ketone
having the constitution :—
CH—CH,
\CO College of Dentistry U. S. C.'

C(CH3)
;CH,
CH
It has been prepared artificially by Wallach as a bye-product in the
reduction of nitrosppinene, C10H17NOH. It is best prepared as follows;
Five grams of nitrosopinene are dissolved in 40 c.c. of warm g;lacial
acetic acid, and sufficient water added to produce a slight cloudiness.
A large amount of zinc-dust is then added. After the reaction has be-
come gradual, the mixture is heated on a water-bath under a reflux con-
denser for four hours. The liquid is then filtered, and the filtrate steam
distilled. I he distillate is exhausted with ether, the ether evaporated
and the pinocamphone distilled in a vacuum. The characters of natural

and artificially prepared pinocamphone are as follows :—
Natural. Synthetic.
Boiling-point 211° to 213° 211b to 213°
Specific gravity . 0-966 0-963
Eefractive index 1-4742 1-4731
Molecular refraction 44-4 44-44
Optical rotation - 13° 42' + 0°
Pinocamphone forms the following compounds suitable for its identi-
fication. The dibromide, C10H14Br2O, is obtained by dissolving 5 grams
of the ketone in 5 c.c. of glacial acetic acid. The theoretical amount of
bromine (four atoms) is then added drop by drop, the vessel being kept
cold by immersion in ice water. On standing in a cold place the di-
bromide solidifies, and can be recrystallised from petroleum ether. It
then melts at 93° to 94°. By treatment with zinc and acetic acid, the
dibromide is converted into the ketone again. The semi-carbazone exists
in two modifications, one melting at 228° to. 229° and ,the other at 182°
to 183°. The oxime melts at 86° to 87°.
FENCHONE.
Fenchone, C10H16O, is found in fennel oil and in the oil of Lavandula
Stoechas, in its dextro-rotatory form, and as laevo-fenchone in oil of
thuja leaves. It can be extracted from these oils by treating the frac-
tion boiling at 190° to 195° with nitric acid, or permanganate of potassium,
and then steam distilling the unaltered fenchone.
When the terpene a-fenchene (isopinene) is hydrated by means of
acetic and sulphuric acids, it yields an isomer of fenchyl alcohol, which
is known as isofenchyl alcohol (q.v.), and which on oxidation yields iso-
fenchone, as fenchyl alcohol yields fenchone. The two ketones, fenchone
and isofenchone, are sharply differentiated by isofenchone yielding iso-
fenchocamphoric acid, C10H1604, on oxidation with potassium perman-
ganate, which is not the case with fenchone. According to Aschan,1 the
hydrocarbon found in turpentine oil, and known as /2-pinolene (or cyclo-
fenchene—as he now proposes to name it), when hydrated in the usual
manner, yields both fenchyl and isofenchyl alcohols, which on oxidation
yield the ketones fenchone and isofenchone. According to Aschan the
relationships of these bodies are expressed by the following formulae :—
(CH3)2C CH—CH,
£-Pinolene.
(CH3)2C
HO—CH
i,.A.
CH
C(CH3)-CH2
CH2 (CH3)2C
CH2
CH
CH9
CH2
C(CH3)-CHOH
Fenchyl alcoho . Isofenchyl alcohol.
1
Annalen, 387, 1.
(CH3)2C- ~CH CH, (CH3)2C-
CH,
CO C(CH3)-CH2 jttc) !(CH3)-CO
Fenchone. Isofenchone.
(CH,)2C -COOH
CH9
CH2 C(CH3)-COOH
Isofenchocamphoric acid.
Fenchone has the following characters :—
Boiling-point . . . . . . . . 192° to 193°
Melting-point + 5° „ + 6°
Specific rotation about + 70°
The most characteristic derivative for the identification of fenchone is
its oxime. Five grams of fenchone are dissolved in 80 c.c. of absolute
alcohol and a solution of 11 grams of hydroxylamine hydrochloride in
11 c.c. of boiling water containing 6 grams of caustic potash, is added.
After a time the oxime separates in the form of fine crystals which on
recrystallisation from alcohol melt at 164° to 165° (active form) or 158°
to 160° (inactive form).
The semi-carbazone melts at 182° to 183° (active form) or 172° to 173°
(inactive form).
By reduction fenchone is converted into fenchyl alcohol, melting at
45°. The alcohol, however, has the opposite optical rotation to that of
the ketone from which it is prepared.
By dehydration fenchone yields w-cymene.
THUJONE.
This ketone, of the formula C10H160, isomeric with those above
described, is found in the oils of thuja, tansy, wormwood, and sage. It
is identical with the bodies formerly described under the names tan-
acetone and salvone. It is best prepared in a state of purity from oil of
wormwood. According to Semmler, 200 c.c. of the oil, 200 c.c. of a
saturated solution of sodium bisulphite, 75 c.c. of water, and 300 c.c. of
alcohol are well shaken at intervals during a fortnight. The crystals
formed, consisting of the compound of thujone with the sodium bisulphite,
are separated, washed with alcohol-ether, and pressed. On treatment
with caustic soda solution, the thujone, amounting to over 40 per cent, of
the oil used, separates, and can be distilled with steam.
The hitherto unanswered question whether the chemically identical
thujonGS isolated from various essential oils are also physically identical,
or whether they are physically isomeric, has now been decided by Wallach
in the last-named sense. He has succeeded in establishing the presence
of two and possibly of three thujones, although with regard to the third
the more probable view is, that it represents a mixture of the other two.
His examination has, moreover, proved that thuja oil contains essentially
a-thujone, and oil of tansy essentially /?-thujone. Wormwood oil is very
rich in /3-thujone, but also contains some of the a-compound. Oils of
artemisia and sage contain mixtures of a- and /2-thujones. The formation
of the semi-carbazones and their fractional crystallisation from methyl
alcohol afford means for the separation and identification of the isomers.
a-thujone is laevo-rotatory, and yields two semi-carbazones, one
dextro-rotatory, melting at 186° to 188°, and one, also dextro-rotatory, of
the indistinct melting-point 110°. Pure a-thujone has the following pro-
perties :—
Refractive index . . . . . . . . 1*4510
a-thujone is partially converted into /?-thujone when heated with
alcoholic potash solution, formic acid, or alcoholic sulphuric acid. The
last-named then effects a further conversion into isothujone (q.v.).
/?-thujone is dextro-rotatory, but is not the optical antipode of a-
thujone. The semi-carbazone exists in a labile dextro-rotatory form of
the melting-point 174° to 176°, which readily passes over into the second
form, melting at 170° to 172°. When mixtures of the semi-carbazones of
/2-thujone or of a-thujone, or of both, are present, they give rise to com-
plications which become even more pronounced owing to the fact that
mixed crystals of uniform appearance are formed which can only be split
up by very frequent recrystallisation. The ketone liberated from the
semi-carbazone by means of phthalic anhydride has the specific rotatory
power [a] + 76'16°. Its oxime melts at 54° to 55°, and is dextro-rotatory.
jS-thujone can also be converted into the isomeric a-thujone by boiling
with alcoholic potash.
The various compounds of this ketone are closely analogous to those
of the isomers already described.
Thujone is easily converted into the isomeric ketones, isothujone and
carvotanacetone. The former results by heating thujone with 40 per
cent, sulphuric acid, whilst the latter is formed by heating thujone in a
closed tube to 280°. The more interesting of these isomers is isothujone,
for on reduction with sodium and alcohol, an alcohol, C10H19OH, results,
which is isomeric with menthol, and which is sufficiently similar to this
body in its properties to be termed thujamenthol. Thujamenthol on
oxidation yields the ketone thujamenthone, which is isomeric with ordinary
menthone. Carvotanacetone yields corresponding compounds carvomen-
thol and carvomenthone. The physical properties of the isomers, thujone
(i.e. a mixture of a- and /2-thujone), isothujone, and carvotanacetone are
given by Wallach as follows :—
Boiling-point. Specific Gravity. Refractive Index.
Thujone . . . . 200° to 201° *912 1*4503
Isothujone . . . . 231° „ 232° -9285 1*48217
Carvotanacetone . . . 228° -9373 1-48350
Tiemann gives the boiling-point of thujone (tanacetone) as 230° and
of carvotanacetone as 230°.
Thujone is best identified by its tribromo-compound, C10H13Br3O,
melting at 121° to 122°. It is obtained by adding 5 c.c. of bromine (at
once) to a solution of 5 grams of thujone in 30 c.c. of petroleum ether.
The tribromo-compound separates on evaporation of the solvent and is
washed with alcohol and recrystallised from boiling acetic ether.
THE CONSTITUTION OF ESSENTIAL OILS 237
Thujone has the following constitution :—

CH3—CH—CH3
CH
>CO
CH—CH3
that of isothujone being as follows :—
CH3—CH—CH3
CH
CH,—C/NCH,
-•-3
CH,—C1 ICO
These constitutions have recently received support from the work of
A. Haller.1 If they are correct, then thujone should be capable of yielding
trialkyl substitution products, whilst isothujone should not be able to go
beyond the dialkyl stage. By alkylation with the assistance of sodium
amide, triallylthujone could be prepared, but no higher substitution pro-
duct than dimethylisothujone could be prepared from isothujone. In the
course of his work, Haller prepared the following alkyl derivatives of the
two ketones:—
,C(CH3)2
Dimethylthujone, C8H14<^ \ . Boiling-point at 12 mm. 92° to
X
CO
15°
94° C.; specific gravity — 0*916; [a]D - 19*45°; does not combine with
hydroxylamine.
/C(C3H5)2
Diallylthujone, C8HU^ I . Boiling-point at 18 mm. 147*5° to
\CO
20°
148-5° C. (corr.); specific gravity — O9352 ; refractive index 1-4850.
Triallylthujone, C19H28O. Boiling-point at 21 mm. 173° to 175° C.
20°
(corr.); specific gravity — 0*9467; refractive index 1-5016.
Dimethylisothujone, C12H20O. Boiling-point at 19 mm. 120° to 122° C.
(corr.).
Allylisothujone, C13H20O. Boiling-point at 18 mm. 144° to 146° C,
20°
(corr.); specific gravity— 0'9280; refractive index 1*4930.
1
PULEGONE.
Pulegone, C10H16O, is found in various essential oils, including those of
Mentha pulegium and Hedeoma pulegoides. It can be extracted from
essential oils containing it, in the usual manner, by means of its bisulphite
compound. It is a colourless liquid having an odour recalling that of
peppermint, and having the following characters :—
Boiling-point . . . . 221° to 222rj
,, ,, at 15 mm. 100° „ 101°
„ rotation . . . . + 22-89°
CH . CH,
H9C CH,
H9C CO
A crystalline oxime is obtained in the usual manner, but as the

reaction causes some alteration of the pulegone, it in reality is the oxime
of an isomeric ketone.1 It is prepared in the following manner: 10
grams of caustic potash dissolved in 5 c.e. of water are added to a solu-
tion of 10 grams of pulegone in three times its volume of alcohol. The
mixture is warmed to 80° and then poured into a solution of 10 grams of
hydroxylamine hydrochloride in 10 c.c. of water. The mixture is now
again heated to 80° for 10 minutes, and then, after cooling, poured
into cold water. The oxime separates in a solid condition, and can be re-
crystallised from petroleum ether. It melts at 118° to 119°, or when
repeatedly recrystallised at 123° to 124°.
The oxime thus obtained appears to be that of isopulegone.
The semi-carbazone, obtained in the usual manner, melts at 172°.
Bayer and Henrich 2 have prepared a bisnitrosopulegone, which is
very useful for the identification of the ketone. A solution of 2 c.c. of
pulegone in 2 c.c. of petroleum ether is cooled in a freezing mixture
and 1 c.c. of amyl nitrite and a trace of hydrochloric acid are added.
Fine needles of the bisnitroso compound quickly separate, which, when
dried on a porous plate and washed with petroleum ether, melt at 81*5°.
By careful reduction pulegone is converted into the alcohol pulegol,
C10H18O, or, by complete reduction into menthol, C10H20O.
When hydrolysed by means of formic acid, pulegone yields acetone
and methyl-cyclohexenone, C7H12O. When this body is again condensed
with acetone, it yields a body isomeric with, and very similar to, natural
pulegone. This body may be termed pseudo-pulegone. A second isomer,
isopulegone, was obtained by Tiemann and Schmidt, by oxidising iso-
pulegol (a body which they obtained in the form of its acetate by heating
citronellal (q*v.) with acetic anhydride). This isopulegone is probably a
mixture of two stereoisomers which have not been separated. Isopule-
gone boils at 90° under a pressure of 12 mm., has a specific gravity 0*921
at 18°, refractive index 1-4690, and optical rotation + 10° 15'. It has
the following constitution :—
1 2
Annalen (1896), 347. Berichte, 28 (1895), 658.
CH . CH3
CO
V
CH 3
The pulegone and the isopulegone series of compounds are very
similar in their physical and chemical properties, but they differ sharply
in the fact that pulegone yields menthol on reduction with sodium, whilst
isopulegone does not.
MENTHONE.
Menthone, a ketone of the formula C10H18O, occurs with menthol in
oil of peppermint. According to the early work of Moriya this body was
described as optically inactive, but this has been shown to be incorrect.
Atkinson describes it as an oily liquid, boiling at 206°, with a rotatory
power of + 21°. Beckmann gives 208° as its boiling-point, and 26° to
28° as its optical activity. Its specific gravity is -894. Oxidation of
natural menthol produces laevo-menthone, but this is easily converted
into dextro-menthone by the action of acids. This, on reduction, yields
dextro-menthol. The various derivatives of the optically active isomers
correspond closely, but complicated stereochemical relationships exist,
which render the chemistry of their derivatives a very difficult question.
The oximes of the two isomers do not correspond in their properties,
that of dextro-menthone being a laevo-rotatory oil, whilst that of laevo-
menthone is a solid, melting at 60° to 61°. The semi-carbazone melts at
184° in both cases. There are numerous bodies isomeric with, and
closely similar to, those of the menthone series. Those of the thuja-
menthol and carvomenthol series have already been mentioned. Men-
thone has the constitution —
CH(CH3)
2c, 'GO
H
menthol being, of course, the corresponding alcohol.
Four isomeric ment hones may exist, with eight corresponding isomeric
menthols (vide supra). But whichever menthone is converted into
menthol, natural laevo-menthol is the predominating resulting compound.
Various specimens of menthone have been prepared and examined
by different chemists, the characters of which fall within the following
limits : —
Specific gravity ........ 0-894 to 0-899
Optical rotation . . . . . . . . - 26°
Boiling-point ......... 207° to 208°
Menthone has been prepared synthetically by Kotz and Hesse l from
methyl hexanone. This body was condensed with ethyl oxalate by adding
1
Annalen, 342 (1905), 306.
an ice-cold mixture of the two in small quantities at a time to a cold
solution of sodium ethylate. After fifteen hours the reaction mass is
mixed with ice-cold dilute sulphuric acid, and the oxalic compound of
methyl hexanone is extracted by means of ether. This product is methyl -
l-hexanone-3-oxalic ester-4. When distilled at normal pressure this ester
loses CO2 and becomes methyl-l-hexanone-3-carboxylie ester, which when
treated with methyl iodide and sodium yields methyl-l-hexanone-3-
methyl-4-carboxylic ester-4. This ester on decomposition with alcoholic
potash yields1 ^-menthone.
Wallach has synthesised i-menthone by condensing 1, 4-methyl-
cyclo-hexanone with bromo-isobutyric ester; from the condensation
product he prepared ^-menthene, which was converted into i-menthenone,
by means of its2 nitrosochloride, whence i-menthone resulted by reduction.
Beckmann has examined the characters of the optically active men-
thones. The oxidation of natural Z-menthol by chromic acid mixture
yielded Z-menthone [a]D = - 28'5° which when treated with 90 per cent,
sulphuric acid is converted into a d-menthone [a]D = + 28'1°, which,
however, is not the optical antipode of the first: it behaves as a mixture
of d- and Z-menthone, but is more strongly dextro-rotatory than it would
be if it were only a mixture of the two optical antipodes.
The reduction of Z-menthone or inverted d-menthone yielded, together
with ordinary menthol, a d-isomenthol melting at 78° to 81° C.; [a] =
+ 2*03 which, on oxidation with chromic acid mixture, yielded an iso-
menthone, the specific rotatory power of which varied between + 30'2°
and + 35-1°.
The treatment of menthylamine by nitrous acid yielded a d-isomenthol
still more strongly dextro-rotatory. A d-isomenthylamine hydrochloride,
having a rotatory power of [a]D = + 17*7°, yielded a d-isomenthol having
[a]D = + 25-6°.
Menthone can be prepared by the reduction of piperitone. For this,
Smith and Penfold 3 give the following method :•—
Pure piperitone was subjected to the action of purified hydrogen, in
the presence of a nickel catalyst, for six hours, the temperature ranging
between 175° to 180° C. The double bond in piperitone was readily
opened out with the formation of menthone, but further action of the
hydrogen under these conditions did not reduce the carbonyl group,
even after continued treatment for two days. Under correct conditions,
however, the reduction to menthol should take place. The ease with
which menthone is formed in this way is of special interest, not only in
connection with the production of this ketone, but also as a stage in the
manufacture of menthol.
The reduction of piperitone to menthone cannot well be brought
about by the action of sodium or of sodium-amalgam in alcoholic solution,
because, with the latter particularly, a solid bimolecular ketone is formed
at once. This is a finely crystallised substance, melts at 148° to 149° C.,.
and has the formula C20H34O2. Piperitone thus follows the rule with
substances having a conjugated double bond, carvone for instance,
also forms a bimolecular ketone on reduction, melting at 148° to 149° C.
Menthone was prepared from piperitone in almost quantitative
yield, and had the characteristic peppermint odour of this substance. It
1 2
Annalen,
9
362 (1908), 261. Berichte, 42, 846.
J. and Pro-. Roy. Soc., N.S. Wales, liv. 45.
was colourless ; boiled at 208° C., had specific gravity at 20° = 0-8978 ;
optical rotation aD - 0*15°, and refractive index at 20° = T4529. The
oxime melted at 80° C., the more soluble semicarbazone at 156° C.,
while the least soluble melted at 187° to 198° C. Any unreduced piperi-
tone can be removed from the menthone by the action of neutral sodium
sulphite.
MENTHENONE.
A'-menthenone, C10H16O, has been isolated by Schimmel & Co.1 from
Japanese peppermint oil. It is an aromatic liquid having the following
characters:—
C.CH.
H2a ,co
CH
H(CH8)2
It yields a semi-carbazone, which exists in two modifications, the
a-modification, which is only slightly soluble in alcohol, melting at
224° to 226°, and the /^-modification, which is easily soluble, melting at
171° to 172°.
With hydroxylamine, menthenone yields a normal oxime, and an
oxaminoxime. The latter body is not very volatile, and the oxime can
be separated by steam distillation, and, when recrystallised from alcohol,
melts at 107° to 108°. The oxaminoxime melts at 164° to 165°.
CAMPHOR.
Camphor, C10H16O, occurs in the wood of the camphor tree (Laurus
camphora) as dextro-camphor. This is the ordinary camphor of com-
merce, known as Japan camphor, whilst the less common laevo-camphor
is found in the oil of Matricaria parthenium. Camphor can also be ob-
tained by the oxidation of borneol or isoborneol with nitric acid. Cam-
phor may be prepared from turpentine in numerous ways, and there are
many patents existing for its artificial preparation. Artificial camphor,
however, does not appear to be able to compete commercially with the
natural product. Amocgst the methods may be enumerated the
following:—
1. Esters of borneol are obtained by the action of dry oxalic acid on
turpentine under suitable conditions. From these, borneol is obtained
by saponification and is oxidised to camphor. Some other acids produce
a similar result, as, for example, salicylic and chlorobenzoic acids.
1
Schimmel's Bericht, October (1910), 79.
VOL. II. 16
2. Pinene hydrochloride is prepared in the usual manner from
turpentine, and this is allowed to react with acetate of silver. Isobornyl
acetate is formed, which is hydrolysed, and the isoborneol oxidised to
camphor. Acetate of lead is also used, as is also acetate of zinc.
3. The action of magnesium on pinene hydrochloride gives rise to
bornyl esters, and camphor can be obtained from these in the usual
manner.
4. Pinene hydrochloride is treated by one of the reagents which
abstract-HC1, and so converted into camphene (q-v.). This is heated
with acetic and sulphuric acids, and so converted into isobornyl acetate.
Camphor results in the usual manner.
Camphor forms a translucent mass, which crystallises well from
alcohol. It has the following characters :—
Boiling-point 205° „ 207°
Specific rotation . . . . . . . . + 44°
Optically inactive camphor melts at 179°.

Camphor is the ketone of the alcohol borneol, and forms a number of
well-characterised crystalline derivatives. Amongst these are the semi-
carbazone, the phenylhydrazide, and the oxime, all characteristic of
bodies containing the . CO . group. -The semi-carbazone,
C10H16: N2H . CO . NH2,
melts at 236° to 238°. The hydrazide, C10H16: N2HC6H5, results from
the action of phenylhydrazine. The oxime, C10H16. NOH, is prepared
by the action of hydroxylamine on camphor. It melts at 118°, and when
reduced by means of sodium, yields the base bornylamine, C10H17NH2.
When distilled with phosphorus pentoxide, camphor yields cymene,
and with iodine, carvacrol. Both of these bodies are jpara-derivatives of
benzene. On oxidation with nitric acid camphor yields many acids, of
which the chief are camphoric acid, C10H16O4, camphanic acid, C10H14O4,
and camphoronic acid, C9H14O6. The constitution of these acids has an
important bearing on that of camphor. Many formulae have been sug-
gested for camphor during the pasb few years, but that of Bredt is now
universally accepted, and has received complete confirmation by Komppa's
synthesisl of camphoric acid. This synthesis confirms the formula for
camphoric acid as—
CH2—CH . COOH
C(CH3)2
CH2—C(CH3) (COOH)
which is in accordance with Bredt's formula for camphor.
Camphor has the following constitution :—
i Berichte, 36, 1332.

CH
CHo
CH . C . CH,
H9C CO
C.CH 8
l
Haller and Louvrier have prepared a number of homologues of cam-
phor by heating the ketone in benzene solution with sodamide and alkyl
iodides. The following are the characters of a number of these :—
Boiling-point. Specific
Gravity at 0°. [ajf.
Monoethylcamphor 108° (14 mm.) 0-927 + 45°

Diethylcamphor . 132° to 133° (14 mm.) 0-969 + 91°
Methylethylcamphor 112° „ 114° (11 „ ) — + 99° 30'
Propylcamphor . 116° (11 mm.) 0*942 + 60° 40'
Dipropylcamphor 157° (14 „ )
— + 53° 50'
Benzylcamphor . — + 147° 40'
—
Dibenzylcamphor 255° (12 mm.) + 103° 10'
Ethylbenzylcamphor 193° (11 „ ) —
— + 91°
Eupe and Iselin 2 have prepared a number of homologues of methylene

camphor by a general method depending on the reaction between chloro-
methylene camphor and various organo-magnesium compounds. Chlorp-
methylene camphor itself can be prepared by the action of thionyl chloride
on hydroxymethylene camphor ; the resulting compound is a colourless
oil boiling at 113° at 12'5 mm. pressure, and having an optical rotation
of + 180° in benzene solution. Ethylidene camphor,
C8H14(C : CH . CH3)CO,
is prepared by the action of magnesium methyl bromide on an ethereal
solution of chloromethylene camphor. It forms radiate crystals melting
at 28° to 29° and boiling at 109° to 110° at 12 mm. It has an optical
rotation + 178'5°. The corresponding propylidene camphor is prepared
in a similar manner, and is a colourless oil, boiling at 121° to 122° at
13 mm. Its specific gravity is 0*9448 at 20°, and optical rotation + 173°.
Butylidene camphor has a specific gravity 0*938 at 20°, and optical rota-
tion + 161°. Amyildene camphor, the last of this series prepared, has a
specific gravity 0*927 at 20°, and optical rotation + 156*6°. Aromatic
substituted camphors were also prepared in the same manner, among
which are the following : Benzylidene camphor is a colourless crystalline
solid, melting at 98-5°, and having the formula
C8H14(C ; CH . CH2C6H5)CO.
It has the extraordinarily high specific rotation + 426*5°. Phenyl-
ethylidene camphor is a faintly greenish oil of specific gravity 1*025 at
1 2
Comptes rendus, 158 (1914), 754. Berichte, 49, 25.
20°, and specific rotation + 129°. Phenyl-propylidene camphor has a
specific gravity 1*0094 at 20°, and specific rotation -h 128°. Phenyl-
butylidene camphor has a specific gravity of 0*999 at 29°, and specific
rotation + 113°. Cyclohexylmethylene camphor was prepared by the
use of magnesium cyclohexyl bromide, and forms colourless prisms melt-
ing at 46° to 48°.
Alpha-n&phihylidene camphor was similarly obtained in long trans-
parent crystals melting at 98° to 99°, boiling at 253°, and having a
rotation + 335*6°. An attempt was made to prepare a diphenyl de-
rivative, but this was unsuccessful. A number of the above-described
compounds were reduced with sodium amalgam in methyl alcohol,
neutrality being maintained by the addition of 50 per cent, acetic acid.
In this method the authors obtained iso-amyl camphor, a colourless,
inodorous oil boiling at 140° at 14 mm., and having a specific gravity
0*9197 at 20°, and specific rotation + 66*8°. Phenyl-ethyl camphor forms
colourless prisms melting at 60° to 61°, and having a specific rotation
+ 22*8°. Phenyl-propyl camphor is a colourless oil boiling at 208° to
210° at 15 mm., and having a specific rotation + 52'4°.
ELSHOLTZIONE.
The oil of Elsholtzia cristata contains a ketone, which has been
examined by Asahina and Murayama, and which has the following con-
stants ;—
„ „ 760 „ 210°
Optical rotation . . . . . . . . . 0°
It has the formula C10H14O2, and forms a semi-carbazone melting at
171° and an oxime melting at 54°.
This ketone has, according to Asahina and Murayama, the following
constitution:—l
HC CH
H3C— G C—CO—CH2— CH(CH3)2
According to Asano,2 however, its constitution is as follows ; —

. CH
CH2Z (C ^
\ o3H7i )/ . CO . C
CH
ACETOPHENONE.
Acetophenone, C6H5 . CO . CH3, is a ketone occurring in oil of lab-

danum resin. It also occurs in the oil of Stirlingia latifolia which con-
tains over 90 per cent, of the ketone.3 It is a fragrant, crystalline
substance melting at 20° and boiling at 200° to 202°. It is prepared
artificially and is useful in synthetic perfumery. As found in commerce
1
2
Jour. Pharm. Soc. Japan (1918), 1.
3
J. Pharm. Soc. Japan, 1919, 454, 999.
See Vol. I. p. 172.
it is generally liquid, either in a state of superfusion, or because of traces
of impurities. It can be prepared by distilling a mixture of calcium
benzoate and calcium .acetate, or by condensing benzene and acetyl
chloride in the presence of aluminium chloride.
Anhydrous aluminium chloride in powder is placed in a capacious
flask attached to a reflux condenser, and covered with dry benzene (30
grams). The flask is kept cold with ice, and acetyl chloride is allowed
to drop slowly into the mixture. A vigorous reaction ensues, and much
hydrochloric acid gas is evolved. After about one hour the reaction is
finished, and the mass is transferred to a mixture of ice arid water, when
a brown oil separates. This mixture is extracted with benzene, the
benzene extract is washed with dilute caustic soda, finally with water,
and dried over calcium chloride, from which the liquid is decanted and
distilled, and when the benzene has come over, the temperature of the
vapour rises to 195°, the fraction 195° to 202° being collected as an almost
colourless oil, which solidifies on chilling and is almost pure acetophenone.
It forms an oxime melting at 56° to 60°, and a semi-carbazone at 185° to
187°. It is extremely powerful and gives good results in soap perfumery,
and is a good auxiliary for such perfumes as new-mown hay, syringa, and
the like.
METHYL-ACETOPHENONE.
Paramethyl-acetophenone, CH3 . C6H4 . CO . CH3, is a synthetic per-
fume ketone, having a powerful floral odour. It is prepared by the
Friedel-Craft reaction in the same manner as acetophenone, by con-
densing toluene with acetic anhydride. It is a strongly odoriferous oil
boiling at 220°, and having a specific gravity 1*0062. Its oxime melts at
88° and its phenylhydrazone at 97°.
OXY-ACETOPHENONE.
This body is a phenolic ketone of the formula C6H4(OH). CO . CH3.

C . CO . CH,
.OH
HCX JCH
It is found naturally in the oil of Chione glabra. It boils at 160° to

165° at. 34 mm., and has a specific gravity 6*850. It forms an oxime
melting at 112° and a phenylhydrazone melting at 108°.
DlMETHYL-PHLOEACETOPHENONE.
This ketone, of the formula C6H2(CO . CH3)(OH)(OCH3)(OCH3), is
found in the essential oil of Blumea balsamifera. It is a crystalline
substance melting at 82° to 83°, and having the constitution —
CH
H,CO
HC ;C . CO . CH3
Y O.CH,
It yields an oxime melting at 108° to 110°, and a bromine derivative,
C10HnO4Br, melting at 187°.
BENZYLIDENE ACETONE.
Benzylidene acetone, C6H5 . CH ; CH . COCH3, is a crystalline body
melting at 42°, having an intense floral odour. It results from the con-
densation of benzaldehyde and acetone under the influence of caustic
soda. It has the following characters :—
Spe2ific gravity 1-0377 at 15°
Melting-point 42°
Its oxime melts at 115° to 116°.
BENZOPHENONE.
This ketone, C6H5 . CO . C6H5, is diphenyl ketone. It is a fragrant
crystalline body melting at 48° and boiling at 307°.
It is prepared artificially by the distillation of calcium benzoate, or
by the condensation of benzene and benzoyl chloride in the presence of
aluminium chloride.
It has not been found naturally occurring in essential oils.
TKIMETHYL-HEXANONE.
Masson l has isolated a ketone, of the formula C9H16O, from oil of
labdanum. It has the following characters :—
at 10 mm. 66° „ 67°
Specific gravity'at 0° . 0-922
It yields a monobromide melting at 41°, a semi-carbazone melting
at 220° to 221 °, and an oxime melting at 106°. When reduced with sodium
and alcohol it yields a secondary alcohol, which forms large crystals
melting at 51°. On oxidation by cold 3 per cent, solution of potassium
permanganate it yields geronic acid, a keto-acid of the constitution—
CH 3 . CO . CH 2 . CH 2 . CH 2 . C(CH3)2 . COOH.
This acid boils at 190° to 191° at 31 mm., and yields a semi-carbazone
melting at 164°.
The ketone itself is trimethyl-1, 5, 5-hexanone-6, of the constitution—
CH3
CH
H2C/\CO
H
2C\^/C(CH3)2
CH2
1
Comptes rendus, 154 (1912), 517.
PAEONOL.
This ketone has been found in the essential oil of Pgeonia Moutan.
It is a crystalline body of the formula C9H10O3. Its constitution is—
C . CO . CH3
C .OH
HCX VCH
. O . CH3
It is therefore jo-methoxy-o-hydroxyphenyl methyl ketone.
It yields an ethyl ether melting at 46*5°, and a phenylhydrazone
melting at 170°.
Paeonol has been prepared synthetically by Hoesch ; l he allowed
5 parts of resorcinmethyl ether to react with 3 parts of acetonitrile, with
zinc chloride and ether. Chlorine was then passed through the mixture
for four hours. The mixture was shaken with ether, and the aqueous
solution steam distilled, when paeonol comes over with the steam, leaving
the non-volatile isopaeonpl in the flask.
Paeonol forms a nitro-compound C6H905N, melting at 153° to 155°.
Hydroxypaeonol, C9H10O4, has also been found in essential oils of the
Xanthoirhaa species. It melts at 79°.
ACETO v AN-ILLONE .
This body, which is found in the essential oil of Apocynum andosaemi-
fofaim, is isomeric with the last described ketone, being w-methoxy-
j9-hydroxyphenylmethyl ketone, of the constitution—
C . CO . CH,
HCX JC . O . CH,
C.OH
ANISIC KETONE.
Anisic ketone, C10H12O2, is found in oil of fennel. It is a liquid
boiling at 263°, and having a specific gravity T095 at 0°. Its oxime
melts at 72°. On oxidation it yields anisic acid. Its constitution is as
follows :—
C . CH 2 . CO . CH3
HC CH
HC«
C . O . CH,
L
Berichte, 48 (1915), 1122.
DlOSPHENOL.
Diosphenol, C10H16O2, or buchu-camphor as it is also called, is a

phenolic ketone found in the essential oil of buchu leaves. It is a crystal-
line substance having the following characters : —
Melting-point ...... 83° to 84°
Boiling-point ...... 232°, with decomposition
„ at 10 mm ..... 109° to 110°
It yields a phenylure thane melting at 41°, a semi-carbazone melting

at 219° to 220°, and an oxime melting at 125°. The OH group appears
to possess alcoholic as well as phenolic functions, forming acetic and
benzoic esters, as well as direct combinations with alkalis.
On reduction by means of sodium amalgam and alcohol, it yields an
alcohol, C10H18O2, melting at 159°.
Diosphenol has the following constitution : —
C— CH3
H C
CH . CH(CH3),
It has been prepared artificially by Semmler and McKenzie l by
oxidation of oxymethylene-menthone, C/nHjgOg, a diketone, C10H16O2, re-
sulting, which is inverted by means of alkalis to diosphenol.
Cusmano 2 has also prepared it artificially by shaking dibromomen-
thenone with 2*5 per cent, solution of caustic potash, and when solution
is effected, saturating the liquid with carbon dioxide.
JASMONE.
Jasmone, CnH16O, is a ketone found in essential oil of jasmin, and
also in neroli oil. It is a dark-coloured liquid with a powerful jasmin
odour, and having the following characters : —
Boiling-point at 775 mm ........ 257° „ 258°
Melting-point of oxime ....... 45°
,, ,, ,, semi-carbazone ..... 201° to 204°
SANTALONE.
Santalone, CnH16O, is a ketone found in small quantity in sandalwood
oil. It has the following characters : —
at 15 mm. 88° „ 89°
Melting point of oxime 75°
semi-carbazone 175°
l
2
Berichte,39 (1906), 1158.
Atti. R. Accad d. Lined (5), 22, ii. (1913), 569.
MUSK AND CIVET KETONES (MUSKONE AND ZIBETHONE).
Two ketones of unknown constitution have been isolated from natural
musk. Of these, muskone, C15H28O (or C16H30O), occurs to the extent of
0*5 to 2 per cent.1 It is a thick, colourless oil with a very powerful odour
of musk. It boils at 327° to 330° at 752 mm., and at 142° to 143° at 2
mm. It yields an oxime melting at 46° and a semi-carbazone melting at
133° to 134°.
Sack 2 has recently isolated a ketone from natural civet. The civet
was boiled for some hours with alcoholic potash, the alcohol evaporated
and the residue extracted, with ether. The residue left on evaporating
the ether was distilled with steam to remove skatole, again extracted with
ether, the ether evaporated and the residue dissolved in alcohol. The
alcohol was evaporated, and the residual ketone purified by conversion
into its semi-carbazone, from which it was regenerated. It has the
formula C17H30O, and its characters are as follows:—
„ „ 342° at 741 mm.
Melting-point 32-5°
„ of oxime 92°
,, ,, ,, semi-carbazone . . . 187°
The name zibethone has been proposed for this ketone.
KAEMPFEBIA KETONE.
The essential oil of Kaempferia Ethela contains a crystalline ketone
of the formula C24H28O4.3 It forms large transparent diamond-shaped
crystals melting at 102° and having a specific rotation + 198° 20' in
chloroform solution. The crystals are practically odourless, but in dilute
alcoholic solution a distinct odour is perceived, which reminds one of
crushed ivy leaves. It is a highly unsaturated compound, and combines
readily with bromine. It does not form a bisulphite compound. It
yields a hydroxylamine-oxime melting at 184°, which forms hard white
crystals, and which when shaken with dilute hydrochloric acid is converted
into the oxime C24H28O3: NOH, melting at 166°.
It forms a benzoyl derivative melting at above 260° with decomposition.
GURJUN KETONE.
A ketone exists in gurjin oil, which according to Semmler has the
formula C15H22O, whilst Deussen and Philipp 4 consider its formula to be
C15H24O. It has the following characters :—
Refractive index 1-527°
The last three figures apparently refer to the ketone in the superfused
condition.
The semi-carbazone melts at 234°, and has a specific rotation + 317°
in chloral hydrate solution.
1 2
Jour, pralct. Cliem., ii. 73 (1906), 488. Chem. Zeit., 39 (1915), 538.
*Chem. Soc. Trans. 107 (1915), 314.
4
Annalen, 369 (1909), 56 ; 374 (1910), 105.
7. PHENOLS AND PHENOLIC COMPOUNDS.

PHENYL-METHYL ETHER.
This ether, C 6 H 5 . O . CH3, known as anisole, is a mobile oil of very
fragrant odour. It is used to some extent in synthetic perfumery. It
is prepared by the action of methyl iodide on sodium-phenol, according to
the following equation :—
C6H5ONa + CH3I = C6H5. 0 . CH3 + Nal.
It boils at 172°.
PHENYL-ETHYL ETHER.
This ether, C6H5 . O . C2H5, is known as phenetole. It is a fragrant
liquid boiling at 172°, and is prepared in a similar manner to the methyl
ether.
DIPHENYL OXIDE.
Phenyl Ether.—Diphenyl oxide, C6H5 . O . C6H5, is a crystalline com-
pound which has been known for many years, but which has suddenly
come into considerable vogue in synthetic perfumery. It has been vari-
ously described as having an odour resembling orange oil, hyacinths, and
geranium. As a matter of fact, it has a powerful odour of geranium
leaves, and is the basis of most of the synthetic geranium oils. It can
be prepared in numerous methods, of which the following are examples:
On distilling copper benzoate, diphenyl oxide results directly, or by
digesting diazo-benzene sulphate with phenol, diphenyl oxide results,
according to the following equation :—
C6H5N : N . HS04 + C6H5OH = (C6H5)2O + N 2 + H2SO4.
It also results by heating phenol with aluminium chloride.
Diphenyl oxide forms long crystals melting at 27° to 28° and boiling
at 252° to 253°. As illustrating the manner in which valuable synthetic
perfumes are overlooked, unless their discoverer happens to be an expert
in odours, we quote the following from a work published in 1899: " Di-
phenyl oxide has an indescribable hyacinth-like odour, but has not found
any practical application ". To-day, it is manufactured in very large
quantities, and, as stated above, forms the basis of all the synthetic
geranium oils. It is readily soluble in alcohol, and most organic solvents,
and is most useful in all blends where a geranium odour is required,
Cresol yields similar oxides, having marked perfume odours, but these
do not yet appear to be commercial articles. The three isomeric ethers
have the following characters: their formula is > (C7H7)2O; the ortho-
compound boils at 272° to 273°; the meta-compound boils at 284° to 286°;
and the para-compound melts at 50°.
CRESOL COMPOUNDS.
Meta-creaol, C7H8O, is a crystalline substance, melting at 4° and boil-
ing at 201°. It occurs to a considerable extent in coal-tar mixtures, and
is present in very small amount in essential oil of myrrh. It forms a
characteristic tribromide, melting at 82°.
Para-cresol, which is also a constituent of coal-tar creasote, occurs in
the es ential oils of jasmin and cassie flowers. It is a crystalline sub-
stance melting at 36° and boiling at 199°. It can be identified in the

following manner. Its alkaline solution is treated with dimethyl sulphate,
which converts it with KS methyl ether, a highly odorous liquid boiling at
175°, and which, on oxidation by permanganate of potassium, yields
anisic acid melting at 180°. Para-cresol yields a benzoyl derivative
Para-cresol methyl ether occurs naturally in oil of ylang-ylang and
similar flower oils. It is also prepared synthetically, and forms a useful
artificial perfume for compound flower odours. It is a liquid boiling at
175°, and, as stated above, yields anisic acid on oxidation.
These three bodies have the following constitutions:—
HC/\CH HC/NCH HC/NCH

HCX ,C . OH HC^
CH C . OH C . O . CH3
ra-cre-ol. jp-cresol. _p-eresol methyl ether.
PHLOROL ETHERS.
Phlorol, C6H4< , or ortho-ethyl phenol, has been identified in pine

\OH
oil, and in the form of its methyl and isobutyl ethers, in oil of arnica.
These two ethers have the formula—
1
TT <r/
C6±i rê-t^x
TI /
4 X
\OCH3 OC4H9
Methyl ether. Isobutyl ether.
Phlorol boils at 225° to 226°.
GUAIACOL.
Guaiacol is the monomethyl ether of the diphenol, catechol, or ortho-

dihydroxybenzene. Its constitution is—
/OH
.CH 3
It has been found in pine oil.
THYMOL.
Thymol, C10H14O, is the principal constituent of the oils of thyme and
ajowan seeds. It is isopropyl-weta-cresol of the constitution—
C.CH 3
HC COH
O . C H CH3)2
It is a colourless crystalline substance, having the characteristic odour

of thyme oil, and possessing very powerful antiseptic properties. Its
characters are as follows : —
Melting-point ........ " 50-5° to 51 '5°
Boiling-point ........ 232° at 752 mm.
24°
Specific gravity at -^ ...... 0'969
Eefractive index ....... 1*5227 (superfused)
It combines with chloral to form a compound melting at 131° to 134°.
Its phenylurethane melts at 107°. It forms a nitroso-compound melting
at 160° to 162°, when treated with nitrous acid.
If thymol be treated with sodium and a current of carbonic acid be
passed through it, o-thymotic acid is formed, which when liberated by
means of hydrochloric acid and purified by distillation, melts at 123°.
Thymotic acid has the constitution—
COOH<2>
C3H7<4>
By oxidation it yields thymoquinone, C6H2(O2)(CH3)(C3H7), melting
at 48°.
Thymol frequently occurs associated with carvacrol, its or£/io-isomer,
and may be separated therefrom by fractional crystallisation of the
phenylurethanes, that of carvacrol being much less soluble in petroleum
ether than that of thymol.
Thymol forms a soluble compound with alkalis, and can be extracted
from the oils in which it occurs by shaking with a 5 per cent, solution of
caustic soda or potash.l
Smith and Penfold have shown that thymol can be prepared by the
action of'ferric chloride on piperitone.
60 grams of pure piperitone were added to a solution of 175 grams
ferric chloride, 160 c.c. glacial acetic acid, and 500 c.c. of water. The
whole was then heated on the sand bath to boiling. The reaction takes
place according to the equation 2FeCl3 + H2O = 2FeCl2 + 2HC1 + O,
and was completed at the expiration of about one hour. The reaction
product was then steam distilled, the phenol separated and absorbed in
a 5 per cent, solution of sodium hydrate, the unabsorbed oil removed by
ether, and the aqueous layer decomposed by hydrochloric acid. The
phenol was finally distilled under reduced pressure when the thymol
came over at 110° to 111° C. at 10 mm. In this way they obtained a
25 per cent, yield of the weight of piperitone taken; but, no doubt,
methods can be devised whereby an almost theoretical yield could be
obtained.
Phillips and Gibbs2 have summarised the history of the preparation of
thymol synthetically and gives the following interesting account thereof.
Starting with cuminal, nitro-cuminal was prepared, the nitro group
entering the para position, meta to the aldehyde group. This compound
when treated with phosphorus pentachloride was converted into nitro-
cymyline chloride, which on reduction with zinc and hydrochloric acid
1
J. and Proc. Royal Soc. N.S. Wales, liv. 40.
*Jour. Ind. Eng. Chem. (1920), 733.
gave 3-aminocymene, and upon diazotisation and subsequent hydrolysis
thymol resulted.
Thymol has since been synthetised by a number of chemists, but only
two of those syntheses need be considered in this connection because of
their close relationship to the present method. Dinesmann (D.E.P..
125,097 (1900)) obtained a patent for a process of making thymol from
2-brom-p-cymene. This process consists in sulphonating 2-brom-p-
cymene, obtaining 2-brom-3- or 5-sulphonic acid, which, when heated
with zinc dust and ammonia in an autoclave at 170°, gives cymene-3-
sulphonic acid. This compound on fusion with potassium hydroxide
gives thymol.
Eecently a patent has been granted to Andrews (U.S. Patent 1,306,512,
1919) for a process for making thymol from cymidine (2-aminocymene).
Cymidine is first acetylated, then nitrated; whereupon the nitro group
enters meta to the methyl group. The acetyl group is hydrolysed off and
the amino group removed through diazotisation and subsequent reduction
of the diazo compound with alkaline stannous chloride or with boiling
alcohol. The nitro compound thus obtained is then reduced to the
corresponding amino compound, which on diazotisation and subsequent
hydrolysis gives thymol.
In the details given by Phillips and Gibbs in the publication referred
to the following experimental procedure is. outlined : The j[)-cymene was
isolated from a crude oil obtained from a sulphite spruce pulp mill. The
oil after standing over lime for about a week was subjected to steam dis-
tillation. To the distillate about one-fourth its volume of sulphuric acid
was added, and the mixture stirred in the cold by means of a mechanical
stirrer. After two hours' stirring the dark acid was separated from the
oil, a fresh quantity of sulphuric acid added and the stirring continued.
This operation was carried on until a sample of the oil after being washed
with water gave a very slight yellowish colour when shaken with sul-
phuric acid. The oil was then washed with water, dried over calcium
chloride and distilled over sodium, using a Glinsky stillhead. Practically
all the material came over from 174° to 175° (759*6 pressure), leaving
only a small amount of dark coloured oil in the flask.
For the preparation of nitrocymene a method developed in the Colour
Laboratory and described in the Jour, of Ind. and Eng. Chem. in
1918, p. 453, was used. The nitro group enters in the ortho position
with respect to the methyl group. The reduction of this compound to
aminocymene or cymidine was accomplished by means of iron powder
and hydrochloric acid in exactly the same way as nitrobenzene is reduced
to aniline.
The conversion of cymidine to cymidine sulphonic acid was effected as
follows: To 61 c.c. of concentrated sulphuric acid 160 grams of
cymidine were added in small quantities at a time, starring after each
addition of the cymidine. The cymidine sulphate was placed in an
oven and, heated for six hours at about 200°. The mass on cooling was
ground and dissolved in hot water. Upon making the solution distinctly
alkaline with sodium hydroxide the cymidine which had escaped
sulphonation separated as an oil and was recovered by steam distillation.
The residue in the flask was concentrated if necessary, boiled with animal
charcoal, filtered, and acidified with hydrochloric acid. Cymidine sul-
phonic acid separated out as a crystalline mass. The yield was about
30 grams (32 per cent, yield calculated on the 60 grams of cymidine
actually used up), and the unused cymidine recovered amounted to 100
grams.
For the preparation of cymene-3-sulphonic acid from cymidine sul-
phonic acid the following modification of Widman's method was used :
22*9 grams of the cymidine sulphonic acid were suspended in about
400 c.c. of 95 per cent, alcohol, 20 c.c. concentrated sulphuric added,
and diazotised in the cold in the usual manner. After diazotisation the
solution was allowed to stand in the cold for an hour and then 10 grams
of copper powder were added in small quantities at a time, allowing the
rapid evolution of nitrogen to subside before making any further additions.
The mixture was filtered and the filtrate distilled on the water-bath.
The residue in the flask was diluted with water, boiled with barium car-
bonate, filtered, and the filtrate containing the barium salt of cymene-3-
sulphonic acid was treated with sodium carbonate, and the sodium
salt of the sulphonic acid obtained. This sodium salt was converted into
thymol as follows : 30 grams of 98 per cent, sodium hydroxide were
treated with a little water and heated iu a nickel crucible, with stirring,
to 280°. To this 10 grams of the sulphonate were added, with stirring.
After all the salt had been added, the temperature was raised to 310°,
and left there for about fifteen minutes, when the reaction was complete.
The melt on cooling was dissolved in water, acidified with hydrochloric
acid and steam distilled. The distillate was extracted with ether, dried
over anhydrous sodium sulphate and fractionated after distilling off the
ether. Nearly all of the product distilled over at the boiling tempera-
ture of thymol. The thymol obtained was identified by its phenylure-
thane derivative (m.p. 107°).
Mr. Max Phillips himself has taken out the following important patent
for the preparation of thymol from para-cymene.
The process of converting para-cymene into thymol is preferably
carried out as follows :' The first step consists in converting cymene into
cymidin by any known process, an example of a good method being:
Pure para-cymene is slowly added to an equal weight of sulphuric acid
(specific gravity 1'84), which is kept at or below 0°C. To this is slowly
added the previously cooled nitrating mixture, consisting of 1 part nitric
acid (specific gravity 1*42) and 2 parts sulphuric acid (1*84), the amount of
nitric acid being used about 5 to 10 per cent, in excess of that necessary
to substitute one nitro group into the cymene molecule. During the
nitration the mixture is stirred efficiently and the temperature kept at
or below 0° C. When all the nitrating mixture has been added, the
mixture is stirred for one hour longer. The mixture is then poured into
cold water, and the oily upper layer separated off. This is washed several
times with water, with sodium carbonate solution, and again with water.
The nitro-cymene thus obtained is then reduced to amino-cymene or
cymidin by means of iron and hydrochloric acid in exactly the same way
as that used in the industrial preparation of aniline from nitrobenzene.
The cymidin is now sulphonated, 100 parts by weight of cymidin
being slowly added to 69 parts by weight of sulphuric acid (sp. gr. 1*84),
contained in a shallow dish, and the solid crystalline mass of cymidin
sulphate thus obtai ed is then converted into cymidin sulphonic acid by1
an identical method to that used in the so-called "baking process"
for the preparation of sulphanilic acid from aniline sulphate.
This produces l-methyl-2-amino-4-isopropyl-3 or 5 sulphonic acid.
l
Zeitsch. angew. Chem., 9, p. 685 (1896); Berichte, 13, p. 1940 (1880); Dingl.
Polyt. Jour., 264, p. 181 (1887).
The cymidin sulphonic acid is then diazotised in the usual manner by
treating with sodium nitrite in acid solution and the diazo body reduced
with alkaline tin chloride solution, or with formic acid and powdered
•copper, or with other relatively gentle reducing agents. The 3 or 5
cymidin sulphonic acid gives by the above process one and the same
cymene sulphonic acid, viz., l-methyl-3-sulphonic-4-isopropyl benzene.
The sodium salt of the cymene sulphonic acid is then fused with
sodium hydroxide in the usual manner, and the hydroxyl group sub-
stituted for the sulphonic group. This gives l-methyl-3-hydroxy-4-
isopropyl-benzene or thymol.
The thymol can be separated by dissolving the product obtained by
the sodium hydroxide fusion in water, acidulating with dilute sulphuric
acid, and then steam distilling ; or it may be extracted with a suitable
solvent or in any other appropriate manner.
The reactions which take place in the process are conveniently
expressed as follows :—
CH, CH,
-NIL,
Diazotised and>>
reduced with |
alkaline
SnCl2,
formic acid
and copper.
CH,
HO,S— H.O
CH
/\
CH, CH,
Thymol.
The latest patent for the preparation of artificial thymol is that of
E. M. Cole (U.S.P. 1,378,939, 24 May, 1921). His method consists
essentially in the electrolytic reduction of nitro-cymene in the presence
of sulphuric acid, and the subsequent diazotisation and reduction of the
para-amidocymenol produced, by electric action, involving the use of
stannous chloride.
Apparatus suitable for the electrolytic reduction comprises a cylindri-
cal tank with a lead lining, which also serves as the anode. In this
vessel is placed a container, sufficiently porous to permit the passage of
ions from one chamber to another, but nearly impervious to the passage
of molecules, and within the container is arranged a carbon or copper
cathode in the form of a hollow perforated cylinder. Within this latter
cylinder is also arranged a stirrer or agitator, preferably of stoneware or
lead-covered iron. The anode chamber is charged with 30° B6 (sp. gr.
1-26) sulphuric acid, and the cathode space with 25° Be (sp. gr. 1*21}
acid. The strength of the acid in the anode chamber is maintained
throughout the process by the addition of water in suitable quantities
as the reaction proceeds. The nitro-cymene is placed in the cathode
space in a quantity approximately 50 per cent, of the weight of 100 per
cent. acid.
A current of density 5-J- amperes per square decimetre of cathode space
and a potential of 3 volts is used, and the temperature is maintained at
between 75° and 85° C. During the electrolytic action, the nitro-cymene
is kept in thorough emulsion in the aqueous acid solution by means of
the agitator.
After the electrolytic action .has continued for a suitable period, the
contents of the vessel are allowed to cool, following which the unchanged
nitro-cymene is separated for re-use, and the l-methyl-2-amino-4-iso-
propyl-5-hydroxy benzol is filtered off from the remaining acid solution,
which latter is strengthened for re-use. The l-methyl-2-amino-4-
isopropyl-5-hydroxy benzol is then diazotised, and further reduced in
an alkaline solution of stannous chloride, in the usual and well-known
manner, with the resulting production of thymol (l-methyl-4-isopropyl-
5-hydroxy benzol).
The reactions taking place in following out this process may be
shown thus:—
CH3
NO2 S \ NH2
Electrolysis-^ | Diazotisation-
H0\/ HON
C3H7
It is interesting to note that thymol, as well as its isomer carvacrol can
be removed from its alkaline 1solution either by distillation by steam, or by
repeated extraction by ether.
THYMOL-METHYL ETHER.
The methyl ether of thymol is found in the oil of Crithmum maritimum*
It is a liquid of the constitution—
1
Berichte, 32 (1899), 1517; and 15 (1882), 817.
C.CH 3
HC^
X
C. CH(CH3)2
0°
boiling at 214° to 216°, and having a specific gravity O954 at -—0.
On treatment with hydrobromic acid in acetic acid solution it yields
thymol.
CAKVACBOL.
Carvacrol, C10H14O, is a phenol isomeric with thymol, with which it
is frequently found associated, especially in certain types of thyme and
origanum oils.
Carvacrol is isopropyl-orô-cresol, of the following constitution :—
C.CH,
HC CH
CH
It results, artificially, from the treatment of carvone by potash or
phosphoric acid, and by. heating camphor with iodine.
Carvacrol is a colourless liquid, with a fragrant odour, solidifying,
when quite pure, in the cold.
Melting-point + 0-5° to 4- 1°
Boiling-point 236°
Refractive index 1 "5240
It yields a phenylurethane melting at 141°.
If carvacrol be treated, in alcoholic potash solution, with amyl nitrite,
nitrosocar acrol, C6H2(CH3)(OH)(C3H7)(NO), results. This body forms
well-defined crystals melting at 153°.
By heating carvacrol with alkalis, it is converted into isocuminic
acid, C6H3(C3H7)(OH)(COOH), melting at 93°. By oxidation with
chromic acid mixture, thymoquinone results. This compound forms,
crystalline tables melting at 45° to 46°.
CHAVICOL.
Chavicol, C9H10O, is an unsaturated phenol, found in oils of betel nut
and bay leaves. It is a colourless, highly odorous liquid, having the fol-
Specific gravity . . . . . . . . . . 1*035
Optical rotation . . . . . . . . . . +0°
Refractive index . . . 1*5441
Boiling-point 237°
VOL. II. 17
It is âra-oxy-allyl-benzene, of the constitution—
C.OH
HO, * CH
O . OJbL2 . OH '. \j±±.)
Like most phenols, it gives an intense blue colour with solution of

ferric chloride. By heating it with alcoholic potash and methyl iodide it
is converted into methyl-chavicol or estragol, the characteristic constituent
of tarragon oil.
ESTRAGOL.
Estragol, or methyl-chavicol, C^HÔ, is a constituent of tarragon,
anise-bark, bay, fennel, and other essential oils. It is a strongly odorous
Boiling-point 215° to 216° (corrected)
„ at 12 mm 97° to 98°
Specific gravity . . . . . . 0*972°

COCH,
HC
C . CH,. CH : CH2
Methyl-chavicol (estragol, isoanethol methyl-^-oxy-allyl-benzene) is
isomeric with anethol, which by a system of cross-naming is also known
as iso-estragol. In common with other phenol ethers, containing the
allyl group, estragol is converted into its isomer, anethol, which contains
the propenyl group, by boiling with alcoholic potash.
This reaction serves as a means of identification of estragol. If it be
heated for twenty-four hours on the water-bath, with three times its
volume of a saturated alcoholic solution of potash, it is converted into
anethol, which, after drying and recrystallisation from petroleum ether,
melts at 22°, and boils at 232° to 233°.
If 30 grams of estragol be shaken with 20 grams of potassium per-
manganate in 2000 c.c. of water, and 20 c.c. of acetic acid, the solution
being kept cold, estragol yields homo-anisic acid, which can be isolated
by rendering the liquid alkaline with carbonate of sodium, filtering,
liberating the acid by the addition of sulphuric acid, and extracting
with ether.
yCH2COOH
Homo-anisic acid, C(.H4<; , forms well-defined crystalline
cablets, melting at 85° to 86°
ANETHOL.
Anethol (isoestragol, methyl-p-oxy-propenyl-benzene) is the principal
constituent of aniseed and star aniseed oil, and occur to a considerable
extent in fennel oil. It is a crystalline solid, having the characteristic
odour of aniseed oil, and possessing the following characters :—
Boiling-point 233° „ 234°
Befractive index at 25° 1-5600
COCH3
HCLîCH
C . CH : CH . CH3
Anethol is the raw material from which most of the artificial hawthorn
perfume is manufactured. This perfume consists of anisic aldehyde,
known commercially under the name "aubepine".
.COOH
Anethol can be identified by oxidation to anisic acid, C6H4<^
XX)CH3
melting at 184°. It is obtained in the following manner: 5 grams of
the anethol containing oil or fraction are heated to 50° with a solution
of 25 grams of bichromate of potassium and 50 grams of sulphuric acid
made up to 100 c.c. with water. The mixture is well shaken, allowed
to cool and the liquid decanted. The solid deposit is washed with water
and finally recrystallised twice from boiling water when it will be found
to melt at 184°.
Anethol dibromide, C^H4 . OCH 3 . C3H5Br2, melting at 67°, is also a
useful crystalline derivative by which anethol can be identified. It is
obtained by the action of bromine in chloroform solution on anethol.
The product is crystallised from petroleum ether, and then melts at 67°.
1
yCHBr . CHBr . CH,
Its constitution is C6H4<^
N3CH34
HYDKOQUINONE ETHYL ETHEE.
The ethyl ether of hydroquinone,^)ara oxyphenetol, C8H10O2, is found
to a small extent in oil of star aniseed. It can also be prepared artificially
by heating joara-diazophenetol sulphate with dilute sulphuric acid, or by
boiling hydroquinone with ethyl iodide and potassium hydroxide under a
reflux condenser. Its constitution is—
COH
HC
,CH
CO . C2H5
It forms white colourless needles, melting at 66° and boiling at
246° to 247°.
TH YMOHYDEOQUINONE .
Thymohydroquinone,C1 1402, is a constituent of the essential oils
of Callitris quadrivalvis, Monarda fistulosa, and Thuja articulata. It is
a crystalline compound melting at 143° and boiling at 290°, or at 130° at
6 mm. pressure. Its constitution is —
C— CH
HOC^JCH
C. CH(CH3)2
By oxidation with potassium permanganate, it yields thymoquinone
THYMOHYDEOQUINONE DIMETHYL ETHEB.

This phenolic compound, C12H18O2, exists in the essential oil of
Eupatorium triplinerve, and in arnica root oil. It is an oil having the
„ at 12 mm 118°
Its constitution is —
C-CH3
HC/^COCH.,
C H . O.
°\/CH
C . <CH(CH3)2
By treatment with hydriodic acid and amorphous phosphorus, it is
converted into thymohydroquinone, which melts at 143°, and which, as
described above, yields thymoquinone on oxidation.
THYMOQUINONE.
This body, although not a phenol or phenolic ether, is conveniently
described here. It is a quinone, of the formula C6H2(O2)(CH3)(C3H7),
occurring in the essential oils of Monarda fistulosa and Thuja articulata.
It is a crystalline body melting at 48° and boiling at 98° to 100° at 6 mm.
By treatment with hydroxylamine it yields isonitrosothymol, C^H^NO,,,
melting at 161°. This body, on oxidation with potassium ferrocyanide
in alkaline solution, yields mononitrothymol, melting at 137°.
CREOSOL.
Creosol is a dipihenol, of the constitution—
C.CH 3
HCi
vO.OH
C.OH
It occurs in oil of ylang-ylang. It is an odorous oil boiling at 220°.
ALLYL-PYROCATECHOL.
Allyl-pyrocatechol, C9H10O2, exists in betel leaf oil. It is a crystalline
body melting at 48° to 49° and boiling at 139° at 4 mm. It yields a
dibenzoyl derivative melting at 71° to 72°. Its constitution is as follows :—
C. OH
HCl ICH
/ . C*H 2 . CH i CH2
By methylation with dimethyl sulphate and potash, it yields methyl-
eugenol, boiling at 248° to 249°; and which on oxidation yields veratric
acid, melting at 179° to 180°.
PYBOGALLOL DIMETHYL ETHER.
.This phenolic ether, C6H3(OH)(OCH3)2, has been identified in the
essential oil of an Algerian plant, whose botanical source is not identified.
It is a crystalline body melting at 51°, and yields a benzoyl derivative
EUGENOL.
Eugenol, C10H12O2, is the characteristic constituent of the oils of
cloves, cinnamon leaf, bay and pimento, and is also found in numerous
other essential oils. It is a liquid of powerful clove odour, having the
Boiling-point . . . . . 252° at 750 mm.
. 123° „ 12 „
Optical rotation . . . . + 0°
It has the following constitution ;—
COH
HCL JCH
C . CH 2 . CH : CH2
It is the raw material from which the bulk of the vanillin of com-
merce is obtained (see under Vanillin), for which purposes very large
quantities are consumed.
Eugenol yields a characteristic benzoyl derivative when treated with
benzoyl chloride in the presence of caustic potash. Benzoyl-eugenol
The diphenylurethane melts at 107° to 108°. By treatment with
methyl iodide in the presence of caustic alkali, eugenol is converted into
methyl-eugenol, which is characterised by its monobromo derivative
For the manufacture of vanillin, eugenol is first isomerised to iso-
eugenol, in which a rearrangement in the side chain has taken place.
ISOEUGENOL.
Isoeugenol, C10H12O2, is found to a small extent in the essential oils

of ylang-ylang and nutmeg, but is principally of importance in the manu-
facture of vanillin, eugenol being first isomerised into isoeugenol, which
is then converted into vanillin. Isoeugenol has the following constitu-
tion : —
COH
. CH3
JCH
. CH : CH . CH3

Boiling-point ..... ..... 262°
Refractive index ........ . . 1-5730
Isoeugenol, when cooled to a very low temperature, crystallises in

fine needles, which melt at 34°, but it usually exists in a state of super-
fusion.
It is a liquid with a powerful carnation odour, and is indispensable
in the compounding of perfumes of the carnation and " ceillet " type.
There are several crystalline compounds useful for the identification
of isoeugenol, amongst which are the following ; —
Benzoyl-isoeugenol, melting at 105°, is prepared by the addition to
10 parts of isoeugenol of a dilute solution of caustic soda, and then of
15 parts of benzoyl chloride. The temperature should be kept low, and
crystals of benzoyl-eugenol will separate.
If equimolecular proportions of isoeugenol and acetic anhydride are
heated for four to five hours to 135°, and the mixture washed with dilute
alkali, acetyl-isoeugenol results, which, when dissolved in benzene and
precipitated by petroleum ether, crystallises in needles melting at 79°
to 80°.
Isoeugenol, shaken with dimethyl sulphate and caustic potash, yields
methyl-isoeugenol, which can be identified by its dibromide, melting at
101° to 102°.
' Isoeugenol yields a diphenyl-urethane, melting at 112° to 113°.
The conversion of eugenol into isoeugenol is a matter of considerable
importance, especially in the manufacture of vanillin (q.v.). It can be
effected by boiling eugenol with alcoholic potash for twenty-four hours,
but the yield is not a satisfactory one. According to De Laire's patent
(France, 209,149), 25 parts of caustic potash and 36 parts of amyl
alcohol are heated, and any carbonate of potash present is separated by
filtration. Five parts of eugenol are added and the mixture heated to
140° for sixteen to eighteen hours, the amyl alcohol being then removed
by steam distillation. The isoeugenol is then liberated by the addition
of dilute sulphuric acid and distilled in a current of steam.
There are several other methods for the isomerisation of eugenol, but
they all, in the main, depend on the action of caustic alkalis at an
elevated temperature.
ACETEUGENOL.
A very small amount of aceteugenol is present in essential oil of

cloves. Its constitution is as follows :—
COOC.CH 3
.CH 3
HCl CH
CH:CH 2
It also results from the action of acetic anhydride on eugenol. Its
characters are as follows ; —
Melting-point .......... 29°
Boiling-point at 752 mm ......... 281°
„ „ 8 „ ........ 146°
Specific gravity (at 15°, superfused) ...... 1-0842
Refractive index ( „ „ „ ) ...... 1-5207
Acetisoeugenol is the corresponding derivative of isoeugenol, and

METHYL-EUGENOL.
The methyl ether of eugenol, C11H14O2, is found in calamus oil, cassie
oil, betel oil, bay oil, and various other essential oils. It can be prepared
artificially by the action of methyl iodide on eugenol sodium. Its con-
stitution is identical with that of eugenol, except that the phenolic group,
OH, has been replaced by the methoxy group, O . CH3.
It is a useful adjunct in the manufacture of perfumes of the carnation
type, modifying the odours of eugenol and isoeugenol to some extent.
Its characters are as follows ; —
Optical rotation .......... ±0°
Refractive index . - ........ 1-5380
Boiling-point .......... 248°
The principal derivative for identification purposes is veratric acid,

C,;H3(COOH)(OCH3)2, which is obtained by oxidising 6 grams of m ethyl -
eugenol with a solution of 18 grams of potassium permanganate in 400
c.c. of water. When recrystallised from alcohol, veratric acid melts at
179° to 180°.
Monobrom-methyleugenol dibromide is also a useful derivative to
prepare. Its constitution is —
. CHBr
CGH,Br— OCH3
It can be obtained by dissolving 50 grams of methyl-eugenol in 100

grams of absolute ether, and adding 30 c.c. of bromine drop by drop, the
mixture being kept cold during the process. The crystalline compound,
having the above formula, melts at 79° to 80°.
METHYL-ISOEUGENOL.
Methyl-isoeugenol, CnH14O2, bears exactly the same relationship to
isoeugenol as methyl-eugenol does to eugenol. It occurs naturally in the
oil of Asarum arifolium, and can be obtained by the action of methyl
iodide on isoeugenol sodium, or by isomerising methyl-eugenol by hot
alcoholic potash.
Methyl-isoeugenol has the following characters :—
Boiling-point 263°
On oxidation it yields veratric acid melting at 179° to 180°, and by
the action of bromine on the phenol-ether dissolved in absolute ether, a
dibromide is obtained, which melts at 101° to 102°. It has the con-
stitution—
/CHBr . CHBr . CH,
TASMANOL.
l
Eobinson and Smith have separated a phenol from the oil of
Eucalyptus linearis, which they have named tasmanol.
The phenol was removed from the crude oil in the usual manner by
shaking with aqueous sodium hydrate, washing the aqueous solution
with ether to remove adhering oil, acidifying and extracting with ether.
The residue, which contained a small amount of acetic and butyric acids,
was washed with dilute sodium carbonate, extracted with ether, the
ether removed and the phenol distilled. It boiled at 268° to 273° C.
(uncor.) and at 175° under 25 mm. pressure. It was optically inactive,
the specific gravity at 23° was 1*077, and the refractive index at 22° was
1*5269. Besides being soluble in alkalies the phenol is soluble in
ammonia, partly soluble also in sodium carbonate but not in bicarbonate.
It also dissolves slightly in boiling water. The reaction with ferric
chloride in alcoholic solution is characteristic, the deep red colour which
is first formed remaining persistent for days, after the alcohol has evapo-
rated. The odour reminds one somewhat of carvacrol. It contains one
methoxy group and appears to have two phenolic groups in the para
position to each other.
AUSTRALOL.
Australol is a crystalline phenol obtained by Baker and Smith 2 from
various, eucalyptus oils, including those of Eucalyptus hemiphloia and
E. wooloiznci. It is a very caustic substance, resembling ordinary phenol
in odour. Its characters are as follows :—
Melting point 62°
Specific giavity at 20° 0-9971 (superfused)
Refractive index a t 2 0 ° . . . . . 1-5195 ( „ )
iJour. ofProc. Roy. Soc.t N.S.W., 48 (1914), 518.

2
A Research on the Eucalypts, 2nd. edition, p. 396.
It forms long thin prisms, which when melted tend to remain in
the liquid condition, but when the liquid is sown with a crystal of the
phenol it at once solidifies. It forms a benzoyl compound, melting at
72° to 73°. It is apparently dihydro-para-allylphenol of the constitu-
tion —
COH
CH2
C . CH2 . CH : CH2
SAFROL.
Safrol, C10H10O.,, is the methylene ether of allyl-dioxybenzene, of the
constitution —
CO— CH2
Hc C
C . CH2 . CH : CH2
It is found to a considerable extent in oils of sassafras, camphor, and
Ilicium religiosum. When pure it is a white crystalline mass at low
temperatures, melting at + 11°. At ordinary temperatures it forms a
colourless oil of characteristic, pleasant odour, and having the following
characters : —
Melting-point + 11°
Boiling-point 233°
at 4 mm. 91°
It is easily converted into isosafrol (containing the propenyl group) by the
action of alcoholic potash. Safrol is used to an enormous extent for per-
fuming cheap soaps, and is also of great commercial value on account of
the fact that on oxidation it yields heliotropin, an artificial perfume which
is now largely employed (q.v.).
Safrol, on oxidation in the following manner, yields homopiperonylic
acid, melting at 127° to 128°. A mixture of 5 parts of safrol and 12*5
parts of potassium permanganate dissolved in water and 5 parts of acetic
acid are heated to 70° to 80°, and the liquid rendered alkaline.
The liquid is filtered, and on extraction with ether yields some pipe-
ronal (heliotropin), melting at 37°. The residual liquid is boiled with
magnesium carbonate-, resinous matter extracted with ether, the liquid
filtered and the acid set free by means of dilute sulphuric acid. Homo-
piperonylic acid crystallises out on evaporation, and forms fine needles
If chromic acid be used as the oxidising agent, piperonal and pipe-
ronylic acid, melting at 228°, are formed.
Safrol yields a pentabromide, C10Br5H5O2, melting at 169° to 170°.
On reduction by nickel in a stream of hydrogsn, safrol yields a dihydro
product, C10H12O2, boiling at 228°, and raeto-propyl-phenol, boiling at 228°
also.
ISOSAFROL.
Whilst safrol is the methylene ether of allyl-dioxy-benzene, isosafrol

is the methylene ether of propenyl-dioxy-benzene, so that the two bodies
are related to each other in the same, way as eugenol and isoeugenol.
Isosafrol results from the isomerisation of safrol by heating with
alcoholic potash, and this conversion is the preliminary step in the manu-
facture of heliotropine since isosafrol yields considerably more heliotropine
on oxidation than safrol does. Isosafrol has the following constitution :—
CO—CH
HCL "JOEL
Yc CH : CH . CH3
Befractive index 1*5780
Isosafrol yields piperonal (heliotropine) melting at 37° as the principal

product of oxidation when potassium permanganate is used as the oxidis-
ing agent. If the oxidation be very energetic piperonylic acid, melting at
228°, is the principal reaction product.
With excess of bromine, isosafrol yields a penta-bromide, melting at
197°. If safrol, dissolved in carbon bisulphide be heated carefully with
bromine, it yields monobrom-isosafrol dibromide, C10H9Br3O2, melting at
109° to 110°.
According to Hoering and Baum,1 commercial isosafrol contains two
geometric isomers, which they term a-isosafrol and /^-isosafrol. They
differ slightly in odour, a-isosafrol being intermediate in this respect be-
tween safrol and /:?-isosafrol. It is not probable that they yield different
products on oxidation, nor is there the slightest reason to believe that
heliotropine is any such corresponding mixture.
ASARONE.
Asarone, or 4-propenyl-l . 2 . 5 . trimethoxybenzene, C12H10O3, is the
trimethyl ether of a triphenol, which is found occurring naturally in the
essential oil of Asarum arifoliurn, and to a small extent in matico and
acorus oils. It is an aromatic crystalline compound having the following
characters:—
Melting-point 62°
Boiling-point 296°
1
Berichte, 42 (1909), 3076.
COCH3
H 3 CO(\!CH
C . CH : CH . CH3
On treatment with bromine in carbon tetrachloride solution, it yields
a dibromide in which two atoms of bromine have been fixed in the pro-
penyl side chain, melting at 85° to 86°.
By oxidation asarone yields asarylic aldehyde, C6H2(CHO)(OCH3)3,
melting at 114°, and finally asarylic acid, G^H2(COOH)(OCH3)3, melting
at 144°. This acid is, of course, identical with trimethoxy-benzoic acid.
ELEMICIN.
Elemicin is isomeric with asarone. It is 4-allyl-l . 2 . 6-trimethoxy-
benzene, and is found in the essential oil of Manila elemi. Its char-
acters are as follows : —
Refractive index ......... T5285

COCH3
HG 1CH
C . CH 2 . CH : CH2
If elemicin be heated with alcoholic solution of potash, the allyl group
is isomerised to the propenyl group, and iso-elemicin results.
Both bodies yield trimethylgallic acid, C6H2(COOH)(OCH3)3, melting
at 169°. on oxidation.
Elemicin has been synthesised by Manthora.1
By boiling allyl bromide and pyrogallol dimethyl ether with acetone
and potassium carbonate, he obtained a dimethoxyphenyl allyl ether,
which was converted into dimethoxyallyl phenol by heating to 220°. On
methylation this yields trimethoxyallyl benzene, identical with elemicin.
MYEISTICIN.
Myristicin, CnH12O3,is 4-allyl-6-methoxy-l. 2-methylenedioxybenzene.
It is found in oil of nutmeg and in parsley oil. It is a fragrant compound
„ „ 149° at 15 mm.
lAnnalen, 414(1917), 250.

CO— CH,
. CH
C . CH, . CH : CH2
On isomerisation with hot alcoholic potash it yields isomyristicin,
which contains the propenyl group in the side chain, and is a solid body
Myristicin and isomyristicin are distinguished by their reactions with
bromine. Myristicin, when treated with two atoms of bromine, yields an
oily liquid, whilst isomyristicin yields a crystalline body melting at 109°.
If the isomers are dissolved in acetic acid, and treated with bromine until
no more is absorbed, the mixture being kept cold all the time, the follow-
ing compounds are obtained : — .
C6Br2(CH2 . CHBr . CH2Br .)(OCH3)(O2CH2).
Dibromomyristicin dibromide. Melting point » 130°.
C6Br2(CHBr . CHBr . CH3)(OCH3)(O2CH2).
Dibromoisomyristicin dibromide. Melting point = 156°.
Both isomers yield myristic aldehyde on oxidation by means of potas-
sium permanganate. This aldehyde has the formula
C6H2(CHO)(OCH3)(O2CH2),
and melts at 131°. By further oxidation it yields myristic acid,
C6H2(COOH)(OCH3)(OoCH2),
melting at 210°
ALLYL-TETKAMETHOXYBENZENE.
This phenol ether has been isolated from French oil of parsley. It is
a crystalline compound of the formula C13H18O4, which can be separated
by freezing the oil and drying the crystals on porous plates for twenty-four
hours, and recrystallising the product several times from alcohol. Its
constitution is as follows : —
COCH3
H,
HC SCOCH 3
C . CH 2 . CH : CH,
Melting-point 25°
The corresponding propenyl isomer is unknown.
On oxidation with permanganate of potassium, this phenol ether
yields tetramethoxy benzoic acid, C(.H(OCH3)4COOH, melting at 87°.
APIOL.
Apiol, the principal constituent of oil of parsley, is an allyl-dimethoxy-
methylene-dioxybenzene of the formula C12H1464. Its physical char-
,, ,, at 33 mm. 179°
Specific gravity 1-1788 (superfused)
liefractive index 1-5380
CO— CH,
H3COO
HCL ,COCH,
C . CH, . CH : CH,
On heating apiol for twrelve hours with alcoholic solution of potash,
it is isomerised, the allyl group being changed into the propenyl group,
isoapiol resulting. Isoapiol, C0H(CH : CH . CH3)(OCH,)2(O2CH,), is a
crystalline compound having the following characters :—
Boiling-point 303° ,, 304"
at 33 mm 183°
Apiol can be identified by its melting-point and its easy conversion
into isoapiol, melting at 55° to 56°.
If apiol, dissolved in carbon bisulphide, be treated with bromine in
the same solvent, and the solvent evaporated, monobrormpiol dibromide,
C<.Br(O2CH2)(OCH3)2(C3H5Br,), melting at 88° to 89° results. It cm be
obtained in a pure state by several crystallisations from absolute alcohol.
The corresponding isoapiol compound melts at 120°. Both apiol and
isoapiol yield apiolic aldehyde and apiolic acid on oxidation, a better
yield being obtained if apipl be first isomerised to isoapiol. Four grams
of isoapiol are dissolved in 40 c.c. of acetic acid, and 5 grams of chromic
acid dissolved in 100 grams of acetic acid are added. After about two
hours, 1000 c.c. of water are added, the mixture neutralised with caustic
soda, and the liquid filtered. On standing in a cold placa, long needles
of apiolic aldehyde, C10H10O5, separates, which when recrystallised from
alcohol, melt at 102° and boil at 315°. To convert isoapiol into apiolic
acid, 30 gram^ of potassium permanganate are dissolved in 1600 c.c. of
water and mixed with 8 grams of isoapiol suspended in 800 c.c. of water
rendered alkaline and heated to boiling temperature. The mixture is
heated for an hour on the water-bath and then filtered and unaltered
isoapiol extracted with ether. The mixture is then acidified with sul-
phuric acid, the yellow precipitate formed is dissolved in boiling water
with the addition of animal charcoal, and the filtrate allowed to cool,
when apiolic acid, C ]() H 10 O (5 , melting at 175°, separates.
DlLLAPIOL.
Dillap ol, C12H]4O4, differs from apiol only by the orientation of its
side chains. It is found in East Indian, Japanese, and Spanish dill oils,
and in certain types of matico oils, etc. It has the following constitu-
tion :—
CO—CH,
H3COC[X JCH
C.CH, .CH:CH,
Its physical characters are as follows ;—
Boiling-point 285°
,, at 11 mm 162°
Refractive index at 25° . . 1-5278
By boiling with alcoholic potash for six to eight hours, the allyl group
is changed into the propenyl group, and iso-dillapiol results. This body
is a crystalline compound, melting at 44° and boiling at 296°.
If dillapiol dissolved in glacial acetic acid be treated with excess of
bromine, a precipitate is obtained, which, after several recrystallisations
from alcohol, forms fine needles, melting at 110°. This body is mono-
brom-dillapiol dibromide of the formula,
C6Br(CH2. CHBr . CH2Br)(OCH3)(O2CH2).
Iso-dillapiol, which has also been found naturally in oil of Piper
aciitifolium, yields the corresponding bromide, melting at 115°.
On oxidation, in the manner described under apiol, there are obtained
from both dillapiol and iso-dillapiol, dillapiolic aldehyde, melting at 75°,
and dillapiolic acid, melting at 151° to 152°.
CHAVIBETOL.
This phenolic constituent of betel oil, C10H12O2, is an allyl-guaiacol, of
the constitution—
COCH3
HC/^COH
HC ,CH
^ CH,. C H:CH 2
C .
It is an oil having the odour of betel oil, and whose characters are
as follows:—
„ at 12 mm 131° „ 133°
Eefractive index " 1*5413
Melting-point 4-8*5°
It yields a benzoyl compound, which crystallises in small plates

melting at 49° to 50°. It also yields an acetyl derivative, boiling at
275° to 277°.
PHLORACETOPHENONE-DIMETHYL-ETHER.
1 9 O 4 , is a constituent of the oil of Blumea balsamifera.
This ether, C1100H
It is a colourless crystalline compound melting at 82° to 83°. Its con-
stitution is as follows : —
CH
HC' ' C • CO • CH3

COCH3
It yields an oxime, melting at 108° to 110°, an acetyl derivative
melting at 106° to 107°, a methyl ether melting at 103°, and a yellow
crystalline monobromide melting at 187°.
/3-NAPHTHOL-METHYL-ETHER.
This substance is an artificial perfume having a neroli-like odour, and
was introduced into commerce under the name yara-yara, and is also
known as nerolin. It is a crystalline compound melting at 72° and
boiling at 274°. Its constitution is—
CH
HG \COCH,
HC ,CH
It can be prepared by digesting /2-naphthol-sodium with the calculated

quantity of methyl iodide in methyl alcohol solution; or by heating
1 part of /2-naphthol, 3 parts of methyl alcohol, and 1 part of hydrochloric
acid in an autoclave to 150°.
/3-NAPHTHOL-ETHYL-ETHER.
This body corresponds with the methyl-ether just described, the CH3
group being replaced by the C2H5 group. It is prepared in the same
manner, substituting ethyl compounds for the methyl compounds. It
was introduced into commerce under the name bromelia, and is, in
common with the methyl-ether, known as nerolin. It is a colourless
crystalline solid melting at 37° and boiling at 282°. Its specific gravity
at 50° is 1*051. The ethyl-ether has a finer odour than the methyl-ether,
and has a suggestion of pine-apple.
/2-NAPHTHOL-BUTYL-ETHER.
This substance is an aromatic compound, similar to the ethel-ether,

and is a useful fixative. It has been sold under the name Fragarol.
8, OXIDES AND LACTONES.

COUMABIN.
Coumarin, C9H6O.?, is, chemically, the S-lactone of coumarinic acid

(o-oxycinnamic anhydride), of the constitution—
CH
HC .CO
C . CH : CH . CO
It is a white crystalline solid, melting at 67° to 68° and distilling at 290°.
It is soluble in hot water, alcohol, ether, vaseline, and oils in general. It
is the active odorous ingredient of the Tonquin bean (Tonca or Tonco
bean), the seeds of at least two species of Dipteryx (N.O. Leguminosa),
in which it occurs up to 3 per cent. Coumarin possesses the character-
istic odour of the Tonca bean, in which it was discovered in 1825 by
Boullay.1 It also occurs naturally in abundance in the dried leaves of
Liatris odoratissima (deer's tongue, hound's tongue), an herbaceous plant
common in North Carolina, 1 Ib. of leaves yielding from 1-J- to 2£ drachms
of coumarin. It has also been found in the following plants, amongst
others :—
Angroecum fragrans. Herniaria glabra.
Myroxylon Pereirce. Ruta graveolens.
Cevatopetalum apetalum. Alyxia stellata.
Ataxia Horsfeldii. Asperula odorata.
Cinna arundinacea. Galium trifolium.
Hierochloa alpina. Liatris spicata.
,, australis. Prunus Mahaleb.
,, borealis. Meliotus officinalis.
Milium effusum. ,, hamatus
Adiantum pedatum. ,, albus.
,, peruvianum. „ leucanthus.
,, trapeziforme. ,, altissimus.
Drynaria Wildenovi. Ageratum mexicanum.
Phoenix dactylifera. Copaifera Salikounda.
Aceras Winthrophora. Trifolium Melilotus.
Nigritella angustifolia. Anthoxanthum odoratum.
Orchis fusca.
Coumarin was first produced synthetically by Perkin.2 He made it
by heating salicylic aldehyde, C6H4(OH)1(COH)2, acetic anhydride, and
sodium acetate. The whole solidifies to a crystalline mass, from which,
on treatment with water, an oil separates containing coumarin and aceto-
coumaric acid. This acid on heating is decomposed into acetic acid and
coumarin, so that the product of distillation is principally coumarin.
Perkin's synthesis proceeds according to the following equation : —
' COONa +
(CH3C°)20 -
' COONa - H °
I 2
Jour. de Pharm., xi. 480. C1tem. Soc. Journ., xxi. 53, 181.
The sodium salt of aceto-coumaric acid on hydrolysis decomposes,
yielding first an acid which loses water, forming coumarin, together with
acetic acid —
/OOC . CH3 pT
: CH . COOH
CO + H>0
CH:CH
l
Anschiitz treated aceto-salicylic chloride with sodium-malonic ester,
with the formation of ethyl acetate and /3-hydroxy-coumarin-alpha-car-
boxylic ethyl ester —
/C(OH) : C . COOC0H5
"
This compound is heated with caustic potash solution, yielding beta-

hydroxy-coumarin. From this body, coumarin is obtained by substituting
a halogen atom for the OH group, and then reducing the product in
alcoholic solution with zinc-dust.
A synthesis of coumarin has been effected by Meyer, Beer, and
Lasch.'2 Ortho-chlorbenzal chloride is heated with glacial acetic acid
and potassium acetate —
CHCL
/\cl + H2CH . COOH + 2CH3COOK =
CH : CH . COOH
2KC1 + /\ ™ + 2CH3coOH
yielding ortho-chlor-cinnamic acid. This is reduced to ortho-chlor-phenyl-

propionic acid—
CH 0 . CH 2 . COOH
/Nci
On heating this under pressure, with a solution of caustic soda, ortho-

hydi oxy-coumaric acid results—
CH 2 . CH 2 . COOH
'H
2
Ânnalen, 202 (1909). Monatshefte, 34 (1913), 1665.
VOL. II. 18
This acid forms needles melting at 81° C., and on boiling, yields hydro-
eoumarin—
CH2 . CH2
>.CO
which melts at 25° C., and boils at 272° C.

By heating this lactoneto 270° and 300°, and passing bromine vapour
slowly over it, coumarin is produced—
CH 2 . CH2 CH : CH
2Br - 2HBr . CO
Coumarin is sometimes adulterated with acetanilide, which should

always be looked for; the ease with which it yields aniline, on heating
with potash solution, renders it very easy of detection. Some samples,
otherwise pure, contain traces of unaltered salicylic aldehyde, which is
revealed by the odour.
Synthetic coumarin is largely used in the place of Tonca beans, and
forms an extremely useful substance for fixing other odours. Traces of
fixed oil are useful in coumarin mixtures, as the coumarin odour appears
to become more fixed in this way. Foin coupe, or new-mown hay, is a
favourite perfume in which coumarin is the cnief ingredient. The follow-
ing table of solubilities of coumarin in alcohol of various strengths and in
water has been compiled by Schimmel & Co.:—
100 Parts of Alcohol atO° C. at 16° to 17° C. at 29° to 30° C.
Of 90 volume per cent. 1 7'1 pa rts 13-7 pa rts 42-5 pa rts

„ 80 ! 6'0 12*3 38'3 ,
,i 70 4-4 9-1 26-0
„ 60 3-2 6-0 16-0
.» 50 1-7 3-4 8-9
„ 40 0-7 1-5 3-9
„ 30 0-3 0-6 1-7
,, 20 0-2 0-4 0-8
„ 10 0-15 0-25 0-5
100 parts of water 0-12 , 0-18 , > 0-27 , •
On heating with concentrated solution of potash, coumarin is con-

verted into o-coumaric acid, HO . C6H4 . CH : CH . COOH, melting at
207° to 208°.
ALANTOLACTONE.
Alantolactone, C15H20O2, also known as helenin, is a constituent of the
essential oil of Inula helenium. It is a crystalline compound, melting at
76° and boiling at 275° (or at 195° to 200° at 10 mm.). Its constitution
is not known but it contains the following grouping : —
p TT / \
14 20
\co
By warming with dilute alkalis it is converted into the corresponding
acid, alantolic acid, C14H20(OH)(COOH), melting at 94°.
Alantolactone forms a hydrochloride melting at 117°, a hydrobromide
melting at 106°, a dihydrochloride melting at 127° to 134°, and a dihydro-
bromide melting at 117°.
An isomeric compound, isoalantolactone, exists in the oil of Inula
helenium. It is a crystalline body melting at 115°, and yielding isoalantolic
acid with alkalis, melting at 237° to 239°.
SEDANOLIDE.
Sedanolide, C12H18O2, is the lactone of sedanolic acid. Both bodies
occur in the essential oil of celery.
Sedanolide is a crystalline compound, melting at 88° to 89°. The
relationships of the acid and its anhydride are shown by the following
formulae : —
CH CH
. CH(OH)C4H9 / ^ C . CH •C4H9
A
H,C, .CH . COOH H,C CH.CO
CH2 t>
Sedanolic a?id. ^ Sedanolide.
Sedanolide is therefore, probably, tetrahydrobutyl-phthalide.
SEDANONIC ANHYDRIDE.
The anhydride of sedanonic acid, C12H18O3, is not a lactone, but an
anhydride resulting from the elimination of a molecule of water from a
monobasic ketonic acid. Sedanonic anhydride occurs in oil of celery.
The acid, which melts at 113°, has the following constitution : —
CH
. CO . C4H9
C.COOH
!H
It is therefore ortf/z-o-valeryl-^'-tetrahydrobenzoic acid. The anhydride
is formed by the elimination of a molecule of water from the two side
chains.
BERGAPTENE.
Oil of bergamot contains about 5 per cent, of an odourless solid body
known as bergaptene. This body has the formula C12H8O4, and melts at
188°. It is the methyl ether of a phloroglucinol derivative, related to
coumarin. Its constitution is as follows : —
CO . CH3
X HC . . CH : CH
CH "
. CO
CH
By treatment with methyl iodide and alcoholic potash, it yields
methyl-b^rgaptenic acid and its methyl ether.
XANTHOTOXIN.
Xanthotoxin, C12H8O4, is isomeric with bergaptene, and is present in
the oil of Fagara xanthoxyloides. It is a solid compound, melting at
145° to 146°, and is a pyrogallol derivative, having the constitution—
C . OCH3
OC . O . CO
CH
.C C, H
CH
It yields nitroxanthotoxin, C12H7O4 . NO2, melting at 230°, and a di-
bromide, melting at 164°.
ClTBAPTENE.
Citraptene, CnH10O4, is the odourless solid constituent of the expressed

oil of lemon. After repeated recrystallisations from acetone and methyl
alcohol, it forms needles melting afc 146° to 147°. By treatment with
bromine in chloroform solution it yields a dibromide, C10H10Br2O4, melting
at 250° to 260°. It appears to be a dimethyl-oxycoumarin of the con-
stitution —
C . CHO
COCH,
C
CO.CH CH
ClNEOL OR EUCALYPTOL.
This body, C10H18O, has been described under several names, the
best known being that now usually adopted, viz. cineol; also cajuputol
(from its occurrence in oil of cajuput) and eucalyptol (from its occurrence
in oil of eucalyptus). It is found in nature in very large quantities in
the above-mentioned oils, as well as in many others, notably wormseed,
lavender (English), and spike-lavender oils. It results also by the
treatment of terpin hydrate with acids. Wallach and Brass, who first
characterised it as a definite compound, give the following method for its
preparation. A current of dry hydrochloric acid gas is passed into
rectified wormseed oil. The resulting crystalline magma of cineol hydro-
chloride is pressed at low temperature to remove as much as possible of
adhering liquid, and the crystals are treated with water and steam dis-
tilled. The crude cineol is again subjected to this treatment, when the
pure body is obtained. When pure, cineol has the following characters :—

Melting-point + 1°
Scammel proposed its separation by means of a definite crystalline

compound with phosphoric acid. This body has the composition
C10H18O . H3PO4. The use of phosphoric acid is the basis of the British
Pharmacopceial test for cineol in essential oils.
Cineol forms a number of crystalline derivatives, amongst which may
be mentioned the hydrobromide, C10H180 . HBr, melting at 56°, and
the compound with iodol, C10H18O . C4I4NH, which forms yellowish-green
crystals, melting at 112°. It also forms a crystalline compound with
resorcinol, which has been used as a basis for its quantitative determina-
tion. This compound consists of 2 molecules of cineol with 1 of resorcin,
and forms needle-shaped crystals, melting at 80°.
Belluci and Grassi1 have prepared compounds of cineol with the
following bodies, in the proportion of 1 molecule of each constituent:—
Phenol . (melting-po i + 8°)
o-Cresol + 50°)
w-Cresol '. ( - 5°)
p-Cresol ' ' + 1-5°)
Pyrocatechol + 39°)
Resorcinol - 15°)
Thymol + 4-5°)
add a compound of 2 molecules of cineol with 1 of hydroquinone, melt-

ing at 106*5.
Cocking has shown 2 that the compound with o-cresol melts, not at
50° but at 55'2°, and has prepared a method for the determination of
cineol based on the preparation of this compound (vide infra). This
method was criticised adversely in Volume I of this work. Further ex-
amination of the method has shown that this criticism is not altogether
justified, and should be deleted, a fuller review of the method given on
p. 282 taking its place.
According to all reliable observations, the oxygen atom in cineol does
not possess alcoholic, ketonic, aldehydic, or acid functions. Apparently
it is quite indifferent, which accounts for the isolated nature, chemically
speaking, of the compound. In commerce, this body finds considerable
employment under its name, eucalyptol.
1
2
Chem. ZentraL, 1 (1914), 884.
P. and E. O. R , 11 (1920), 281.
Cineol has the constitution—
CH3
C O
ELC/NCH,
H2C CH0
CH
C—
CH3 CH3
The quantitative determination of cineol has been fully dealt with in
Vol. I. of this work under Eucalyptus Oil, but as this body occurs in
various other oils, and its determination is a matter of considerable im-
portance, details of its estimation are also dealt with here.
The earlier attempts in this direction gave distinctly too low results.
The chief method adopted was a series of fractionations, retaining all
those fractions distilling between 173° and 190°, cooling them to — 15°,
filtering off the still liquid portion, retaining the crystals of cineol, refrac-
tionating the liquid portions and again freezing, subsequently weighing
the crystallised cineol. An average loss of about 10 per cent., in the
author's opinion, takes place in this process, assuming the oil to contain
50 to 60 per cent, of cineol. Scammers process, above-mentioned, has
been more successfully applied to the quantitative determination of cineol
and yields the most satisfactory results so far, although an error of several
per cent, is scarcely avoidable.
There is some diversity of opinion on this matter, some chemists
maintaining that a very close result is obtained, others that very large
errors occur.
To a known weight of oil from 1 to 1-J times its weight of phosphoric
acid, of specific gravity 1'75, should be added, drop by drop, the oil being
kept cold and continually stirred. The crystalline magma formed is
pressed between filter paper, after as much as possible has drained off;
and when the adherent terpenes and phosphoric acid have been re-
moved as far as possible, the crystals are decomposed by hot water in
a graduated tube. On cooling, the cineol is measured, and from its
specific gravity ('930) the weight is easily calculated. The separated
cineol should readily crystallise on cooling to - 3°, otherwise it must
be regarded as impure and the process repeated. Oils rich in cineol
yield a correspondingly high fraction distilling between 170° and 190°.
If the oil be first diluted with petroleum ether, before treatment
with phosphoric acid, the results are rather more concordant in the
hands of different analysts.
It has been assumed that the cineol and phosphoric acid enter into
combination in molecular proportions, forming a solid compound of
definite composition. Helbing and Passmorel have described a method
in which the compound is weighed, and assume that the percentage of
cineol in the phosphoric compound is 61*1 per cent, based on the for-
mula C10H18O. H3PO4.
1
Pharmacological Record, XXXV.
Baker and Smith in their Research on the Eucalypts1 state, however,
that correctly speaking no general formula can be given, as commercial
phosphoric acid has not always the same concentration. They found
that the mean cineol content in the perfectly dry powdery compound
was 59*4:7 per cent. The theoretical mean for the cineol from the
H3PO4 found was 59*56 per cent., thus being in very fair agreement.
The results showed that 59*5 was approximately the amount of cineol in
100 parts of cineol-phosphate, and not 61*1 per cent, as was previously
supposed.
Baker and Smith have devised an improved rapid method which they
find works well with oils containing 20 per cent, and over. Eucalyptus
oils which give a compound that cannot be satisfactorily pressed by the
British Pharmacopoeia method may be readily determined in this way
and the decomposition of the cineol phosphate by long pressing (parti-
cularly in hot countries) is prevented.
The richest cineol oils give the best results when they are first diluted
with the addition of one-third the volume of freshly distilled pinene (tur-
pentine or the non-cineol portion of the more pronounced phellandrene
oils. The method is to be applied in the following manner:—
If a preliminary test indicates from 60 to 80 per cent, of cineol, the
oil is diluted as directed above; if about 60 per cent, or below it can be
used directly.
Ten c.c. of the oil to be assayed are placed in a suitable vessel which
is stood in a bath of ice and salt, and 4 c.c. of phosphoric acid are slowly
added, a few drops at a time (3 c.c. if below 30 per cent.), incorporating
the acid and the oil between each addition by stirring. The cineol phos-
phate is then allowed to remain in the bath for fully five minutes in order
that the combination may be complete. A test tube containing 10 c.c.
of petroleum ether, boiling below 59° C., is placed in the bath and when
quite cold is added to the cake of cineol phosphate and well incorporated
with the mass, using a flat-ended rod for the purpose. The mixture is
at once transferred to a small Buchner funnel 5 cm. in diameter, upon
which is placed a closely fitting filter paper. The non-combined portion
is then rapidly sucked away by the aid of a filter pump. The thus dried
cake is then transferred to a piece of fine calico, the calico folded over
and the cake spread with a spatula to cover an area of about 6 cm. by
8 cm., finally folded into a pad which is placed between several layers of
absorbent paper and the whole strongly pressed for three minutes. The
cake is then broken up with a spatula on a glazed tile or on glass, trans-
ferred to a measuring flask with graduated neck, decomposed with warm
water, the cineol lifted into the neck of the flask, cooled, and when the
separation is complete, the volume is measured. If the original oil were
diluted, a correction is of course necessary. Baker and Smith have ob-
tained very concordant results with the same sample and now use this
method constantly.
Schimmel & Co. recommend the absorption of the cineol by a 40 to
50 per cent, solution of resorcin in water, and reading the unabsorbed
portion in the neck of a Hirschsohn flask.
Ten c.c. of the oil containing cineol are mixed in a cassia flask of
100 c.c. capacity with so much 50 per cent, resorcinol solution that the
flask is filled to about four-fifths. The mixture is shaken thoroughly
1
2nd Edition, 1920, p. 359.
for five minutes, and the oil portions which have not entered into reac-
tion are brought into the neck of the flask by adding resorcinol solution,
and their volume determined. By subtracting the volume from 10 the
cineol-content of the oil is obtained, which is then expressed in per
cent, by volume by multiplication with 10.
Messrs. Schimmel & Co. have since modified the method by recom-
mending the oil to be first fractionated and the portion boiling between
170° to 190° C. to be treated with the resorcin solution. In some cases
this gives results fairly concordant with the phosphoric acid method
usually adopted, as the following results will show:—
Cineol by Direct Cineol by Absorption Cineol by
Absorption with with Resorcin Phosphoric
Resorcin Solution. after Fractionation. Acid Process.
Cajuput Oil, normal 62 per cent. 54 per cent. 52 per cent.

,, ,, abnormal 53 „ 17 „ 14
Eucalyptus Oil I. . . 82 „ 68 65
C. T. Bennett l has, however, shown that this method is quite un-

reliable, only yielding accurate results in certain isolated cases.
In other cases, however, the results obtained are obviously too high.
An oil which yielded 95 per cent, distilling between 170° to 190° C.,
all of which was absorbed by resorcin solution, had the following char-
acters :—
EUCALYPTUS OIL II.
Optical rotation . Nil
Cineol by phosphoric acid method 78 per cenb.
, , , , resorcin method . . . . 95
Other samples gave results as under :—
Ciueol by Ciueol by Cineol by
Direct Absorption after Phosphoric
Absorption. Fractionation. Acid Process.
Eucalyptus Oil III. . . . 100 per cent. 89 per cent. 70 per cent.
,, ,, IV. . . . Crystallised 97 75 „
92 ,, 73
It is evident that this modified method is not absolutely accurate,

since other constituents besides cineol are undoubtedly included in the
portion boiling between 170° and 190° C. A further objection is the
separation of the solid crystalline double compound with 'oils rich in
cineol.
The method has been criticised by H. G. Harding,2 who states that
a pure white oil from Eucalyptus dives, which contained no cineol, showed
an absorption of 32 per cent, by the resorcinol test. Kectifying the oil
and applying the test to the portion distilling between 170° and 190° does
not entirely remove the difficulty, as the results are always slightly high,
2
. and E.O.R. (1912), 269. Analyst (1914), 475.
owing to retention of other constituents by the resorcinol solution. His
experiments show that the method is more reliable when.the percentage
of cineol does not exceed 40 to 50 per cent., oils containing a higher per-
centage requiring to be diluted. Ordinary turpentine oil must not be
used for dilution, as it is likely to produce serious errors. By employing
the fraction of turpentine distilling between 156° and 160° for dilution the
error is minimised, and the following method is recommended : 100 c.c.
of the oil to be tested is distilled, the portion distilling between 170° and
190° collected, and this is diluted to 100 c.c. with the turpentine fraction.
If a trial shows the percentage of cineol to be above 70 per cent., the
cineol fraction is further diluted with the turpentine so that the percentage
is not over 50. The temperature is noted, and 6 to 10 c.c. is shaken with
warm 55 per cent, resorcinol solution. After five minutes' shaking more
solution is added so as to bring the oil into the graduated neck. It is
then cooled and the volume read.
A method for the determination of cineol has recently been proposed
by Dodge.1
The process is based on the fact that the terpenes of the essential oils
to be examined are readily oxidised at 0° C. by a 5 to 6 per cent, solution
of potassium permanganate, whilst the eucalyptol remains unattacked.
Ten c.c. of essential oil are gradually added to 400 or to 100 c.c. of per-
manganate solution, according to whether the essential oil is more or less
rich in terpenes. When the reaction is finished, the sohition is allowed
to stand in the cold for twelve to eighteen hours, with occasional agitation ;.
sulphurous acid or a mixture of sodium sulphite and hydrochloric acid is
added and the oily portion of the residue is brought up into the neck of
the flask, from which it is removed by means of a slender pipette. This
oil is washed with a little alkali, then transferred to a graduated tube
where its volume is determined which indicates the percentage of euca-
lyptol.
This method cannot be relied on, as the action of potassium per-
manganate is such as to react with some and not with other bodies
present in various types of eucalyptus oil.
The whole question of cineol determination in eucalyptus oil has
recently been carefully studied by Turner and Holmes,2 who consider
that all methods so far published are either inaccurate or at best only
approximate. They suggest the following process :—
The determination of cineol in cineol-bearing oils by means of arsenic
acid is carried out as follows :—
Deliver from a pipette 10 c.c. of the oil into a glass dish (preferably a
round-bottom one) of 50 c.c. capacity, which is imbedded in finely cracked
ice. Add 10 c.c. of concentrated arsenic acid (containing about 85 per
cent, arsenic acid), and stir until precipitation is complete. When the
mixture ceases to congeal further, allow to stand ten minutes in the ice.
At this point if the mixture forms a hard mass, indicating an oil rich in
cineol, 5 c.c. of purified petroleum ether should be added, and the mass
mixed well. Transfer immediately to a hardened filter paper by means
of a pliable horn spatula, spread evenly over the surface of the paper, and
lay a second hardened filter paper over the top. Outside of the hardened
filters place several thicknesses of absorbent or filter paper, and transfer
the whole to an ordinary letter-press, bringing to bear all the pressure
1 2
Jour. Ind. and Eng. Cliem., 4, 592. P. and E.O.R. (1915), 21.
possible for about one minute. Change the outside absorbent papers and
press again, repeating the operation, if necessary, until the cineol arsenate
is apparently dry and separates readily when touched with a spatula.
The pressing is not complete when a hard mass remains which is broken
up with difficulty. The method usually requires two changes of filter
paper, pressing each time for about two minutes. If left too long in the
press the compound may decompose. Now transfer completely the com-
pound by means of the horn spatula to a glass funnel inserted into a 100
c.c. cassia flask with neck measuring 10 c.c., graduated in ^ c.c. Wash
the precipitate into the flask with a stream of hot water from a wash
bottle, assisting the disintegration with a glass rod. Place the flask in
boiling water and rotate until the compound is thoroughly broken up ;
add enough water to cause the cineol to rise into the neck of the flask,
cool to room temperature, and read off the volume; on multiplying the
latter by 10 the percentage of cineol in the oil is obtained.
In judging whether or not petroleum ether should be added, the fol-
lowing rule should be observed: Add enough petroleum ether to soften
the cineol arsenate, so as to obtain a plastic mass; the quantity neces-
sary never exceeds 5 c.c., and decreases with oils containing less than
80 per cent, of cineol. The object of adding petroleum ether is merely
to soften the hard mass and to aid in the separation of non-cineol con-
stituents of the oil; a large excess of petroleum ether will decompose
the compound.
The above method is applicable directly to all oils containing above
50 per cent, of cineol; in oils containing lower proportions of cineol
the precipitate is not solid enough to permit convenient handling; and
if the cineol-content drops below 25 per cent, the separation of cineol
arsenate is not quantitative. It was found that the addition of an equal
volume of eucalyptol to such oils (i.e. mixing 5 c.c. of the oil with 5 c.c.
of eucalyptol) successfully overcomes this difficulty; it then only be-
comes necessary.to subtract from the volume of cineol, as observed in
the neck of the flask, 5 c.c., and to multiply the difference by 10, in order
to obtain the percentage of cineol in the oil.
A new method, based on the combination of cineol with ortho-cresol
has recently been described by T. Tusting Cocking.1 The method is a
physical one and consists in determining the freezing-point of a mixture
of eucalyptus oil and ortho-cresol in proportions corresponding to mole-
cular weights of cineol and ortho-cresol. The apparatus required con-
sists of: (a) A stout-walled test-tube about 15 mm. in diameter and 80
mm. in length, fitted with a wire loop for suspending it from the stirrup
of a balance; (b) a small wide-mouthed bottle fitted with a cork bored
to take the test-tube; (c) a thermometer graduated in fifths of a degree ;
and (d) a couple of pipettes to introduce the liquids into the tube.
Ihe determination is carried out as follows:—
The tube is suspended from a balance and into it is accurately
weighed 3 grams of the oil and 2'1 grams of melted ortho-cresol.
It is then removed from the balance, inserted through the bored cork
into the wide-mouthed bottle, stirred with the thermometer and the
freezing-point noted. The tube is then gently warmed until the contents
are completely melted, stirred vigorously with an up-and-down motion
until solidification begins and the freezing-point again noted. This is
1
P. and E.O.R. (1920), p. 28.1.
repeated until concordant figures are obtained. It is found that in
nearly all cases \îth the mixtures of high cineol content the first figure
noted is two to three degrees lower than the subsequent ones. This is
due to the rapid crystallisation which takes place before the two liquids
are properly mixed. In order to obtain accurate results with weaker
cineol mixtures it is necessary to introduce a minute crystal of the double
compound (to which the name " cresineol" has been given by the
author) to promote crystallisation, as the solubility of the compound in
the terpene and excess cresol is so great that only a small quantity of
cresineol separates out.
Pure ortho-cresol melting at 30° should be employed, and the results
obtained with mixtures of known cineol content were as follows :—
Percentage of Cineol Freezing-points. Freezing-points.
in Mixture. Terpene Mixture. Sesquiterpene Mixture.
100 55-2° C. 55-2° C. !

95 534° C. 53-6° C. i
90 51-2° C. 51-7° C.
85 48-5° C. 49-7° C.
j 80 45-8° C. 47-7° C. !
75 43-2Q C. 45-7° C. !
70 40-6° C. 43-8° C. ;
65 37-4° C. 41 '2° C. '
60 34-2° C. 37-4° C.
55 29-0° C. 33*6° C.
: 50 25-4° C. 29-8° C.
45 22-2° C. 26-2° C.
The greatest difference recorded is equivalent to 6 per cent, of cineol,

and, by taking the mean, the maximum error is reduced to + 3 per
cent.
The effects on the freezing-point of other essential oil constituents
were compared by mixing ortho-cresol with mixtures of cineol and
camphor, geraniol, geranyl acetate, terpineol and terpinyl acetate. The
results showed that camphor has the same effect as sesquiterpenes,
geraniol gives a result 2*3 per cent, lower, terpineol 1 per cent, higher
and the two esters 3*1 to 3*3 per cent, higher than sesquiterpenes.
As compared with the B.P. phosphoric acid process the results were
from 4*4 per cent, higher in the case of 80 per cent, oils to 10*5 per cent,
higher in the case of cajuput oil indicating 50 per cent, by the B.P.
process.
This method has been examined carefully and it appears to be more
accurate than the phosphoric acid method as set on in the British
Pharmacopoeia and likely to give practically identical results in different
hands and under different atmospheric conditions.1
It should be emphasised, however, that, as the cresol method gives
higher results than the B.P. method, a minimum of 60 or even 65 per
cent, cineol should be required if the new method is made official in the
British Pharmacopoeia.
The value of Cooking's method was not fully appreciated when
volume I. of this work was published. It appears, on investigation, to
have much to recommend it.
1
See P. and E.O.R., 1921, pp. 44-46.
DlCITRONELL-OxiDE.
1
Spornitz has isolated from Java citronella oil a compound of the
formula C20H34O, which is an oxide having the following-characters :—
Boiling-point at 12 mm 182 to 183°
Optical rotation —4°
CARLINA OXIDE.
The essential oil of Carlina acaulis contains an oxide, C13H10O, which
*
Specific gravity at —o 1'066
On oxidation with potassium permanganate it yields benzoic acid, and

on reduction with sodium and alcohol, it is converted into the tetrahydro-
der vative C13H14O. The constitution of this oxide is probably—2
C6H5. CH : C : CH—Cl|
It is possible, however, that the chain joining the benzene and furfurol
rings may be differently arranged.
COSTUS LACTONE.
Semmler and Feldstein have isolated a lactone from costus root oil,
which they named costus lactone. It is an oil of the formula C15H2002,
Dihydro-costus lactone, C15H22O2, is also present in the oil.
ANGELICA LACTONE.
E. Bocker and A. Hahn have recently isolated a crystalline lactone of
the formula C15H16O3 in the last runnings of angelica root oil. From 200
grains they obtained 10 grams of a lactone which, when recrystallised
from ethyl ether and light petroleum, melted at 83°. It boils without
decomposition at 250°. The lactone is an unsaturated body; when
brominated in a glacial acetic acid solution it yields a dibromide, which
when recrystallised from glacial acetic acid, melts with decomposition at
143° to 145°.
] 3
Berichte, 47, 2478. Seminler, Berichte (1909), 2355.
ASCABIDOL.
Ascaridol is the principal constituent of the oil of Chsnopodium

ambrosoides, var. anthelminticum.
It is an oxide having the following characters : —
Optical rotation , - 4° 14'
When ascaridol is treated with a solution of ferrous sulphate, care

being taken to avoid any rise of temperature, it fixes the elements of water
with the formation of a glycol, C10H18O3, melting at 62 -5° to 64° C. and
yielding a benzoate melting at 136° to 137° C. The glycol possesses the
Specific gravity .......... 1*0981
Optical rotation .......... +0°
Refractive index .......... 1-4796
Molecular refraction ..... . . . 48 '63
It yields a dibenzoate (melting-point, 116*5° to 117*5° C.) when it is heated

for two hours at 150° C. with benzoic anhydride.
On oxidation the glycol yields a dibasic acid, C10H16O5, called
ascaridolic acid (melting-point, 116*5° to 117° C.), and another solid acid,
melting at 186° to 187° C., to which Nelson attributes the formula
Nelson regards ascaridol as a peroxide possessing the constitution I

(see below).
O. Wallach x has also examined the constitution of ascaridol. He:
considers it to be an oxide having the formula II —
CH
n
i
vy I
O
HC< CH
CH
CH
H3C CH3 H
I. II.
Nelson. Wallach.
1
Ann. Chem., 392, 49.
9, NITROGEN COMPOUNDS.
NlTEOBBNZENE.
Nitrobenzene, C6H5NO2, also known as oil of mirbane, is an artificially

prepared benzene derivative, having a coarse, but powerful odour re-
sembling that of oil of almonds. Its coarse odour renders it quite un-
suitable for fine perfumery, but it finds considerable employment in the
manufacture of cheap soaps, polishes, and other articles where more or
less rancid fats are used, as it covers the bad odour of the fat and gives
the product a coarse almond perfume.
Nitrobenzene is an oily liquid, resulting from the direct nitration of
benzene, having the following constitution : —
CH
HCx/CH
C . NO2
Solidifying-point + 5°
Boiling-point 209°
Specific gravity. 1*2200 at melting-point
at 15° 1-2060
On reduction with iron and acetic acid, nitrobenzene yields aniline.
ARTIFICIAL MUSK.
There are a number of nitro-compounds known under the name of
artificial musk, all of which may conveniently be grouped together here.
The natural odorous constituents of musk appear to be, in the main,
ketonic compounds free from nitrogen, so that the term artificial musk
must be understood to mean artificially prepared bodies, having musk-
like odours, but not having any direct chemical relationship with natural
musk perfume.
For many years attempts have been made to artificially imitate the
odour of musk. To a certain extent successful experiments were made
by Margraff and Eisner.1 Eough pieces of amber, ground to powder and
mixed with sand, are distilled in an iron retort; the oil which distils over
is separated from the foetid liquor and succinic acid which accompanies
it, and after being rectified at a gentle heat with about six times its volume
of\water, is gradually added to and digested with 3£ parts by weight of
fuming nitric acid, artificial cold being employed to prevent any portion
of the oil carbonising. A resinous matter of a yellowish colour forms,
which, after being dried, is the product which is required. It is said to
be also formed by digesting for ten days an ounce of foetid animal oil,
obtained by distillation, and half an ounce of nitric acid, then adding a
pint of rectified spirit, and digesting for one month. Another artificial
musk has been patented in England 2 by Schnaufer & Hupfeld, of Frank-
1 2
Jour, filr Praktische Chemie, 1842. No. 18,521, 18 December, 1888.
furt. The specification of this patent states that " 3 parts of metaxylol,
2 parts of isobutyl alcohol, and 9 parts of chloride of zinc are heated in a
digestor to from 220° to 240°, until the pressure, which at the commence-
ment is from 25 to 29 atmospheres, sinks to below 6 atmospheres. The
resulting hydrocarbon, corresponding to the formula C12H18, is collected,
-and the fraction which distils over at from 190° to 230° is nitrated with
HNO3, or with HNO ? and H2SO4, whilst being cooled. The product of
the reaction is poured into water, whereupon a reddish-brown oil separates,
which is washed several times with alkaline water. The formula of this
oil is C12H17N02, and in a concentrated condition it possesses a sweet
smell, whilst in a dilute solution it gives off a penetrating and enduring
musk-like odour."
The complete specification states that " aromatic hydrocarbons con-
taining the isopropyl, isobutyl, or isoamyl group, on treatment with
fuming nitric acid or a mixture of strong nitric acid (40° to 44° B.) and
sulphuric acid (66° B.), produce derivatives which, in very dilute alcoholic
solution, furnish a liquid possessing an odour resembling tincture of musk
in the highest degree ". Only one example of the process is given in the
provisional specification, but of course the u process may be carried out
with the other well-known hornologues. The hydrocarbons may be
produced in the ordinary way, but we produce them by the following
operation : Toluene or xylol is heated in a digester with isopropyl or
isobutyl, or isoamyl alcohol in molecular quantities, with the addition
of from four to five times the quantity of chloride of zinc, to the boiling-
point of the hydrocarbon, or to about 40° or 50° above the boiling-point
of alcohol, until the pressure, which at the commencement was equal to
about 26 atmospheres, sinks to a little above 2 or 3 atmospheres. The
product of the reaction is subjected to fractional distillation.
" By the above process the following hydrocarbons are obtained :—
1. From toluene :—
Methylisopropyl-benzene.
Methylisobutyl-benzene.
Methylisoamyl-benzene.
2. From xylol:—
Dimethylisopropyl-benzene.
Dimethylisobutyl-benzene.
Dimethylisoamyl-benzene.
11
To produce the ' musk-substitute ' :—
" We add to the -above-mentioned hydrocarbons, which during the
operation should be kept thoroughly cool, a little more than the molecular
quantity of fuming nitric acid or nitro-sulphuric acid. The acid should
be gradually run in and the whole then allowed to stand undisturbed for
from one to two hours, the resulting mass being then poured into water
in order to get rid of the excess of acid. The well-washed substances
thus obtained are then subjected to distillation by means of steam,
whereupon simultaneously formed bodies, which smell like nitro-benzol
and overpower the musk odour, readily distil over, whilst the pure sub-
stances remain behind."
The artificial musk which was the first to achieve marked success
was that manufactured under the patent of Albert Baur (English patent
No. 4963 of 1889). The provisional and complete specifications of this
patent are as follows :—
Provisional Specification.—I, Albert Baur of Gispersleben, in the Empire of
Germany, Doctor, do hereby declare the nature of this invention to be as follows :—
The object of this invention is to produce a compound or material, or series of
compounds or materials, having the properties of musk.
To this end I purpose to make a nitrated hydrocarbon of the CnH16 group, and
proceed as follows :—
Toluene is mixed with a haloid combination of butane and boiled with addition
of chloride or bromide of aluminium. Water is added to the product and it is then
distilled with steam, and that portion which distils over at a temperature between
170° and 200° C. is taken and treated with fuming nitric acid and fuming sulphuric
acid. The resulting product is washed with water and crystallised from alcohol.
The product may be dissolved in alcohol, and on addition of a small quantity of
ammonia or sal-ammoniac will exhibit all the essential properties of a tincture of
musk.
Complete Spscification.—I, Albert Baur of Gjspersleben, in the Empire of
Germany, Doctor, do hereby declare the nature of my invention and in what manner
the same is to be performed to be particularly described and ascertained in and by
the following statement:—
The object of this invention is to produce a compound or material, or series of
compounds or materials, having the properties of musk.
To this end I make a nitrated hydrocarbon of the C n H ]fi group, and proceed as-
follows:—
Toluene is mixed with a haloid combination ol butane and boiled with addition
of chloride or bromide of aluminium. Water is added to the product and it is then*
distilled with steam, and that portion which distils over at a temperature between
170° and 200° C. is taken and treated with fuming nitric acid and fuming sulphuric-
acid. The resulting product is washed with water and crystallised from alcohol.
The product may be dissolved in alcohol, and on addition of a small quantity of
ammonia or sal-ammoniac will exhibit all the essential properties of a tincture of
musk.
For carrying the invention into practice, 5 parts of toluene are mixed with 1
part of butyl bromide, or butyl chloride or butyl iodide, and to these may be added
gradually whilst boiling ^ part of aluminium chloride or aluminium bromide; this-
results in the development of hydrobromic acid, or hydrochloric acid or hydriodic
acid respectively, and a product of reaction is obtained from which by the action of
steam the hydrocarbon CnH]H and unchanged toluene are distilled. By the admission
of steam the hydrocarbon is carried along and may be obtained in a condenser
as a colourless oil floating on the water. The oil removed and dried by means
of chloride of calcium is fractionated, and in this manner the necessary hydro-
carbon for the production of artificial musk is obtained, 100 parts of the former
giving a like quantity of musk preparation. Three parts of fuming nitric acid of 1*52'
specific weight and 6 parts of fuming sulphuric acid are mixed together, and to this
mixture is carefully added whilst cooling 1 part of the hydrocarbon aforesaid. Each
drop causes a violent reaction. As soon as all the hydrocarbon is added, the wholfr
mixture is heated up to a temperature of about 100° C. After cooling, the nitro
product is precipitated by pouring into cold water of about 5 to 6 times the volume,,
and is separated from superfluous acid by washing with cold water. The nitro pro-
duct separates first as a heavy viscid oil, which after some time hardens into a firm
crystalline substance.
The raw nitro product is then purified by recrystallisation from alcohol of 90 per
cent, strength. The purified product crystallises out in yellowish-white needles,,
possessing a strong smell of musk.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I claim is—
The process for producing artificial musk substantially as described.
The original scientific account of the preparation of this body stated *
that weta-isobutyl toluene was heated on a water-bath for twenty-four
hours, with five times its weight of a mixture of sulphuric and nitric acids.
The product was subjected to a repetition of the same treatment, so as to-
convert it into trinitro-butyl toluene, which crystallises from alcohol in
white needles melting at 96° to 97°. It is insoluble in water, but soluble
in organic solvents. Even in very dilute solutions this compound has a.
1
Comptes rendus, cxi. 238.
strong odour of musk, and for many purposes can replace the natural
product. The homologues of isobutyl toluene behave similarly, and
trinitro-isobutyl metaxylene has an exactly similar odour. In a later
communication 1 Baur stated that his previous view was incorrect, and
that the "artificial musk" was the trinitro-derivative of tertiary butyl
xylene, and not of isobutyl xylene, owing to the occurrence of an intra-
molecular change during the reaction. Tertiary butyl xylene is easily
prepared by the interaction of tertiary butyl chloride and xylene in the
presence of aluminium chloride as follows :—
C4H9C1 + C6H4(CH3)2 = C4H9. C,.H3. (CH3),, + HC1.
The mono- and dinitro products have no musk odour, and therefore
the nitration of the hydrocarbon should be carried as far as possible.
The constitution of this artificial musk, or " xylene musk " as it is often
called, is probably—
C . CH3
;j. NO.,
L>±i3. LA ,u. m^
C1TJ ('11 C^ C* TT
c. NO,
This is the most common form of artificial musk of commerce. It
melts, when pure, at 110° to 113°.
Still later 2 Baur has shown that if an acetyl group is introduced into
the butyl toluene molecule, and the methyl ketone thus formed is nitrated,
artificial musk (ketone musk) is produced. One part of butyl toluene,
10 parts of carbon disulphide, and 6 parts of aluminium chloride are
cooled in a flask and 6 parts of acetyl chloride are run in quickly. After
distillation on a water-bath, the residue is poured on to ice and treated
in the usual manner. The acetyl derivative is obtained as an oil with a
pleasant aromatic odour, boiling at 255° to 258°, of the formula—
CH 3 .CO.C,H.
6 '» «
By nitrating this ketone a dinitro derivative—

(NO,),,
CH 3 . CO . C...H—CH;j
is obtained in needles melting at 131°, and having a strong musk odour.

In this compound one of the nitro groups of the original artificial musk,
trinitro-butyl toluene, has been replaced by the acetyl group. Which
group has been so replaced is uncertain. A quite similar body is obtained
from butyl xylene, the resulting ketone—
C4Ha
CH 3 . CO . C tf H 2 —CH 3
CH:j
1
Iterichte, xxiv. 2882. -Ibid., xxxi. 1344.
ii. 19
melting at 48°, and yielding a dinitro derivative —
(N02)2
CH3 . CO . C6— C4H!(
melting at 136°, and having a strong musk odour. These bodies are
known as "ketone musk". Instead of using acetyl chloride, either
butyryl chloride or valeryl chloride may be used, and higher homologues
produced. Butyl-xylyl-propyl ketone —
C4H9
C3HV . CO . C0H,— CH3
CH3
melts -at 50° and boils at 290°. It forms a dinitro derivative, melting at
128°, with a powerful musk odour. The corresponding butyl-xylyl- butyl
ketone is an oil boiling at 185° to 190° at 14 mm., and its dinitro deriva-
tive melts at 151°, and has also a powerful musk odour.
There are also, although not much met with, an aldehyde and a
cyanide musk. The former is dinitro-tertiary - butyl-xylyl-aldehyde,
C6(CH3)2C(CH3)3(N02)2CHO, melting at 112°, and the latter is dinitro-
tertiary- butyl-xylyl-cyanide, C6(CH3)2CN . C(CH3)3(NO3)2, melting at 110°.
Musk ambrette, which is usually regarded as the finest of all the
artificial musks, is a nitro-compound of the methyl ether of butyl-meta-
cresol, usually described as dinitro-butyl-meta-cresol methyl ether. It
should melt at 85°.
Some of the artificial musks of commerce are mixtures of two or more
of the bodies above described, a fact which is easily demonstrated by
fractionally crystallising the specimen, when the fractions will show
altered melting-points. The principal adulterant of artificial musk is
acetanilide. This can, of course, be easily detected by the phenyl-iso-
cyanide reaction or by dissolving it out with hot water.
DAMASCENINE.
Damascenine, C10HI3NO3, is a nitrogenous compound of an alkaloidal
nature, which is present in the oil of Nigella damascena to the extent of
about 9 per cent. It can be extracted from the oil by shaking it with
dilute hydrochloric acid, rendering the aqueous liquid alkaline and ex-
tracting the alkaline liquid with petroleum ether.
Damascenine has the following characters : —
Melting-point ........ 26°
Boiling-point ...... ' . 270° at 750 mm.
„ „ ........ 157° „ 10. „
It yields salts with the usual alkaloidal reagents, such as platinum,
gold, and mercuric chlorides. Its constitution is —
CO . CH3
HC/\CNHCH,
HC C . CO. OCH,
HC
It is, therefore, the methyl ester of 2-methylamino-3-methoxybenzoic
acid.
It has been prepared synthetically by E wins l in the following manner :
Meta-oxybenzoic acid is converted with the aid of dimethyl sulphate
into w-methoxybenzoic acid, which is then nitrated, and from the nitra-
tion products 2-nitro-3-methoxybenzoic acid is separated. This is re-
duced to 2-amino-3-methoxybenzoic acid which on heating with methyl io-
dide, yields 2-methylamino-3-methoxybenzoic acid. On warming this with
freshly precipitated silver chloride it yields damascenine hydrochloride.
HYDROCYANIC ACID.
Hydrocyanic acid, HCN, also known as prussic acid, or formo-nitrile,
is the product of decomposition of numerous glucosides found in a very
large number of plants, usually together with some other volatile com-
pound, so that essential oils containing hydrocyanic acid do not, for
practical purposes, exist in the first instance as such in the plant, but are
only developed on the decomposition of the glucoside.
Hydrocyanic acid is one of the most powerful poisons known. It is a
colourless liquid, boiling at 26*5°, of specific gravity O700.
It can be detected and estimated in essential oils by the following
method:—
Hydrocyanic acid may be approximately estimated by dissolving 1
gram of oil in 5 c.c. of alcohol, and adding 50 c.c. of water. Then add
ammonio-silver nitrate solution and shake well. Acidify slightly with
nitric acid, and collect, wash, and dry the silver cyanide precipitated.
Ignite and weigh the silver, 4 parts of which correspond to practically
1 of hydrocyanic acid.
For an exhaustive examination of the various processes proposed for
the determination of hydrocyanic acid, the reader is referred to a series
of papers by Eunne in the Apotheker Zeitung.2
ALLYL CYANIDE.
Allyl cyanide, CH 3 . CH : CH . CN, occurs in some of the oils of the
mustard type. It is a liquid of specific gravity 0*8365 boiling at 120° to
123°, and yields, on boiling with alcoholic potash solution, crotonic acid,
melting at 72°.
BENZA'L CYANIDE.
Benzyl cyanide, C(.H5. CH,CN, or phenyl-aceto-nitrile, is a constituent
of cress oil, and probably of neroli oil. It is a strong smelling liquid
boiling at 231'5°, and having a specific gravity 1-0146 at 18°. On boiling
with alcoholic potash it yields phenyl-acetic acid, which can be identified
by its melting-point, 77°, and by the analysis of its silver salt.
PHENYL-PBOPIONITRILE.
Phenyl-propionitrile, C6H5. CH 2 . CH 2 . CN, is present in nasturtium
oil. It is a powerfully smelling oil, boiling at 261°. On hydrolysis by
alcoholic potash it yields phenyl-propionic acid, melting at 47°.
*Jour. Chem. Soc., 101 (1912), 544.
-Apotheker Zeitung, 24 (1900), 288, 297, 306, 314, 325, 333, 344, 356.
INDOL.
Indol, C8H7N, is the mother substance of the indigo group of com-
pounds. It exists in various essential oils including neroli oil and oil
of jasmin flowers. It is a crystalline compound, melting at 52° and
boiling at 253° to 254°. Its odour is powerful and disagreeable, being
distinctly faecal in character. Its constitution is as follows : —
CH
Indol is prepared artificially by numerous methods, most of which

have been patented.
Indol can be isolated from, and determined in, essential oils in the
following manner: The oil is mixed with 10 per cent, of picric acid and
heated to 60°. Excess of petroleum ether is then added. A picric acid
compound of indol separates in long red crystals, which are washed with
petroleum ether and decomposed by caustic alkali, and the free indol ex-
tracted by ether, and the residue left on evaporation of the ether steam-
distilled, when pure indol passes over.
Indol, in alcoholic solutions, turns a pine shaving, moistened with
Tiydrochloric acid, a cherry-red colour. When shaken with a solution of
oxalic acid, indol gives a red coloration.
SKATOL.
Skatol, C9H9N, is /2-methyl-indol, of the constitution—
CH
C.CH,
HC C CH
CH NH
It is found in civet and in the wood of Celtis reticulosa. It forms crystals
melting at 95° and boiling at 265° to 266°. It yields a hydrochloride,
2(C 9 H 9 N). HCl, melting at 167° to 168°, and a picric acid compound
melting at 172° to 173°. Skatol yields a blue colour with a solution of
dimethyl-aminobenzaldehyde.
Skatol is a foul-smelling compound, but when used in very minute
amount is useful in the manufacture of flower blossom perfumes.
10. S U L P H U R COMPOUNDS.
DIMETHYL SULPHIDE.
Dimethyl sulphide, (CH3).2S, is a foul-smelling liquid, found in minute
quantity in the essential oils of peppermint and geranium. It boils at 37°.
VINYL SULPHIDE.
Vinyl sulphide, CH2 = CH2S, has been identified in the oil of Allium
ursinum. It is an evil-smelling liquid of specific gravity O912. It boils
at 101°.
DlALLYL DlSULPHIDE.
Diallyl disulphide, (C3H5)S.S(C3H6), is a light yellow oil of garlic odour,

found to the extent of about 60 per cent, in oil of garlic. It is a liquid of
specific gravity 1*023, and boils at 80° to 81° at 16 mm. pressure.
ALLYL-PROPYL DISULPHIDE.
Allyl-propyl disulphide, (C3H6)S . S. (C3H7), exists to the extent of
about 5 per cent, in garlic oil. It is a bright yellow oil of foul odour,
having a specific gravity 1*023 and boiling at 66° to 69° at 16 mm.
pressure.
DIALLYL TBISULPHIDE.
Diallyl-trisulphide, (C3H5)S . S . S . (C3H5), is probably the compound
of the formula C6H10S3 isolated from garlic oil by Semmler.1 It boils at
112° to 122° at 16 mm., and has a specific gravity 1*0845.
BUTYL ISOTHIOCYANATE.
Secondary butyl isothiocyanate, CH 3 . CH2 . CH(CH3) . N : C : S, has
been isolated from the oils of Cardamine amara and Cochlearia. It is a
liquid with a powerful, irritating sulphur odour, having a specific gravity
0'9415 and boiling at 159° to 160°. Warmed with alcoholic solution of
ammonia, it yields a thiourea, melting at 135° to 136°.
The artificial cochlearia oil of commerce is not identical with secondary
butyl isothiocyanate, but consists of isobutyl isothiocyanate. It is a liquid
boiling at 162° and yields a thiourea, melting at 93*5°.
ALLYL ISOTHIOCYANATE.
Allyl isothiocyanate, CH 2 : CH . CH2N : C : S, also known as " artificial
mustard oil," is the principal constituent of natural oil of mustard. This
body results from the hydrolysis of the glucoside sinigrin under the in-
fluence of the ferment myrosin, according to the equation—
C10H16NS2KO9 + H20 =.SCNC3H5 + C6H12O6 + KHSO4,
Sinigrin. " Mustard oil." Glucose.
It can be prepared artificially by the action of allyl iodide on an
alcoholic solution of thiocyanate of potassium, the latter body being
isomerised to the isothiocyanate under the influence of heat.
Allyl isothiocyanate is a colourless liquid, gradully becoming yellow
on keeping, and having an intensely irritating odour of mustard. Its
characters are as follows :—
Refractive index 1'52S5
Boiling-point 152°
„ „ 30° to 31° at 5 mm.
1
Arch. Pliarm., CCXXX. 434.
When treated with alcoholic solution of ammonia, it yields thio-
sinamine (allyl thiourea), of the formula C3H5 . NH . OS . NH2. This
body melts at 74°. The formation of this body forms the basis for a
method of its determination, which, with other methods, will be found
fully described under " Oil of Mustard" (Vol. I, p. 474).
CROTONYL" ISOTHIOCYANATE.
Crotonyl isothiocyanate, C 4 H 7 . N : C: S, has been found in Indian
rape-seed oil. It is an oil of odour somewhat similar to that of the cor-
responding allyl compound, and having the following characters :—
Boiling-point . . . . 175° t o 176°
Optical rotation . . . . + 0° 3' (probably due to impurities)
Refractive index . . . . 1'52398
BENZYL ISOTHIOCYANATE.
Benzyl isothiocyanate, C6H5. CH 2 . N : C : S, has been found in
Tropaolum oil, probably resulting from the decomposition of the
glucoside, glucotropseolin, C14H18KNS2O9, It has the characteristic
odour of the plant, and yields a thiourea melting at 162°.
PHENYL-ETHYL ISOTHIOCYANATE.
Phenyl-ethyl isothiocyanate, C6H5(C2H4)N : C: S, has been found in
the oils of reseda root, nasturtium, and some varieties of Brassica. It is
an oil of powerful odour, yielding a thiourea, melting at 137°. The latter
body, when treated with silver nitrate and baryta water, yields phenyl-
ethyl-urea, melting at 111° to 112°.
OXYBENZYL ISOTHIOCYANATE.
Para-oxybenzyl isothiocyanate, C^H4 . OH . CH2NCS, is a liquid of

intense odour, occurring in the essential oil of white mustard. It is also
known as acrimyl thiocarbimide. It is produced by the hydrolysis of the
glucoside sinalbin, C30H42N2S2O15. It can also be obtained artificially by
the action of carbon bisulphide on /?-oxybenzylamine, and treating the
resulting compound with mercurous chloride.
11. ACIDS.
FORMIC ACID.
Formic acid, H . COOH, is found in traces in a number of essential
oils. It is a colourless corrosive liquid or crystalline solid, having the
Melting-point 8°
Boiling-point . '. 101°
It can be prepared artificially in various ways ; for example, by dis-
tilling oxalic acid with glycerine, when at about 130° formic acid comes
over according to the equation—
C2H2O4 = HCOOH + CO2.
To prepare it in a completely anhydrous condition the 90 per cent,
acid may be dehydrated by means of phosphorus pentoxide.
ACETIC ACID.
Acetic acid, CH3 . COOH, occurs in traces in the free state in many
essential oils, but principally in the form of esters, of which it is the usual
acid constituent.
It is a crystalline solid, or a liquid at ordinary temperatures, having
Melting-point 16'7°
Boiling-point 118°
It can be obtained by the oxidation of ethyl alcohol, either chemically
or by fermentation under the influence of the organised ferment Myco-
derma aceti.
PROPIONIC ACID.
Propionic acid, C 2 H 5 . COOH, has been found in lavender and a few
other oils in traces. It is a liquid of rancid odour having the following
characters :—
Congealing-point - 24°
Boiling-point . . . . . . . . . . 141°
BUTYRIC ACID.
Butyric acid, C3H7 . COOH, is an oily liquid having an odour of
rancid butter. It has been found in the oils of Eucalyptus globulus,
Heracleum giganteum, and in nutmeg, niaouli, and other essential oils. It
Congealing-point -6°
Its constitution is CH3 . CH2 . CH2 . COOH. Isobutyric acid, which
has the constitution (CH3)9CH . COOH, exists in Spanish hop oil, arnica
root oil, and a few others. It is a liquid of specific gravity 0*949 at 20°,
boiling at 155°.
VALERIASic ACID.
The isomeric valerianic acids have the formula C5H10O2. Normal
valerianic acid does not appear to be found in any essential oils. Iso-
valerianic acid, (CH3)2CH . CH2 . COOH, is found in valerian and other
oils ; it is a liquid boiling at 174°, of specific gravity '947. Another
isomer, also found in champaca and coft'ee oils, is methyl-ethyl-acetic
acid, (C,H5)(CH3) . CH . COOH. This is an optically active liquid, boil-
ing at 175°, of specific gravity '941 at 21°.
CAPKOIC ACID.
Caproic acid,C5Hn. COOH, has been found in lemon-grass, palmarosa,
and several other essential oils. It is a liquid having the following char-
acters :—
Congealing point . . . . . . . . — 2°
Boiling-point . . . 205°
Specific gravity 0*928 at 20
HIGHER FATTY ACIDS.

The fatty acids of higher molecular weight than caproic acid are of
little interest or importance so far as essential oils are concerned, and for
their characters, the reader is referred to standard works on general
organic chemistry.
ANGELIC AND TIGLIC ACIDS.
These two acids, of the formula C5H802, are geometrical isomerides.
They are both unsaturated, and belong to the acrylic acid series. Tiglic
acid forms crystals melting at 64*5° and boiling at 198*5°, whilst angelic
acid melts at 45° to 46° and boils at 185°. They have the following con-
stitutions :—
CH 3 . CH CH 3 . CH
il II
CH 3 . C . COOH COOH . C . CH,
Angelic Acid. Tiglic Acid.
These two acids occur chiefly as esters in Roman chamomile oil.

Tiglic acid is also found as geranyl tiglate in geranium oil.
TERESANTALIC ACID.
Teresantalic acid, C10H14O^, is a hydro-cyclic acid, found in sandal-
wood oil. Its characters are as follows :—
Boiling-point at 11 mm • 150° (approximate)
Melting-point 157°
ClTRONELLIC AdD.
Citronellic acid, C9H17 . COOH, is the acid corresponding to the

alcohol citronellol, and is present in the essential oil of Barosma pulchel-
lum. It has the following characters :—
at 5 mm. 143° „ 144°
It forms a crystalline amide melting at 81° to 82°, which can be ob-
tained by converting the acid into its chloride, and then acting on this
with aqueous ammonia.
BENZOIC ACID.
Benzoic acid, C(;H,- . COOH, is the simplest acid of the benzene series.
It is found either free or in the form of esters in vetivert, jasmin, ylang-
ylang, neroli, and numerous other essential oils. It is a crystalline body
with a slight aromatic odour, having the following characters :—
Boiling-point 249°
It is prepared artificially on a large scale, usually by hydrolysing the

chlorination product of toluene.
SALICYLIC ACID.
Salicylic acid, C(.H4(OH)COOH, is ortho-hydroxy-benzoic acid of the
constitution—
CH
HCX /CH . OH
COOH
It is the acid constituent of the ester forming almost the whole of
wintergreen and birchbark oils, and is a crystalline solid melting at 159°.
Commercially pure samples, however, rarely melt at above 157°. It is
prepared artificially on an enormous scale by heating sodium phenol,
under pressure, with carbon dioxide.
PHENYL-ACETIC ACID.
This acid, C 6 H 5 . CH2COOH, is a sweet-smelling substance, especially
recommended for sweetening soap perfumes. It occurs in neroli oil, and
has a sweet honey-like odour. It is formed by converting toluene into
benzyl chloride which is converted into benzyl cyanide, which is digested
with dilute sulphuric acid, and so converted into phenyi-acetic acid. It
is a crystalline body, melting at 76° to 76*5° and boiling at 266°. It has
been isolated from oil of neroli.
CINNAMIC ACID.
This acid, of the formula C6H5CH : CHCOOH, occurs in a number
of, essential oils in the free state. It is prepared artificially by heating
benzal chloride with sodium acetate. It has a sweet odour. It is a
crystalline substance, melting at 133° and boiling at 300°.
HYDRO-CINNAMIC ACID.
This acid, C6H5. CH 2 . CH2COOH, has a sweet and powerful odour,
and can be used to advantage in many rose odours. It is recommended
especially for perfuming powders and sachets. It is a crystalline com-
pound, melting at 47° and boiling at 280°. It can be obtained by the
reduction of cinnamic acid by means of sodium.
PARA-METHOXY-CINNAMIC ACID.
This acid, CH3O . C6H4. CH : CH . COOH, is methyl-^-couma ric acid,
and is present in kaempferia oil. It is a crystalline solid melting at 171°.
ANISIC ACID.
Anisic acid is jo-methoxy-benzoic acid, C)3H4 . COCH3. COOH.. It is.
found in aniseed oil, and also in Tahiti vanillas. It is a crystalline body
melting at 184°.
VERATKIC ACID.
Veratric acid, (CH3O)2. CGH3 . COOH + H2O, is present in the essential1
oil of sabadilla seeds. It melts at 179° to 181°.
ANTHRANILIC ACID.
Anthranilic acid, or o-amidobenzoic acid, CtiH4 : (NH2)(COOH),. is the
acid constituent of the ester found in neroli, petit-grain, jasmin, and
mandarin oils. It is a solid crystalline substance melting at 145°. It is
prepared artificially, and then converted into synthetic methyl anthranilate..
To prepare anthranilic acid, o-nitrobenzaldehyde is reduced by tin and
hydrochloric acid to anthranil,
CflH / I
\CO
the internal anhydride or lactame of anthranilic acid. This is converted'
into anthranilic acid by boiling with alkalis :—
/NH X NH,
C6H4< i + NaOH = C0H4<
\CO \COONa
Methylanthranilic acid, which has been found as an ester in similar
oils, melts at 179°, and forms an acetyl derivative melting at 186°.,
ALANTOIC ACID.
Alantoic acid, C15H2203, is present in oil of elecampene, both as free
acid and in the form of its lactone. Its constitution is—
,OH
^14-"-20\
\COOH
It is a crystalline compound melting at 94°, and can be obtained by
hydiolysing alantolactone.
EUDESMIC ACID.
Eudesmic acid, C14H18O2, is found in the form of its amyl ester in the oil!
of Eucalyptus aggregata. It is a crystalline compound melting at 160°..
It is monobasic and unsaturated, and yields a dibromide melting,at 102°
to 103°.
COSTIC ACID.
Costic acid, C15H22O2, is a free acid isolated from costus root oil. It
is an unsaturated bicyclic acid of specific gravity 1*0501. It forms > a*,
methyl ester, boiling at 170° to 175° at 11 mm.
CHAPTER III.
THE ANALYSIS OF ESSENTIAL OILS.
IN general, the analysis of essential oils merely involves the application
of the ordinary principles of analytical chemistry to this special group of
bodies, which possess many features in common. Of course, many special
processes have to be used in certain cases, to which attention will be
drawn where necessary. The pfesent chapter will be devoted to the
details of a few methods which are in very common use in the analysis
of these bodies, aud which are absolutely necessary in order to form an
opinion on the purity of very many oils. Particular processes are men-
tioned as required under the essential oils or compounds concerned.
These remarks may be prefaced by saying that the obtaining of the results
of an analysis of an essential oil is not always as difficult a matter as the
interpretation of the same when obtained.
The adulteration of essential oils is now practised to a considerable
extent in a very scientific manner, the adulterants being so chosen that
the final mixture shall have, as far as possible, as many of the ascertain-
able characters of a pure oil as possible.
SPECIFIC GRAVITY.
The first thing to be done in examining an essential oil is to determine
its specific gravity. For this purpose hydrometers are useless. Approxi-
mate accuracy is useless in this work, and hydrometers are only capable
of yielding approximate results. Besides, one frequently has far too
little oil at one's disposal to use a hydrometer. For ordinary work a
specific gravity bottle is generally used, holding from 10 to 50 c.c.
There are two points to be noted in connexion with this. The graduated
bottles sent out by apparatus firms seldom contain the exact quantity
they are supposed to do. It is therefore advisable to check the contents
of the bottle, and to use the necessary correction when calculating a specific
gravity. Secondly, the counterpoise of a 50 c.c. bottle should be about
60 mgs. less than its apparent weight when empty on account of the air
contained in the bottle. A consideration of the laws of hydrostatic
pressure will show that if this be not so the specific gravity as determined
will be the ratio
weight of oil - '06 gram
weight of water - *06 gram
instead of the correct ratio
weight of oil
weight of water*
This correction of '06 gram is not absolutely accurate, but is sufficiently
so for all practical purposes and may be omitted in most cases.
(299)
It is essential that great care should be taken that the temperature
be accurately determined when taking the specific gravity. The bottle
filled with oil takes some time to assume the exact temperature of the
water in which it is immersed, especially if these differ much at first.
Hence it is always advisable not to depend only on an observation of the
temperature of the water, but to use a very small bulbed thermometer
with which the actual temperature of the oil itself in the bottle can be
taken. Specific gravities are usually expressed as the ratio of the weight
of a volume of the oil to that of an equal volume of water, both at 60° F.,
or approximately 15*5° C. This is written 7^7?^ . Any variation in
Cl _L 0 * O
temperature can thus easily be expressed. For example, the specific
gravity of, say, otto of roses at 30°, as given in the British Pharmacopoeia,
^30°
is intended to be interpreted
r as ^-K- eo - that is, with the water to which
'
it is compared at 15*5°. Wherever the specific gravity of an oil is referred
to in this work, it is to be understood as referring& to ,., , e u , except
r when
alo-5
otherwise quoted.
Fro. 8.
Frequently one has less than 50, and sometimes even less than 10 c.c.
of an oil at one's disposal. The specific gravity should then be determined
in a Sprengel tube. The above diagram shows the most convenient
form of tube for general use. With a very small knowledge of glass-
blowing they can be made in five minutes out of a few inches of glass-
tubing. The only important point is to choose a piece of thick walled
tubing, otherwise it is impossible to draw out satisfactory capillaries. The
oil should be sucked into the tube through the opening, B, by means of a
small india-rubber tube fixed on to the end, A, up to the small glass bulb
C. The tube is theji placed in a beaker of water at the desired tempera-
ture, the bent arms serving to support it on the side of the beaker. Owing
to its small content, from 2 to 5 c.c., it very rapidly acquires the tempera-
ture of the water, and by gently tilting the end, A, upwards, the oil runs
out at B until it just reaches the graduation mark, D. Taking care to
wipe off the last drop of oil exuding at B, the tube is again levelled, when
the liquid flows back into the bulb, so obviating any possibility of loss.
It is then carefully wiped and suspended by a copper wire loop to the
hook on the balance and weighed, and the specific gravity calculated
THE ANALYSIS OF ESSENTIAL OILS 301
from the weight of the oil and the weight of the corresponding volume of
water. The accuracy of these tubes depends on the fineness of the capil-
laries and the rapidity with which their contents assume the exact
temperature of the water in which the tube is immersed.
It is rarely that any greater degree of accuracy than that attained
in the above methods is required. If, however, scientific accuracy is
necessary in specific gravity determinations, the usual standard of com-
parison, at whatever temperature the determination may be made, is
water at its maximum density temperature, namely 4°. If no correction
is made for the weight of the air contained in the bottle or tube, accuracy
to the fourth place of decimals is ensured by reducing the observed
weighings to vacuum weighings. This can be done by the equation—
J° tn,~ T, T-
d =
±° w(Q - L + L
) '
where m is the observed weight of the substance, w that of the water, Q
the density of water at t9 (compared with water at 4°), and L is taken as
0*0012, which is approximately the density of air over a reasonable range
of temperature.
For practical purposes the alteration in specific gravity of essential
oils may be taken as 0*00075 for every degree centigrade, so that to
correct a specific gravity observed at 20° it is usual to add 0*00075 x 5
to correct it to 15°, and so on.
OPTICAL METHODS.
1. Refraction.
The author and several other chemists have for some years past
persistently advocated the use of the refractometer in the examination of
essential oils. Although this determination was regarded as of little use
by many chemists, it is now generally recognised that it is indispensable.
But its value is only to be properly estimated by a very careful considera-
tion of the results obtained.
The refractive index of a given sample of oil is in many cases of very
little value, in indicating adulteration. There are certain well-recognised
exceptions, wrhere the oil and the adulterant have refractive indices which
vary very widely. Such, for example, is the case with otto of roses and
geraniol, or aniseed oil and petroleum. But the chief value of this de-
termination lies in a careful examination of the various fractions obtained
when an oil is distilled in vacua. Here a consideration of the boiling-
points, specific gravity, optical rotation, and refractive index of the various
fractions will lead to most important indications. For example, an oil of
peppermint adulterated with, on the one hand, a small quantity of copaiba
or cedar-wood oil, and, on the other hand, with a small quantity of
glyceryl acetate, would give a refractive index not much different from
that of the genuine oil. But when distilled in vacua and the residues or
high boiling fractions examined, the high index in the one case would at
once suggest the presence of sesquiterpene bodies, whilst in the other-
case the very low index would indicate bodies belonging to the open-chain
series.
Experience alone will enable one to make the best use of these in-
dications, but it is important that as many figures should be available as
.302 THE CHEMISTEY OF ESSENTIAL OILS
possible. All determinations recorded in this volume are made on instru-
ments of the Pulfrich or the Zeiss Abbe types.1 Of these the Pulfrich
instrument is the more elaborate, but the Zeiss Abbe* refractometer, which
ris illustrated below, is the most useful instrument for ordinary work. Its
great advantage lies in the fact that it requires only a few drops of
fluid for a determination, and gives results which are accurate to one
or two points in the fourth place of decimals. The author has made a
very large number of determinations with it, and finds it to be absolutely
reliable. Eefractive indices between 1*3 and T7 can be determined by
FIG. 4.—The daylight which falls upon the mirror passes through the double prism,
closed for the purpose of measurement, into the telescope ; the arrows indicate
the direction of the circulation of hot water round the prisms to retain a constant
temperature. The magnifier is fitted with a reflector, not shown in the figure.
it, which figures cover the range found in essential oils. The following
is the method of using this instrument:—
The method of measurement is based upon the observation of the
position of the border line of the total reflection in relation to the faces of
a prism of flint-glass, into which the light from the substance under in
vestigation enters by the action of refraction.
1
An instrument of the Zeiss Abbe type is now made in England, and is fully
-equal in every respect to the German instrument.
The refractometer is mainly composed of the following parts :—
1. The double Abbe prism, which contains the fluid and can be rotated
•on a horizontal axis by means of an alidade.
2. A telescope for observing the border line of the total reflection
•which is formed in the prism.
3. A sector rigidly connected with the telescope, on which divisions
(representing refractive indices) are engraved.
The double prism consists of two similar prisms of flint-glass, each
•cemented into a metal mount and having a refractive index nd = 1'75 ;
the fluid to be investigated (a few drops) is deposited between the two
adjoining inner faces of the prisms in the form of a thin stratum (about
'0'15 mm. thick). The former of the two prisms, that farther from the
itelescope (which can be folded up or be removed), serves solely for the
purpose of illumination, while the border line is formed in the second
flint prism.
The border line is brought within the field of the telescope by rotating
the double prism by means of the alidade in the following manner :
.Holding the sector, the alidade is moved from the initial position, at
which the index points to nd = 1*3, in the ascending scale of the refractive
indices until the originally entirely illuminated field of view is encroached
upon, from the direction of its lower half, by a dark portion ; the line
dividing the bright and the dark half of the field then is the " border
line ". When daylight or lamplight is being employed, the borderline,
•owing to the total reflection and the refraction caused by the second
prism, assumes at first the appearance of a band of colour, which is quite
unsuitable for any exact process of adjustment. The conversion of this
band of colour into a colourless line, sharply dividing the bright and
•dark portions of the field, is effected by a compensator.
The compensator, which finds its place in the prolongation of the
itelescope tube beyond the objective, i.e. at a point between the objective
and the double prism, consists of two similar Amici prisms, of direct
vision for the D-line and rotated simultaneously, though in opposite
•directions, round the axis of the telescope by means of the screw head.
In this process of rotation the dispersion of the compensator passes
through every value from zero (when the refracting edges of the twro
Amici prisms are parallel and on different sides of the optical axis) up to
•double the amount of the dispersion of a single Amici prism (the refract-
ing edges being parallel and on the same side of the axis). The above-
mentioned dispersion of the border line, which appears in the telescope
as a band of colour, can thus be rendered innocuous by rotating the screw
head, thereby giving the compensator an equal, but opposite, dispersion.
The opposite equal dispersions will then neutralise each other, with the
result that the border line appears colourless and sharply defined.
The border line is now adjusted upon the point of intersection of the
crossed lines by slightly inclining the double prism to the telescope by
means of the alidade. The position of the pointer on the graduation of
the sector is then read off by the aid of the magnifier attached to the
alidade. The reading supplies the refractive index nd of the substance
under investigation itself, without any calculation.
As the refractive index of fluids varies with the temperature, it is of
importance to know the temperature of the fluid contained in the double
prism during the process of measurement.
If, therefore, it be desired to measure a fluid with the highest degree
of accuracy attainable (to within 1 or 2 units of the fourth decimal of nd\
it is absolutely necessary to keep the fluid, or rather the double prism
containing it, to a definite known temperature and to keep it constant.
The refractive index of a substance is, of course, a relative expression,
as it refers to a second substance, which, in ordinary determinations, is
always the air. The term refractive index indicates the ratio of the
velocities with which light traverses the two media respectively. This is,
as is easily demonstrated by a consideration of the wave theory of light,
identical with the ratio of the sine of the angle of incidence, and the sine
of the angle of refraction, thus—
V sin i
n=
V1 = sTn~?
where V and V1 are the velocities of light in the two media, i is the
angle of incidence, and r the arigle of refraction.
To correct a refractive index determined for air /liquid to the absolute
index vacuum/liquid, the observed value should be multiplied by r00029.
This correction is, however, too small to be of the slightest value in
practice.
The molecular refraction is a constant frequently quoted for individual
chemical compounds,1 and is of considerable value as evidence of constitu-
tion, since it is generally true that the molecular refraction of a compound
is composed additively of the refractive powers of the atoms contained in
the-molecule. The molecular refraction is the value obtained by multi-
plying the refractive power by the molecular weight.
The refractive power is a value which attempts to correct the effects
of temperature, pressure, and concentration of the substance, all of which
cause the refractive index, n(l1 to vary with the slightest alteration of the
conditions. The most accurate expression for the refractive power is
that of Lorenz and Lorentz, which is
ri* - 1
(n2 + 2)r/'
where n is. the observed refractive index and d is the density of the
substance. The molecular refraction then becomes
2X
where M is the molecular weight of the compound.
Briihl found that the increase of CH2 in all the homologous series of
fatty compounds corresponds to a difference of 4*57 in the molecular
refraction for the red hydrogen line. By deducting n times this value
from the molecular refraction cf an aldehyde or ketone of the formula
CMH2MO, he found 2*328 to be the value for intra-radical oxygen.
Similarly the values of other groupings have been determined which may
be summarised as follows :—
Atomic Refractions for
the Sodium Line.
Carbon . . 2-494
Hydrogen 1-051
O' (hydroxyl oxygen) 1-517
O" (intra-radical oxygen) 2-281
O (simple ether oxygen) 1-679
Cl . 5-976
Br . 8-900
j 14-120
= double linkage between carbon atom s 1-700
== triple linkage between carbon atoms 2-220 (for hydrogen red line)
To indicate the value of this constant in deciding the constitution
of a compound, the case of geraniol, C10H18O, may be examined. Calcu-
lated from the above values the molecular refraction would be the 'sum
of the atomic refractions, as follows:—•
Carbon 2'494 x 10 = 24'940
Hydrogen 1-051 x 18 = 18-918
Oxygen (hydroxyl) 1-517 = 1'577
45-375
But by experimental determination the molecular refraction is found
to be 48*71, which is 3*235 in excess of the value calculated from the
atomic refractions. Two double bonds between carbon atoms would
account for 3*414 in excess, so that it is evident that geraniol contains
two such double linkages. No alcohol of the formula C10H18O with two
double linkages can contain a ring, so that geraniol must belong to the
open chain series, a conclusion entirely supported by its chemical
characters.
The refractive indices of most essential oils have been given under
each oil in Volume I. ; if a temperature correction is required, as it
frequently is, the addition of 0*0004 for each degree centigrade by which
it is necessary to reduce the temperature, and a similar subtraction for
a rise of 1°, should be made. This figure varies slightly, but unless
accuracy to the fifth place of decimals is required, it is sufficiently ac-
curate for practical purposes.
2. Polarimetry.
The polarimeter is an instrument with which the essential oil chemist
cannot possibly dispense. The hypothesis, first seriously enunciated by
Le Bel and van t'Hoff, that substances which contained an asymmetric
carbon atom (i.e. a carbon atom directly united to four different atoms or
radicles) were capable of rotating the plane of polarisation of a beam of
polarised light, has now become a fundamental theory of organic chemistry.
The majority of essential oils contain one or more components containing
such a carbon atom, and so possess the power of effecting this rotation.
In general, the extent to which a given oil can produce this effect is fairly
constant, so that it can be used, within limits, as a criterion of the purity
or otherwise of the oil.
Without discussing the theories of the polarisation of light it will be
desirable to briefly illustrate the fundamental principles upon which t-eir
application depends. Ordinary light consists of transverse vibrations in
numerous planes in which is no polarity or two-sidedness, if the expres-
sion is justifiable; whilst plane polarised light consists of vibrations in
one plane only. This may be roughly illustrated in the following manner ;
If a string, fixed at its ends, be plucked, it will vibrate in a certain plane
dependent on the direction of the plucking. If the string be passed
through a slit, just wider than it is itself, in a piece of cardboard, so that
the slit is in the direction of the vibrations, these will not be interfered
with; but if the slit be turned round, the vibrations will be interfered
with, and when it is at right angles to the direction of the vibrations, they
will be totally suppressed. Light waves (for convenience, the expression,.
a ray of light, is more general) may be plane polarised in several ways, so
that the vibrations in the one plane may be similarly interfered with, and
VOL. n. 20
upon this depends the use of the polarimeter. This instrument, of which
the theory is described fully in the following pages, is constructed
on several different principles, of which by far the most useful for all
general purposes is the Laurent half-shadow instrument. In the an-
nexed diagram, A is a small telescope, B is a magnifying glass used to
read the graduation on the dial and vernier, C is one of the verniers, D
is a dial graduated to half degrees, E is the analysing Nicol's prism (a
specially prepared prism of calc-spar, capable of polarising light) which is
fixed to the graduated dial and telescope, F is the groove in which tubes
containing the liquids to be examined are inserted, H is a pointer attached
to the polarising Nicol's prism, G is the fixed Laurent plate (vide infra),
and J is a plate of bichromate of potassium.
This apparatus can only be used with sodium light, as for quantitative
results light of definite refrangibility must be used. A Bunsen lamp of
convenient construction, into the flame of which a little common salt can
be introduced on a platinum wire, is placed about 4 or 5 inches from the
FIG. 5.
end J. The light is further sifted by means of the bichromate plate, so

that light approximately corresponding to ths D line of the spectrum falls
on to the polariser, and that which passes through is plane polarised.
The plate G- is a special contrivance, half of which is made of quartz or
gypsum, and the other half of plain glass; the thickness of this is care-
fully graduated, and the result—the optical theory of which need not here
be discussed—is that when the analyser is in a certain position with re-
ference to the polariser and plate, the two halves of this plate appear
equally illuminated. By adjusting the prisms by means of the movable
pointer, H, and the screw, E, which govern the delicacy of the instrument,
the zero marks on the dial and on the vernier are made to correspond
when the position of equal illumination is attained. A slight rotation of
the analyser in either direction by means of the projecting screw handle
at once causes the two halves of the field to become unequally illuminated.
Having set the instrument at zero, a tube containing an optically active
liquid is inserted in the groove, F. It will now be found that the analyser
has to be rotated a certain number of degrees either to the right or the
left in order to restore the position of equal illumination of the two halves
of the field. This is the angle through which the plane of polarisation
has been rotated. The beginner will find a little difficulty in using this
instrument; for example, when examining oils with high rotations or when
the dial has been rotated too far, and has been taken beyond the range of
sensitiveness; half an hour with some one who understands the instru-
ment will explain its use far better than pages of printed matter. The
rotation of the dial in the direction of the movement of the hands of the
clock, as the observer sees it, is conventionally termed dextro-rotation,
and conversely. In general, the optical rotation is expressed for a column
of 100 mm. The specific rotatory power is a different figure, and is ex-
pressed by the symbol [a], and, taking the decimetre as the unit of length
for this purpose, is the observed rotation in the decimetre tube divided by
the specific gravity of the liquid. It is to be noted, however, that the
expression [a] is very frequently used to mean the observed rotation for
100 mm. The molecular rotation refers of course only to pure compounds
and not to mixtures, and need not be discussed here, otherwise than to
mention that it is the product of the specific rotary power and the mole-
cular weight. In the sequel, the optical rotation will be understood to
refer to the rotation produced by a column 100 mm. long, unless other-
wise mentioned.
The theory of the half-shadow polarimeter is, briefly, as follows : The
light, of approximately constant refrangibility, falls on the polarising
Nigel's prism, which is a rhomb of calc-spar cut obliquely by a plane
perpendicular to the principal section. The cut faces are polished and
cemented together again by a thin film of Canada balsam. Calc-spar is
a doubly refracting substance, and in the ordinary way the incident ray
is divided 1by the spar into two rays, the ordinary and the extraordinary,
the former following the ordinary laws of refraction, the latter behaving
abnormally. Two rays, then, will be found to emerge. But the refrac-
tive index of the balsam is greater than that of the spar for the extra-
ordinary ray, and less than that tor the ordinary ray, both of which are
plane polarised. According to the usual laws of refraction, total reflection
can only occur in passing from a more to a less refracting medium.
Hence the extraordinary ray will always be transmitted, but by arranging
the angle of incidence properly the ordinary ray can be totally reflected.
Hence only the extraordinary ray now falls on to the Laurent plate, and
it is in a plane polarised condition. This plate is made of quartz or
gypsum over one-half of the field, and plain glass over the other. It is a
doubly refracting substance and refracts the incident ray as ordinary and
extraordinary rays. The thickness is so adjusted that it introduces a re-
tardation of -£A. (where X is the wave length of the light used) between
the two rays. Consequently, the light emerges plane polarised from the
crystalline plate, but the planes of polarisation of the rays emerging from
the two halves will be inclined at an angle 2a, if a is the inclination of
the incident single polarised ray to the optical axis of the quartz. Hence
when this plate, with its two polarised rays, is viewed through the ana-
lysing Nicol, the two halves will be in general unequally illuminated,
except when the principal plane of the Nicol be parallel to the optical
axis of the crystalline plate. In this position we have the zero point of
the instrument. The insertion of an optically active liquid .destroys this
condition by rotating the plane of polarisation, and the angle through
which it is necessary to rotate the analyser in order to restore the " equal
shadows " measures the rotation of the plane of polarisation.
Another simple instrument, known as the Biquartz polariser, depends
on a rather different principle. Here two semicircular plates of quartz
are placed in juxtaposition, each cut at right angles to its axis, one pos-
sessing dextro- and the other laevo-rotatory power. The two plates are
of the same thickness, and produce equal rotations in opposite directions.
The incident light in this case is white, and the lights of different re-
frangibilities are rotated through different angles. Hence when viewed
by an analysing Nicol, waves of different refrangibilities will be quenched
in the two halves, and they will in general appear of different colours.
When the principal plane of the analyser, however, is parallel to the
direction of the incident vibrations, the two halves will always be of the
same colour, dependent on the complementary colours which are quenched.
By suitably adjusting the thickness of the plate, the brilliant yellow may
be quenched, and the delicate grey-violet tint, known as the tint of
passage (Biot's teinte sensible), appears when both halves have the same
colour. This point, the zero point of the apparatus, is easily fixed, for
the slightest rotation to the right or left renders one-half of the field blue
and the other red. Having set the instrument, it is found that when an
optically active substance is introduced, the tint of passage disappears,
and the analyser must be rotated in order to restore it, according to the
optical activity of the substance.
To most observers it is easier to obtain equal illumination in the two
halves of the field than to correctly obtain the tint of passage, hence the
popularity of the former apparatus.
The angle of rotation is, of course, directly proportional to the thick-
ness of the layer of active substance through which the polarised light
passes. The expression optical rotation or rotatory power is universally
understood to be the observed angle of rotation produced by a column of
100 mm. of the optically active substance. If tubes of other lengths be
used, the optical rotation becomes a = d,-, where a is the observed angle,
and I is the length of the tube in decimetres. If, as is usually the case,
this is observed with sodium light the optical rotation is expressed by the
symbol, ad.
It is usual to express this value as for the temperature 20°. A slight
correction may be made for difference in temperature, but as it has no
appreciable effect on the results obtained, it may be regarded as negligible
if the observation be made at any temperature between 15° and 20°.
The expression " specific rotation " is symbolised by [a]d, and indicates
the optical rotation divided by the specific gravity : [a]d = r^ r—.
If expressed for white light instead of sodium light, it is expressed
by [a],.
For solid substances the substance is dissolved in a neutral solvent,
and the specific rotation is calculated from the formula—
lOOa
[a] =
* -pis-
Where a is the observed angle, p is the percentage of active substance,
I is the length of the tube in decimetres, and d is the specific gravity of
the solution.
But, since the specific rotation of dissolved substances vary with the
concentration and the nature of the solvent, these data should always be
given when the specific rotation is quoted.
MELTING- AND SOLIDIFYING-POINTS.

Many oils possess the property of becoming solid at temperatures
slightly below the ordinary, and a determination of the solidifying- or
melting-points becomes an important criterion of purity in these cases.
The melting-point is not usually the same as the solidify ing-point, on
account of the peculiar properties of bodies, included under the term
superfusion, etc. In addition, the temperature recorded differs some-
FIG. 6.
what with the method used in the determination. For general work
the following apparatus gives the best results in a convenient manner:—
Here the outer vessel contains a sufficient quantity of the freezing
mixture, such as a mixture of ice and salt, or a solution of one of the
usual salts. The longer test tube acts as an air cover to the inner tube
in which the thermometer is placed. A small quantity of the oil—just
enough to cover the bulb of the thermometer—is placed in this tube, and
in certain cases the platinum stirrer is used. The melting-point is de-
termined by freezing the oil and then removing the freezing mixture and
allowing the temperature to rise slowly, and noting the temperature at
which liquefaction takes place. The solidification-point is determined
by cooling the oil down without disturbing it until the temperature is
clearly below the point of solidification. A slight agitation of the stirrer
will now usually induce solidification, if not, the introduction of a crystal
of the compound solidifying—anethol, for example, in the case of aniseed
oil—will do so. A disengagement of heat occurs on solidification, which
causes the thermometer to rise. The maximum reading during the
process of solidifying may be regarded as the solidifying-point.
BOILING-POINT AND DISTILLATION.

The determination of the temperature at which an oil begins to boil
is often of importance, as is also the percentage of the oil which distils
within definite limits of temperature. The results obtained in distillation
processes must, however, be interpreted very carefully, as the quantitative
results depend so largely on the exact conditions of distillation. For
ordinary purposes, an ordinary .Wurtz flask is useful for determining the
temperature at which the liquid first boils, but when an examination of
FIG. 7.—Fractionating columns. FIG. 8. FIG. 9.

Fractionating Wurtz flask.
flask.
any of the fractions or any estimation of the quantity boiling between

given temperatures is needed, a fractional distillation flask is better.
These flasks are illustrated above.
It is often advisable to distil or fractionate an oil under reduced
pressure, especially when the constituents decompose when boiled at
atmospheric pressures.
The value of fractional distillation in the examination of essential
oils cannot be overestimated. The various fractions may be examined
and their specific gravities, optical rotations, and refractive indices deter-
mined. The combination of these figures will often give the experienced
analyst the most useful information and save him many hours' needless
work. Experience alone, however, will teach the chemist to make the
fullest use of the results so obtained. In most cases distillation under
reduced pressure is necessary on account of the risk of decomposing the
various constituents of the oil. The use of a Bruhl receiver (or any
similar contrivance), which is easily obtained from any apparatus maker,
saves the necessity of breaking the vacuum when collecting the different
fractions.
But by applying the process of fractional distillation to a sample,
and determining the characters of numerous fractions, the actual number
of available determinations may be, and frequently is, so largely increased
that there is practically no chance of the adulterator being able to
standardise his oils to meet all these figures. This proposition, of course,
fails where it is possible to use a substance obtained from a cheaper source
which is identical with one contained naturally in the oil, and which is
added in such amount as not to materially exceed, in the total, the
amount naturally occurring in the essential oil in question.
In fractionally distilling an oil, in order to compare it with oils of
known purity similarly treated, it should be remembered that the details
of the process should be as constant as possible for all the samples ex-
amined. Thus the size of the distilling flask, the nature of the condensing
apparatus, and the rate of distillation are of the highest importance.
Experience alone will tell whether it is better to distil the oil at normal
pressure or under reduced pressure. Then again, in some intances it is
advantageous to separate the fractions according to their temperature,
noting the quantities collected. In others, it is better to collect definite
amounts and note the variations in temperature.
THE DETERMINATION OF ESTERS.

Esters, or salts of alkyl radicles, such as linalyl acetate, etc., are fre-
quently the most important constituents of essential oils. Their importance
is especially noteworthy in such cases as lavender, bergamot, peppermint,
and wintergreen oils, and their estimation is very frequently necessary.
The principle upon which this depends is the fact that most esters are
decomposed by solution of caustic alkali (preferably in alcohol) according
to the equation—
EA + KOH = E . OH + KA,
where E is the alkyl, and A the acid, radicle.
Strictly speaking the amount of free acids present in an essential oil
should be determined, and the acid value deducted from the saponification
value, the difference being the ester value.
In many cases the amount of free acids is negligible, but in a number
of cases this is not the case, and with oils of lavender, bergamot, geranium,
and similar oils, the deduction for the free acids becomes of importance.
To use this principle for the estimation, from 2 to 5 grams of the oil,
according to the magnitude of its ester content, are exactly weighed into
a small flask capable of holding about 150 to 250 c.c., and from 25 to
35 c.c. of solution of caustic potash in alcohol are added. The strength of
this should be approximately half-normal. The whole is then boiled in
the water-bath under a reflux condenser for an hour. It is then diluted
with water and the excess of potash is estimated by titration with semi-
normal sulphuric acid, using phenol-phthalein as an indicator. To de-
termine the amount of potash originally employed, it is best to perform
a blank experiment with the same quantity of potash solution, merely
omitting the oil, so that the blank and the oil have been treated in an
exactly similar way. The difference in the two titrations gives the
amount of potash used in decomposing the esters. Care should be taken
N
that the number of c.c. of -^ potash absorbed does not exceed the number
2
of c.c. unabsorbed, as otherwise the percentage of esters tends to be
underestimated. If any free acids are present these will have neutralised
some of the potash, and it is then necessary to determine by a preliminary
titration how much is used for this purpose, and to deduct the result
from the total quantity of potash used.
The number of milligrammes of KOH used to saponify 1 gram of the
oil (minus that required for the free acids) is termed the ester number.
From this figure, which is now known, the percentage of esters present
in a given oil mayjbe rapidly calculated from the formula—
M x A . . .
-g = percentage of ester,
ODU
where M is the molecular weight of the ester, and A the ester number.
(This is assuming, as is usually the case, that the ester is a combination
of a monobasic acid with a monatomic alcohol.)
As the free acids present in essential oils consist in the main of acetic
acid, they are, when necessary, calculated in terms of acetic acid ; in the
same way the esters are conventionally calculated from the alkali required
for their hydrolysis, in terms of the principal ester present, for example,
linalyl acetate in the case of lavender and bergamot oils, and geranyi
tiglate in the case of geranium oil.
The molecular weights of the esters commonly found in essential oils
are as follows :—
Geranyi, linalyl, and bornyl acetates M = 196
Menthyl acetate (for peppermint oil) M = 198
Geranyi tiglate (for rose-geranium oil) M = 236
Santalyl acetate (for sandalwood oil) M = 262
Sabinyl acetate (for savin oil) . M = 194
The Detection of Artificial Esters in Essential Oils.—The custom of
valuing certain essential oils, such as lavender, bergamot, geranium,
petit-grain, etc., by the determination of their ester-content, has led to the
use of scientific adulterants in the form of artificial esters which have
been deliberately employed for the purpose of misleading the analyst.
Of course, the ester determination is not a true criterion of value, as most
of this class of oils owe their perfume value to various other bodies as
well. The first compounds of this nature employed for adulteration were
ethyl succinate and ethyl oxalate.1 For the detection of these in lavender
oil the following test was proposed by Guildemeister and Hoffman :—
" Two grams of the oil are saponified ; the portion insoluble in water
separated by shaking with ether, and the aqueous solution neutralised
with acetic acid. The solution is diluted to 50 c.c. and 10 c.c. of cold
saturated solution of barium chloride added. It is then warmed for two
hours on a water-bath and allowed to cool. If a crystalline deposit is
formed, the oil is to be considered adulterated, as the acids contained in
normal lavender oil, acetic and butyric acids, give soluble barium salts."
It is evident that this test will only detect those acids whose barium
salts are insoluble. A more comprehensive test is therefore needed, as
several other esters have since been employed for adulteration purposes.
Glycerin acetate, prepared by the acetylation of glycerine, was first de-
1
Schimmel's Eeport, April, 1897, 25.
tected in peppermint oil by Bennett.1 The acetic radical was overlooked
in the preliminary experiments since the oil itself contained acetic esters.
By fractionation a substance of high molecular weight and low refractive
index was separated, and this proved to be triacetin or glycerin acetate.
Ethyl citrate was detected later by the same worker 2 in a sample of
lavender oil.
The high saponification value of these two bodies render them par-
ticularly suitable for adulteration, a small proportion being sufficient to
materially raise the ester value.
The following esters are amongst those used as adulterants:—3
Per Cent. Linalyl

Boiling-point. Specific Gravity. Acetate Indicated
by Addition of
1 per Cent.
Acetine 261° to 264° 1*19 2'00

Monacetine Decomposes 1-21 1-62
Diacetine . 260° to 265° 1-184 2-22
Triacetine . 258° 260° 1-165 2-62
Ethyl Citrate 286° 289° 1-140 2-13
,, Laurinate 270° 310° 0-866 0-75
,, Oleate 330° 345° 0-680? 0-64
„ Phthalate . 290° 293° 1-124 1-77
,, Succinate . 212° 218° 1-044 2-26
Methyl Phthalate 271° 275° 1-195 2-02
It is not easy to outline a general method which will detect this

adulteration of ester-containing oils. As a general rule, however, the
synthetic esters may be partially separated by fractional distillation, and
by comparing the physical characters of the last fractions with those
obtained from oils of known purity, an indication of the presence of
abnormal constituents may usually be obtained. By saponifying the
high-boiling ester-containing portion with alcoholic potash, neutralising
with acetic acid, evaporating the alcohol and extracting the oily matter
by shaking with ether, abnormal potassium salts may be detected in the
aqueous portion by evaporating to dryness, dissolving in water, and ap-
plying the usual chemical reagents such as barium chloride, calcium
chloride, ferric chloride, etc.
The table on next page shows the reactions of the more common
acids with these reagents.
The natural esters present in essential oils are usually those of acetic,
butyric, and valerianic acids, and in the case of geranium oil, tiglate acid.
The detection of phthalic acid by fusion with resorcin has been found
to be unreliable as a fluorescein reaction is frequently obtained with pure
oils.
Denige's test for citric acid in the saponification liquor is as follows :—•
Ten c.c. of the neutral solution of the potassium salt is shaken with
1 to 1*5 grams lead peroxide ; 2 c.c. of a solution of mercuric sulphate is
added (prepared by dissolving 5 grams HgO in 20 c.c. concentrated
H2SO4 and water to 100 c.c.). The solution is filtered and a 2 per cent.
1 2
CJiemist and3 Druggist, 62, 591. Ibid., 69, 691.
P. and E.O.R., July, 1912, 170.
solution of KMn04 is added until it is no longer decolorised. A white or
pale yellow flocculent precipitate indicates the presence of citric acid.
BaCl2. CaClo. FeCl3.
Benzoate nil nil Buff ppt.

Butyrate » »> nil
Cinnamate . White ppt. White ppt Buff ppt.
Citrate . ,, White ppt. on Green colour
boiling
Formate nil nil Red „
Oleate . White ppt. White ppt. Brown ppt.
Oxalate ,, ,, Green ,,
Phthalate . nil nil Brown „
Succinate . M » >» »»
Tartrate White ppt. White ppt. ? Green colour
Brown ppt. on
heating.
Valeriana:e . » »» Brown ppt.
The following methods for the determination of a number of artificial

esters are reproduced, for the sake of completing the subject here, from
Volume I of this work :—
Terpinyl acetate in the absence of esters of high molecular weight,
or ethyl esters of the fatty acids of coconut oil, is indicated by a difference
to be observed in the apparent ester value by different times of saponifi-
cation. This ester is far more resistant to the action of caustic alkali
than is linalyl acetate, and requires two hours at least for complete
saponification. Hence, if the oil shows a difference in the saponification
value in thirty minutes and in two hours, which amounts to more than
from 1 to 2, terpinyl acetate is almost certainly present. The following
tablel shows the effect of this partial-saponification on the two esters
and on adulterated oils :—
Time of Saponification. 5 mins. 15 mins. 30 mins. 45 mins. 1 hr. 2hrs.
Linalyl Acetate E. No. 191-5 217-5 223'2 223-7 223-1 224-7

Terpinyl „ , 108-2 166-8 209'7 233-4 245*8 262-7
Bergamot Oil , 80-3 94-5 97-3 97-5 97-8 98-5
„ „ + 6°/ Terpinyl Acetate , 82-5 94-8 101-2 102-1 104-7 1072
„ +io°/ 0 „ „ , 79-9 96-4 102-8 105-2 108-3 112-5
» . „ +25% 78-8 100-6 108-1 116-4 119-0 126-8
Fractional saponification, with the use of varying amounts of caustic

alkali, will also reveal the presence of terpinyl acetate.
The following table will indicate the differences observed when about
N
2*5 grams of the oil are saponified (1) with 20 c.c. of -^ alkali for two
A
N
hours, and (2) with 10 c.c. of ~- alkali, diluted with 25 c.c. of alcohol for
A
one hour:—
1
20 c.c. x 10 c.c. (and

Oil. 2 hours. 25 c.c. Alcohol) Difference.
x 1 hour.
Bergamot (1) . 100-5 98-6 1-9

Bergamot (2) 103 105-5 2-5
,, with 5 per Cent. Terpinyi
Acetate . . . . 117 102-5 14-5
,, with 10 per Cent. Terpinyi
Acetate . . . . J21 104-0 17-0
The table on next page represents the behaviour on fractionation at

3 mm. pressure of two samples of bergamot adulterated with terpinyl
acetate and a sample of pure bergamot oil.
The author l has recommended the examination of the last 10 per
cent, left on evaporation of the oil on a water-bath, since the heavy arti-
ficial esters accumulate in this fraction. The-refractive index of this 10
per cent, should not be below 1*5090, and the saponification value should
not exceed 190. The following figures (see p. 317) represent nine
samples of adulterated oil, all sold as genuine bergamot oil.
Glyceryl acetate, which is an artificial ester commonly used in the
adulteration of bergamot oil, is detected fairly easily on account of its high
solubility in dilute alcohol. The test is carried out as follows : 2 Ten c.c.
of bergamot oil and 20 c.c. of 5 per cent, alcohol are well shaken in a.
separating funnel, and after the solutions have separated and become
clear the watery solution is run off and filtered. Ten c.c. of the filtrate
are exactly neutralised with deci-normal alkali, and then 5 c.c. of semi-
normal alkali run in, and the whole saponified under a reflux condenser
for one hour. In the case of pure bergamot oil 0*1 or at most 0*2 c.c. of
semi-normal alkali will have been used up by the saponification, whilst
each 1 per cent, of glyceryl triacetate present in the oil will be represented
by practically 0*5 c.c. of semi-normal alkali.
Glyceryl acetate is so easily washed out with ordinary hot distilled
water, that an adulterated oil when washed several times with hot water
will show a distinctly lower ester value and refractive index than the
original unwashed oil.
Pure oils of lavender, bergamot and similar oils show practically no-
reduction either in refractive index or ester value by such treatment.
Hall and Harvey3 prefer to determine glyceryl acetate in essential
oils by a method in which the glycerol is separated and weighed. This-
method is as follows :—
A quantity, if possible not less than 10 grams, of the oil to be ex-
amined is mixed with about 50 c.c. of '830 alcohol and saponified with
N/2 alcoholic potash; it is then digested on the water-bath for a period
of one hour; the solution is neutralised by means of N/2 HC1, and
evaporated to dryness upon the water-bath in order to remove the alcohol;
about 20 c.c. of water is added and the oily proportion extracted by
methylated ether, the water solution being run in a 6-oz. round-bottomed
flask; the ether extract should again be washed with a further quantity
of about 10 c.c. of water, which is then added to that already in the flask
1 2
P. and E.O.R., 1911, 14. SchimmePs Bericht, April, 1911, 151.
* P.
lO XO rH rH
S TH TH 00 CO
p
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Pure Bergamot 0
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rH JO rH CM rH
«D. 0
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o O
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GO
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OS
rH
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CM CM O GO O
P s '
rH rH rH rH rH rH
O
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lO CM
CO
CO
lO
CM
TH s
-• s CO
CO
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CO
rH
rH
00 CO ^ 1
1
+ + 1 ' I I
00 rH rH rH
\ 1
TH lO
CM 00 CJ CM CD 1O CM
fH
CO rH CM rH
O O OO C<I 00 C<l 00
TH lO CO t~ t>- 00 00 O3 ^
ô O j; - ~ - - ~
e3 O O 00 CM 00 CM
£
'8 1
rH CM CO TH lO* CO* t-" 00* C5
1. 2. 3. 4. 5. 6. 7. 8. 9.
!
w
Specific Gravity 0-885 0-884 0-884 0-8855 0-886 0-886 0-886 0-885 0-878 >
Optical Rotation . . . . . . + 16° + 16° 30' + 16° 30' + 18° + 23° + 17° + 20° + 26° + 27° >
Refractive Index at 20° 1-4660 1-4660 1-4662 1-4658 1-4660 1-4660 1-4681 1-4675 1-4691 GO
Apparent Esters as Linalyl Acetate . 39% 39-5 °/0 39% 38-8 % 39-5 % 40% 41% 34% CO
O
Fixed Residue . . . . 6-5
^ u °/
/o 6-3 °/ 4-2 °/ 6-4 °/ 6-1 °/ 7-2 °/ 4-5 °/ 6-9 °/ w
1
ESSENTL
,, ,, Saponification Value of 257 225 160 239 236 252 172 242 162
„ „ of Saponified Oil . 5 4-7 % 5-4 % 4-2 %
'3 % 5% 4-9 % 4%
Refractive Index of last 10 per cent. . 1-5040 1-5042 1-5085 1-5042 1-5040 1-5050 1-5070 l'£050 1-5091
k**
Increase in Ester Value in one hour . — — 3-8 % — — — 4'1% —
—
0
All these were adulterated with ethyl citrate except Nos. 3 and 7, which contained terpinyl acetate, and No. 9, which was adulterated
with lemon terpenes.
and the whole evaporated to a syrupy condition. This residue contains
the glycerol origin lly present as glyceryl acetate which is estimated in
the usual way by the triacetin method, the amount of glyceryl acetate
being calculated therefrom.
Schimmel & Co. have proposed to detect esters of fixed acids by an
estimation of the amount of volatile acids obtained by distilling the acidified
saponification residues, and comparing this figure with the amount of
acid indicated by the saponification value.
In this determination about 2 grams are saponified in the usual
manner, and the saponification residue rendered slightly alkaline, and
evaporated to dryness on a water-bath. The residue is dissolved in 5 c.c.
of water and acidified with 2 c.c. of dilute sulphuric acid. This liquid is
now distilled by passing a current of steam through it, and when no
FIG. 10.
further acid comes over the distillate (about 300 c.c.) is titrated with deci-
normal alkali, using phenolphthalein as indicator. The alkali consumed in
this neutralisation is nearly identical with that used in the direct saponi-
fication, if all the esters present are those of volatile acids, as is the case,
with pure bergamot oil. The distillation value should not be more than
5 to 10 below the direct saponification value (i.e. milligrams of KOH per
1 gram of oil). When esters of non-volatile acids have been used as
adulterants the difference is enormous. For example, an oil containing
2 per cent, of ethyl citrate yielded a direct saponification value of 109*1
and a distillation value of 92'8, and one containing 5 per cent, of ethyl
succinate gave a direct value of 127'6 and a distillation value of 91*5.
Umney l has made a critical study of this method, and recommends
the following apparatus to be used in the process :—
3
P. and E.O.R., 1914, 116.
(a) A 3 litre Jena glass flask.
(b) A rubber connection, the removal of which, of course, immediately
cuts off the steam supply.
(c) A long-necked C02 flask of Jena glass and 150 c.c. capacity.
(d) The most suitable splash head for the operation.
(e) A Davies' condenser.
(/) A 500 c.c. Erlenmeyer flask.
The results obtained, unless the special precautions described be
adopted when calculated as percentages of ester in the oil, are consider-
ably too high. Whilst some of the causes may be apparent to many,
nevertheless the following is a list constructed to include the more im-
portant of these causes, and will serve to indicate in what manner the
necessary amendments should be made :—
1. The use of methylated spirit (unpurified by further distillation)
in the preparation of the standard potash solution employed by some
experimenters in the saponification of the oil.
2. The use of hydrochloric acid in neutralising the excess of alkali
after saponification.
3. The employment of water in the steam generating flask which
has been insufficiently boiled to free it from carbon dioxide and other
impurities.
4. The sulphuric acid, used to acidulate before distillation, may be
advantageously replaced by phosphoric acid. This modification, whilst
in many cases not absolutely essential, is desirable on account of the fact
that sulphuric acid is liable to become reduced by certain constituents of
oils, particularly of old oils, which frequently contain substances of a
resinous nature. In such cases the volatile acid products of the reduc-
tion pass over along with the true acids of the oil undergoing examina-
tion.
The relations which the abnormal results obtained bear to the above
outlined conditions are clearly shown by the figures on next page.
It is evident that, in order to obtain accurate results, the method of
working must be clearly and minutely adhered to, especially so in view
of the fact that the determination of ester by the' method of steam distilla-
tion is a very valuable indication as to the purity of an oil, serving to
detect the fraudulent addition to oils of such esters as diethyl succinate,
triethyl citrate, and diethyl oxalate, the free acids of which are non-
volatile in steam. It will not detect glyceryl acetate, terpinyl acetate,
nor the esters of coconut oil fatty acids.
The method yielding reliable results and including modifications,
devised to remove the sources of error above-mentioned, is as follows:—
About 2 grams of the oil (bergamot or lavender) is accurately weighed
into a carbon dioxide flask, and 15 c.c. neutralised alcohol added along
with a few drops of phenolphthalein solution, and the whole is just boiled
on the steam-bath. The acid number is ascertained by titration with
deci-normal alcoholic potassium hydroxide, 25 c.c. semi-normal alcoholic
potash (made with 90 to 96 per cent, spirit, preferably distilled over
potash) is now added, and the whole boiled under a reflux condenser for
one hour, the excess of potash, after saponification and addition of 40 c.c.
of carbon dioxide-free water, being neutralised by means of semi-normal
sulphuric acid. This titration gives the figure from which the ester per-
centage is calculated.
Method. Percentage of Ester

found.
1. Oil saponified by solution of potash in unpurified methy-

lated spirit. Excess of alkali neutralised by hydro-
chloric acid, and the acids liberated, previous to dis-
tillation by sulphuric acid 47-28
2. As 1, but the excess of alkali after saponification neutra-
lised by sulphuric acid 43-51
3. As 2, but the methylated alcoholic potash replaced by a
solution of potash in 96 per cent. (60 o.p.) alcohol 41-38
4. As 2, methylated alcoholic potash (the spirit being
previously purified by distillation over potash) being
used instead of the solution of potash in unpurified
spirit 41-45
5. As 2, the methylated alcoholic potash being replaced by
a solution of potash in Absolute alcohol purified by
distillation over potash . . . . . . . 41-00
6. A "blank" experiment, employing for distillation the 1-5 c.c. deci-normal 1;
residue resulting from the evaporation of 25 c.c. of the sodium hydroxide
alcoholic potash used in 5, previously neutralised by was required for
means o f sulphuric acid . . . . . . . the neutralisation
of the distillate
7. Ester found in 5 less the amount of ester equivalent to
the volume of deci-normal sodium hydroxide used up in
t h e blank experiment . . . . . . . 39-69
A few drops of semi-normal alcoholic potash are added, and the liquid
allowed to evaporate on the steam-bath.
To the residue is added 10 c.c. of dilute phosphoric acid, prepared by
mixing about 3-5 c.c. of 88 per cent, acid with 100 c.c. of carbon dioxide-
free distilled water.
The carbon dioxide flask is now immediately attached to the appara-
tus, and the distillation is commenced.
It should here be noted that the distilled water in the steam generat-
ing flask must have been allowed to become entirely free from carbon
dioxide by at least half an hour's preliminary boiling.
The whole apparatus must be thoroughly cleansed and freed from air
by allowing steam from the generator to blow through for a few minutes
before attaching the carbon dioxide flask.
Distillation is allowed to proceed, the water in the generator being
kept boiling as quickly as possible, and the volume of liquid in the
smaller flask being kept at about 10 c.c. by means of a small flame.
The time taken for the collection of the required 250 c.c. of distillate-
is usually about thirty minutes.
The distillate is collected in a 500 c.c. Erlenmeyer flask having a
mark upon it to indicate the level of 250 c.c. Phenolphthalein solution
and a sufficient excess of deci-normal sodium hydroxide solution are added
to the distillate and the excess of alkali determined by titration.
The best general method for the detection of added esters, other than
those of acetic acid and formic acid, is to separate the acids and identify
them.
For this purpose 10 c.c. of oil are saponified for one hour with 20 c.c.
of 2/N alcoholic potash. 25 c.c. of water are then added and the hulk
of the alcohol evaporated off. The solution is then almost neutralised to
phenolphthalein and the unsaponified oil removed by shaking out three
times with ether.
The aqueous solution is then made acid to methyl orange, and shaken
out with ether.
The ethereal solution will now contain acids such as ben zoic, cinnamic,
oleic, phthalic and lauric, and these will be obtained in a moderately
pure condition by evaporating off the ether.
The aqueous solution will contain the readily water soluble acids
such as citric, oxalic and tartaric, etc. This solution should therefore be
made just alkaline to phenolphthalein, excess of barium chloride solution
added, and the whole warmed for about ten minutes.
A crystalline precipitate of barium salt will be obtained, from which
the acid can be readily liberated and identified.
THE DETERMINATION OF ALCOHOLS.
The determination of alcohols in essential oils depends on the con-
version of these compounds into their acetic esters, and then carrying out
an ester determination as described above.
Ten c.c. of the oil (spike, sandalwood and citronella are typical) are
boiled under a reflux condenser for two hours with 20 c.c. of acetic
anhydride and 2 grams of anhydrous sodium acetate. After the liquid
has cooled, it is diluted with water and allowed to stand in the water-
bath for fifteen minutes in order to decompose the excess of acetic
anhydride. The liquid is then transferred to a separator and repeatedly
washed with brine until the wash water is perfectly neutral in reaction.
The last washing may be effected with brine containing a little sodium
carbonate when the washings should be alkaline. The oil is then separ-
ated and the last traces of water removed by digestion with ignited
potassium sulphate for an hour. About 2 to 3 grams, depending on the
alcohol content of the acetylated (esterified) oil, are then saponified as
described under ester determination care being taken to neutralise the
oil before saponification, as traces of free acid always remain in the
acetylated oil. The amount of ester in the acetylated oil is easily cal-
culated, but to convert this into the percentage of free alcohol in the
original oil requires a more tedious calculation. The following formula,
can be used for this :—
_ N xM
x
~ 10(W - -042N)'
where x is the percentage of the alcohol in the original oil, M is the-
molecular weight, and N is the number of c.c. of normal alkali used, and
W the weight of the acetylated oil. Here the factor -042N is on account
of the increase of the weight due to acetylation. This formula is only
true if the original oil contains no esters. In cases where esters and
alcohols occur together the best method is to—
1. Estimate the esters in the original oil by a preliminary saponifica-
tion of a small quantity.
2. Saponify about 20 grams and separate the resulting oil, which now
contains all the alcohols in the free state.
3. Estimate the total alcohols in 2 by the acetylation process.
VOL. n. 21
4. Calculate the total alcohols in the original oils from 3, by allowing
for the decrease in weight of 1 when saponified.
5. Deduct the alcohols combined as esters from the total alcohols,
which gives the amount of free alcohols.
In these estimations it -is necessary to calculate all the esters and all
the alcohols to one formula, expressing the result, for instance, as menthyl
acetate, although as a matter of fact small quantities of the corresponding
propionate and butyrate may also be present, which it is impossible to
estimate separately.
Cocking l has constructed a simple formula by which the amount of
free alcohol may be accurately determined in the presence of any ester
or mixture of esters, providing that these are unaffected by acetylation.
The formula is as follows : —
Percentage of free alcohol
A = Saponification value of the original oil.
B = Saponification value of the original oil after acetylation (not of
saponified oil).
Y = Molecular weight of alcohol if monatomic.
In certain cases the results thus obtained are very nearly scientifically
accurate, but in certain cases the alcohol breaks down under the influence
of the acetic anhydride and the results are considerably lower than the
truth, the variation depending entirely on the conditions of the experi-
ment, which should therefore be kept constant as above recommended.
Linalol and terpineol are two oases in point. To meet such cases Boulez 2
has recommended diluting 5 grams of the oil with 25 grams of turpentine,
and then boiling with 40 c.c. of acetic anhydride and 3 to 4 grams of
pure sodium acetate. A blank experiment to allow for the " alcohol
value " of the turpentine must be performed, and the proper deduction
made. It is claimed by Boulez that this method yields accurate results,
but, although in the case of terpineol the results are fairly good, the
process does not give scientifically accurate results.
The following tables have been prepared by Schimmel & Co., who
gave permission for them to be reproduced in a previous edition, in order
to save calculations. Having determined the Saponification value of the
oil before or after acetylation, the amounts of esters or alcohols respec-
tively can be calculated. It must be borne in mind that the alcohol values
are only strictly accurate when there are no esters present in the oil.
Table L give& the values for alcohols of the formula C10H]8O and C10H200
(geraniol and citronellol) and their acetic esters. Table II. gives the
corresponding values for the alcohols Cl5H24Oand C15H26O. Table III.
gives the ester values for geranyl tiglinate.
., 1918,37.
*Bull. Soc. CUm., iv. (1907), L 117.
TABLE I.
C10H180. doHÔ.
Sap. Acetate. Alcohol in Acetate.
Alcohol. the Alcohol in
Alcohol. the Sap.
Figure. Orig. Oil. Orig. Oil. Figure.
1 0-35 0-28 0-27 0-35 0-28 0-28 1

2 0-70 0-55 0-55 0-71 0-56 0-56 2
3 1-05 0-83 0-83 1-06 0-84 0-84 3
4 1-40 1-10 1-10 1-41 1-11 1-12 4
5 1-75 1-38 1-38 1-77 1-39 1-40 5
6 2-10 1-65 1-66 2-12 1-67 1-68 6
7 2-45 1-93 1-94 2-47 1-95 1-96 7
8 2-80 2-20 2-21 2-83 2-23 2-24 8
9 3-15 2-48 2-49 3-18 2-51 2-52 9
10 3-50 2-75 2-77 3-54 2-79 2-81 10
11 3-85 3-03 3-05 3-89 3-06 3-09 11

12 4-20 1 3-30 3-33 4-24 3-34 3-37 12
13 4-55 i 3-58 3-61 4-60 3-62 3-66 13
14 4-90 3-85 3-89 4-95 3-90 3-94 14
15 5-25 4-13 4-17 5-30 4-18 4-23 15
16 5-60 4-40 4-45 5-66 4-46 4-51 16
17 5-95 4-68 4-74 6-01 4-74 4-80 17
18 6-30 4-95 5-02 6-36 5-01 5-08 18
19 6-65 5-23 5-30 6-72 5-29 5-37 19
20 7-00 5-50 5-58 7-07 5-57 5-66 20
21 7-35 i 5-78 5-87 7*42 5-85 5-94 21

22 7-70 6-05 6-15 7-78 6-13 6-23 22
23 8-05 6-33 6-44 8-13 i 6-41 6-52 23
24 8-40 6-60 6-72 8-49 | 6-69 6-81 24
25 8-75 6-88 7-01 8-84 ! 6-96 7-10 25
26 9-10 7-15 7-29 9-19 7-24 7-39 26
27 9-45 7-43 7-58 9-55 7-52 7-68 27
28 9-80 7-70 7-87 9-90 i 7-80 7-97 28
29 10-15 7-98 8-15 10-25 | 8-08 8*26 29
30 10-50 8-25 8-44 10-61 8-36 8-55 30
31 10-85 8-53 8-73 10-96 8-64 8-84 31

32 11-20 8-80 9-02 11-31 8-91 9-13 32
33 11-55 9-08 9-31 1167 9-19 9-43 33
34 11-90 9-35 9-59 12-02 9-47 9-72 34
35 12-25 9-63 9-88 12-37 9-75 10-01 35
36 12-60 9-90 10-17 12-73 10-03 10-31 36
37 12-95 10-18 10-47 13-08 10-31 10-60 37
38 13-30 t 10-45 10-76 13-44 10-59 10-90 38
:
39 13-65 10-73 11-05 13-79 10-86 11-19 39
40 ! 14-00 11-00 11-34 14-14 11-14 11-49 40
41 14-35 11-28 11-63 14-50 11-42 11-78 41

42 i 14-70 11-55 11-93 14-85 11-70 12-08 42
43 ! 15-05 11-83 12-22 15-20 11-98 12-38 43
44 1 15-40 12-10 12-51 15«56 12-26 12-68 44
45 15-75 12-38 12-81 15-91 12-54 12-97 45
46 i 16-10 12-65 13-10 16-26 12-81 13-27 46
47 16-45 12-93 13-40 16-62 13-09 13-57 47
48 i 16-80 ! 13-20 13-69 16-97 13-37 13-87 48
49 1715 ! 13-48 13-99 17-32 13-65 14-17 49
50 17-50 1 13-75 14-29 17-68 13-98 14-47 50
1
TABLE I. (continued).
CioHisO- C10H200.
Sap. Acetate. Alcohol in Alcohol in
Alcohol. the Sap.
Figure. Alcohol. the Orig. Oil. Acetate. Orig. Oil. Figure.
51 17-85 14-03 14-58 18-03 14-21 14-77 51

52 18-20 14-30 14-88 18-39 14-49 15-07 52
53 18-55 14-58 15-18 18-74 14-76 15-38 53
54 18-90 14-85 15-48 19-09 15-04 15-68 54
55 19-25 15-13 15-77 19-45 15-32 15-98 55
56 19-60 15-40 16-07 19-80 15-60 16-28 56
57 19-95 15-68 16-38 20-15 15-88 16-59 57
58 20-30 15-95 16-68 20-51 16-16 16-89 58
59 20-65 16-23 16-98 20-86 16-44 17-20 59
60 21-00 16-50 17-28 21-21 16-71 17-50 60
61 21-35 16-78 17-58 21-57 16-99 17-81 61

62 21-70 17-05 17-88 21-92 17-27 18-11 62
63 22-05 17-33 18-18 22-27 17-55 18-42 63
64 22-40 17-60 18-49 22-63 17-83 18-73 64
65 22-75 17-88 18-79 22-98 18-11 19-04 65
66 23-10 18-15 19-10 23-34 18-39 19-34 66
67 23-45 18-43 19-40 23-69 18-66 19-65 67
68 23-80 18-70 19-70 24-04 18-94 19-96 68
69 24-15 18-98 20-01 24-40 19-22 20-27 69
70 24-50 19-25 20-32 24-75 19-50 20-58 70
71 24-85 19-53 20-62 25-10 19-78 20-89 71

72 25-20 19-80 20-93 25-46 20-06 21-20 72
73 25-55 20-08 21-24 25-81 20-34 21-51 73
74 25*90 20-35 21-55 26-16 20-61 21-83 74
75 26-25 20-63 21-85 26-52 20-89 22-14 75
76 26-60 20-90 22-16 26-87 21-17 22-45 76
77 26-95 21-18 22-47 27-22 21-45 22-77 77
78 27-30 21-45 22-78 27-58 21-73 23-08 78
79 27-65 21-73 23-09 27-93 22-01 23-39 79
80 28-00 22-00 23-40 28-29 22-29 23-71 80
81 28-35 22-28 23-72 28-64 22-56 24-02 81

82 28-70 22-55 24-03 28-99 22-84 24-34 82
83 29-05 22-83 24-34 29-35 23-12 24-66 83
84 29-40 23-10 24-65 29-70 23-40 24-97 84
85 29-75 23-38 24-97 30-05 23-68 25-29 85
86 30-10 23-65 25-28 30-41 23-96 25-61 86
87 30-45 23-93 25-60 30-76 24-24 25-93 87
88 30-80 24-20 25-91 31-11 24-51 26-25 88
89 31-15 24-48 26-23 31-47 24-79 26-57 89
90 31-50 24-75 26-54 31-82 25-07 26-89 90
91 31-85 25-03 26-86 32-17 25-35 27-21 91

92 32-20 25-30 27-18 32-53 25-63 27-53 92
93 32-55 25-58 27-49 32-88 25-91 27-8£ 93
94 32-90 25-85 27-81 3324 26-19 28*17 94
95 33-25 26-13 28-13 33-59 26-46 28-49 95
96 33-60 26-40 28-45 33-94 26-74 28-82 96
97 33-95 26-68 28-77 34-30 27-02 29-14 97
98 34-30 26-95 29-09 34-65 27-30 29-47 98
99 34-65 27-23 29-41 35-00 27-58 29-79 99
100 35-00 27-50 29-73 35-36 27-86 30-11 100
C10H180. CioH2ftO.
Sap. Alcohol in Acetate. Alcohol in Sap.
Figure. Acetate. Alcohol. the Orig. Oil. Alcohol. the Orig. Oil. Figure.
101 35-35 27-78 30-05 35-71 28-14 30-44 101

102 35-70 28-05 30-37 36-06 28-41 3077 102
103 36-05 28-33 30-70 36-42 28-69 31-09 103
104 36-40 28-60 31-02 36-77 28-97 31-42 104
105 36-75 28-88 31-34 37-12 29-25 31-75 105
106 37-10 29-15 31-67 37-48 29-53 32-08 106
107 37-45 29-43 31-99 37-83 29-81 32-41 107
108 37-80 29-70 32-32 38-19 30-09 32-74 108
109 38-15 29-98 32-64 38-54 30-36 33-07 109
110 38-50 30-25 32-97 38-89 30-64 33-40 110
111 38-85 30-53 33-30 39-25 30-92 33-73 111

112 39-20 30-80 33-62 39-60 31-20 34-06 112
113 39-55 31-08 33-95 39-95 31-48 34-39 113
114 39-90 31-35 34-28 40-31 31-76 34-73 114
115 40-25 31-63 34-61 40-66 32-04 35-06 115
116 40-60 31-90 34-94 41-01 32-31 35-39 116
117 40-95 32-18 35-27 41-37 32-59 35-73 117
118 41-30 32-45 35-60 41-72 32-87 36-06 118
119 41-65 32-73 35-93 42-07 33-15 36-40 119
120 42-00 33-00 36-26 42-43 33-43 36-73 120
121 42-35 33-28 36-60 42-78 33-71 37-07 121

122 42-70 33-55 36-93 43-14 33-99 37-41 122
123 43-05 33-83 37-26 43-39 34-26 37-75 123
124 43-40 34-10 37-60 43-84 34-54 38-08 124
125 43-75 34-38 37-93 44-20 34-82 38-42 125
126 44*10 34-65 38-27 44-55 35-10 38-76 126
127 44-45 34-93 38-60 44-90 35-38 39-10 127
128 44-80 35-20 38-94 45-26 35-66 39-44 128
129 45-15 35-48 39-27 45-61 35-94 39-78 129
130 45-50 35-75 39-61 45-96 36-21 40-13 130
131 45-85 36-03 39-95 46-32 36-49 40-47 131

132 46-20 36-30 40-29 46-67 36-77 40-81 132
133 46-55 36-58 40-63 47-02 37-05 41-16 133
134 46-90 36-85 40-97 47-38 37-33 41-50 134
135 47-25 37-13 41-31 47-73 37-61 41-84 135
136 47-60 37-40 41-65 48-09 37-89 42-19 136
137 47-95 37-68 41-99 48-44 38-16 42-53 137
138 48-30 37-95 42-33 48-79 38-44 42-88 138
139 48-65 38-23 42-67 49-15 38-72 43-23 139
140 49-00 38-50 43-02 49-50 39-00 43-58 140
141 49-35 38-78 43-36 49-85 39-28 43-92 141

142 49-70 39-05 43-71 50-21 39-56 44-27 142
143 50-05 39-33 44-05 50-56 39-84 44-62 143
144 1 50-40 39-60 44-39 50-91 40*11 44-97 144
145 50-75 39-88 44-74 51-27 40-39 45-32 145
146 51-10 40-15 45-09 51-62 40-67 45-67 146
147 51-45 40-43 45-44 51-97 40-95 46-02 147
148 51-80 40-70 45*78 52-33 41-23 46-38 148
149 52-15 40-98 46-13 52-68 41-51 46-73 149
150 52-50 41-25 46-48 53-04 41-79 47-08 150
TABLE I* (continued).
Ci0H180. C10H200.
Sap. Acetate. Alcohol. Alcohol in Alcohol in Sap.
Figure. the Orig. Oil. Acetate. Alcoho the Orig. Oil. Figure.
"
151 52-85 41-53 46-83 53-39 42-06 47-44 151
152 53-20 41-80 47-18 53-74 42-34 47-79 152
153 53-55 42-08 47-53 54-10 42-62 48-15 153
154 53-90 42-35 47-88 54-45 42-90 48-50 154
155 54-25 42-63 48-23 54-80 43-18 48-86 155
156 54-60 42-90 48-58 55-16 43-46 49-21 156
157 54-95 43-18 . 48-94 55-51 43-74 49-57 157
158 55-30 43-45 49-29 55-86 44-01 49-93 158
159 55-65 43-73 49-65 56-22 44-29 50-29 159
160 56-00 44-00 50-00 56-57 44-57 50-65 160
161 56-35 44-28 50-36 56-92 44-85 51-01 161

162 56-70 44-55 50-71 57-28 45-13 51-37 162
168 57-05 44-83 51-07 57-63 45-41 51-73 163
164 57-40 45-10 51-42 57-99 45-69 52-09 164
165 57*75 45-38 51-78 58-34 45*96 52-46 165
166 58-10 45-65 52-14 58-69 46-24 52-82 166
167 58-45 45-93 52-50 59-05 46-52 53-18 167
168 58-80 46-20 52-86 59-40 46-80 53-55 168
169 59-15 46-48 53-22 59-75 47-08 53-91 169
170 59-50 46-75 53-58 60-11 47-36 54-28 170
171 59-85 47-03 53-94 60-46 47-64 5464 171

172 60-20 47-30 54-31 60-81 47-91 ,55-01 172
173 60-55 47-58 54-67 61-17 48-19 55-38 173
174 60-90 47-85 55-03 61-52 48-47 55-75 174
175 61-25 48-13 55-40 61-87 48-75 56-12 175
176 61-60 48-40 55-76 62-23 49-03 56-48 176
177 61-95 48-68 56-13 62-58 49-31 56-85 177
178 62-30 48-95 56-49 62-94 49-59 57-23 178
179 62-65 49-23 56-86 63-29 49-86 57-60 179
180 63-00 49-50 57-22 63-64 50-14 57-97 180
181 63*35 49-78 57-59 64-00 50-42 58-34 181

182 63-70 50*05 57-96 64-35 50-70 58-71 182
183 64-05 50-33 58-33 64-70 50-98 59-09 183
184 64-40 50-60 58-70 65-06 51-26 59-46 184
185 64-75 50-88 59-07 65-41 51-54 59-84 185
186 65-10 51-15 59-44 65-76 51-81 60-21 186
187 65-45 51-43 59-81 66-12 52-09 60-59 187
188 65-80 51-70 60-19 66-47 52-37 60-97 188
189 66-15 51-98 60-56 66-82 52-65 61-35 189
190 66-50 52-25 60-93 67-18 52-93 61-72 190
191 66-85 52-53 61-31 67-53 53-21 62-10 191

192 67-20 52-80 61-68 67-89 53-49 62-48 192
193 67-55 53-08 62-06 68-24 53-76 62-86 193
194 67-90 53-35 62-43 68-59 54-04 63«24 194
195 68-25 53-63 62-81 68-95 54-32 63-63 195
196 68-60 53-90 63-19 69-30 54-60 64-01 196
197 68-95 54-18 63-57 69-65 54-88 64-39 197
198 69-30 54-45 63-95 70-01 55-16 64-78 198
199 69-65 54-73 64-33 70-36 55-44 65-16 199
200 70-00 55-00 64-71 70-71 55-71 65-55 200
C10H180. C10H*Q.
Sap.
Figure. Acetate. Alcohol. Alcohol in
the Orig. Oil. Acetate. Alcohol. theAlcohol in Sap.
Orig. Oil. Figure.
201 70-J5 55-28 65-09 71-07 55-99 65^93 201

202 70-70 55-55 65-47 71-42 56-27 66-32 202
203 71-05 55-83 65-85 71-77 56-55 66-71 203
204 71-40 56-10 66-23 72-13 56-83 67-09 204
205 71-75 56-38 66-62 72-48 57-11 67-48 205
206 72-10 56-65 67-00 72-84 57-39 67-87 206
207 72-45 56-93 67-39 73-19 57-66 68-26 207
208 72-80 57/20 67-77 73-54 57-94 68-65 208
209 73-15 57-48 68-16 73-90 58-22 69-04 209
210 73-50 57-75 68*55 74-25 5850 69-44 210
211 73-85 58-03 6S-93 74-60 58-78 69-83 211

212 74-20 58-30 69-32 74-96 59-06 70-22 212
213 74-55 58-58 69-71 75-31 59*34 70-62 213
214 74-90 58-85 70-10 75-66 59-61 71-01 214
215 75-25 59-13 70-49 76-02 59-89 71-41 215
216 75-60 59-40 70-88 76-37 60-17 71-80 216
217 75-95 59-68 71-28 76-72 60-45 72-20 217
218 76-30 59-95 71-87 77-08 60-73 72*60 218
219 76-65 60-23 72-06 77-43 61-01 73-00 219
220 77-00 60-50 72-45 77-79 61-29 73*40 220
221 77-35 6078 72-85 7o-14 61-56 73-80 221

222 77-70 61-05 73-25 78-49 61-84 74-20 222
223 78-05 61-33 73-64 78-85 62-12 74-60 223
224 78-40 61-60 74-04 79-20 62-40 75-00 224
225 78-75 61-88 74-44 79-55 62-68 75-40 225
226 79-10 62-15 74-84 79-91 62-96 75-81 226
227 79-45 62-43 75-23 80-26 63-24 76-21 227
228 79-80 62-70 75-63 80-61 63-51 76-62 228
229 80-15 62*98 76-03 80-97 63-79 77-02 229
230 80-50 63-25 76-44 81-32 64-07 77-43 230
231 80-85 63-53 76-84 81-67 64-35 77:83 231

232 81-20 63-80 77-24 82-03 64-63 78-24 232
233 81-55 64-08 77-64 82-38 64-91 78-65 233
234 81-90 64-35 78-05 82-74 65-19 79-06 234
235 82-25 64-63 78-45 83-09 65-46 79-47 235
236 82-60 6490 78-86 83-44 65-74 79-88 236
237 82-95 65-18 79-27 83-80 66-02 80-29 237
238 83-30 65-45 79-67 84-15 66-30 80-71 238
239 83-65 65-73 80-08 84-50 66-58 81-12 239
240 84-00 66-00 80-49 84-86 66-86 81-53 240
241 84-35 66-28 80-90 85-21 67-14 81-95 241

242 84-70 66-55 81-31 85-56 67-41 82-36 242
243 85-05 66-83 81-72 85-92 67-69 82-78 243
244 85-40 67-10 82-13 86-27 67-97 83-20 244
245 85-75 67-38 82-54 86-62 68-25 83-61 245
246 86-10 67-65 82-96 8698 68-53 84-03 246
247 86-45 67-93 83-37 87'33 68-81 84-45 247
248 86-80 68-20 83-78 87-69 69-09 84-87 248
249 87-15 68-48 84-20 88-04 69-36 85-29 249
250 87-50 68-75 | 84-62 88-39 69-64 , 85-71 250
1
CioH180. C10H200.
Sap. Acetate. Alcohol. Alcohol in Acetate. Alcohol. Alcohol in Sap.
Figure. the Orig. Oil. the Orig. Oil. Figure.
251 87-85 69-03 85-03 88-75 69-92 86-14 251

252 88-20 69-30 85-45 89-10 70-20 86-56 252
253 88-55 69-58 85-87 89-45 70-48 86-98 253
254 88-90 69-85 86-29 89-81 70-76 87-41 254
255 89-25 70-13 86-71 90-16 71-04 87-83 255
256 89-60 70-40 87-13 90-51 71-31 88-26 256
257 89-95 70-68 87-55 90-87 71-59 88-69 257
258 90-30 70 95 87-97 91-22 71-87 89-11 258
259 90-65 71-23 88-40 91-57 72-15 89-54 259
260 91-00 71-50 88-82 91-93 72-43 89-97 260
261 91-35 71-78 89-25 92-28 72-71 90-40 261

262 91-70 72-05 89-67 92-64 72-99 90-83 262
263 92-05 72-33 90-10 92-99 73-26 91-27 263
264 92-40 72-60 90-52 93-34 73-54 91-70 264
265 92-75 72-88 90-95 93-70 73-82 92-13 265
266 93-10 73-15 91-38 94-05 74-10 92-57 266
267 93-45 73-43 91-81 94-40 74-38 93-00 267
268 93-80 73-70 92-24 9476 74-66 93-44 .268
269 94-15 73-98 92-67 95-11 74-94 93-87 269
270 94-50 74-25 93-10 95-46 75-21 94-31 270
271 94-85 74-53 93-54 95-82 75-49 94-75 271

272 95-20 74-80 93-97 96-17 75*77 95-19 272
273 95-55 75-08 94-40 96-52 76-05 95-63 273
274 95-90 75-35 94-84 96-88 76-33 96-07 274
275 96-25 75-63 95-28 97-23 76-61 96-51 275
276 96-60 76-90 95-71 97-59 76-89 96-96 276
277 96-95 76-18 96-15 97-94 77-16 97-40 277
278 97-30 76-45 96-59 98-29 77-44 97-84 278
279 97-65 76-73 97-03 98-65 77-72 98-29 279
280 98-00 77-00 97-47 99-00 78-00 98-73 280
281 98-35 77-28 97-91 99-35 78-28 99-18 281

282 98-70 77-55 98-35 99-71 78-56 99-63 282
283 99-05 77-83 98-80 100-06 78-84 100-08 283
284 99-40 78-10 99-24
285 99-75 78-38 99-68
286 100-10 78-65 100-13
•
TABLE II.
(^15^24^. Cx 5H260.
Per Cent. Per Cent.
Ester Per Cent Per Cent.
Number Acetate. Alcohol. Alcohol in th Per Cent. Per Cent. Alcohol in the Ester
Original Oil. Acetate. Alcohol. Original Oil. Number.
1
1 0-47 0-39 0-39 0-47 0-40 0-40 1
2 0-94 0-79 0-79 0-94 0-79 0-79 2
3 1-40 1-18 1-18 1-41 1-19 1-19 3
4 1-87 1-57 1-58 1-89 1-59 1-59 4
5 2-34 1-96 1-97 2-36 1-98 1-99 5
6 2-81 2-36 2-37 2-83 2-38 2-39 6
7 3*28 2-75 2-76 3-30 2-78 2-79 7
8 3-74 3-14 3-16 3-77 3-17 3-19 8
9 4-21 3-53 3-56 4-24 3-57 3-59 9
10 4-68 3-93 3-96 4-71 3-96 3-99 10
11 5*15 4-32 4-36 5-19 4-36 4-40 11

12 5'61 4-71 4-76 5-66 4-76 4-80 12
13 6-08 5-11 5-16 6-13 5-15 5-20 13
14 6-55 5-50 5-56 6-60 5-55 5-61 14
15 7-02 5-89 5-96 7-07 5-95 6-01 15
16 7-49 6-29 6-36 7-54 6-34 6-42 16
17 7-95 6-68 6-77 8-01 6-74 6-83 17
18 8-42 7-07 7-17 8-49 7-14 7-23 18
19 8-89 7-46 7-57 8-96 7-53 7-64 19
20 9-36 7-86 7-98 9-43 7-93 8-05 20
21 9-83 8-25 8-38 9-90 8-33 8-46 21

22 10-29 8-64 8-79 10-37 8-72 8-87 22
23 10-76 9-03 9-19 10-84 9-12 9-28 23
24 11-23 9-42 9-60 11-31 9-51 9-69 24
25 11-70 9-82 10-01 11-79 9-91 10-10 25
26 12-16 10-21 10-42 12-26 10-30 10-51 26
27 12-63 10-60 10-83 12-73 10-70 10-92 27
28 13-10 11-00 11-24 13-20 11-10 11-34 28
29 13-57 11-39 11-65 13-67 11-49 11-75 29
30 14-04 11-79 12-06 14-14 11-89 12-17 30
31 14-51 12-18 12-47 14-61 12-28 12-58 31

32 14-98 12-57 12-88 15-08 12-68 13-00 32
33 15-45 12-96 13-29 15-55 13-08 13-41 33
34 15-91 13-35 13-71 16-02 13-48 13-83 34
35 16-38 13-75 14-12 16-50 13-88 14-25 35
36 16-85 14-14 14-54 16-97 14-27 14-67 36
37 17-32 14-54 14-95 17-44 14-76 15-09 37
38 17-79 14-93 15-37 17-91 15-06 15-51 38
39 18-25 15-32 15-78 18-38 15-46 15-93 39
40 18-71 35-71 16-20 18-86 15-86 16-35 40
41 19-18 16-10 16-62 19-33 16-25 16-77 41

42 19-65 16-50 17-04 19-80 16-65 17-19 42
43 20-12 16-89 17-46 20-27 17-05 17-61 43
44 20-59 17-28 17-88 20-74 17-44 18-04 44
45 21-05 17-68 18-30 21-21 17-84 18-46 45
46 21-52 18-07 18-72 21-69 18-24 18-89 46
47 21-99 18-46 19-14 22-16 18-63 19-32 47
48 22-46 18-85 19-56 22-63 19-03 19-74 48
49 22-93 19-25 19-98 23-10 19-82 20-17 49
50 23-39 19-64 20-41 23-57 19-43 20-59 50
TABLE II. (continued).
C15H240. C^HÔ.
Ester 3er Cent. Per Cent. Per Cent. Per Cent.

lumber. Acetate. Alcohol. Alcohol in the Per Cent. Per Cent. Alcohol
Acetate. Alcohol. in the Ester
Original Oil. Original Oil. Number.
51 23-86 20-03 20-83 24-04 20-22 21-02 51

52 24-33 20-42 21-26 24-51 20-62 21-45 52
53 24-80 20-82 21-68 24-99 21-01 21-88 53
54 25-26 21-21 22-11 25-46 21-41 22-31 54
55 25-73 21-60 22-54 25-93 21-81 22-74 55
56 26-20 22-00 22-96 26-40 22-20 23-17 56
57 26-67 22-39 23-39 26-87 22-60 23-61 57
58 27-14 22-78 23-82 27-34 23-00 24-04 58
59 27-61 23-17 24-25 27-81 23-39 24-47 59
60 28-07 23-57 24-68 28-29 23-79 24-91 60
61 28-54 23-96 25-11 28-76 24-19 25-34 61

62 29-01 24-35 25-54 29-23 24-58 25-77 62
63 29-48 24-75 25-97 29-70 24-98 26-21 63
64 29-95 25-14 26-41 30-17 25-38 26-65 64
65 30-41 25-53 26-84 30-64 25-77 27-09 65
66 30-88 25-93 27-27 31-11 26-17 27-53 66
67 31-35 26-32 27-71 31-59 26-57 27-97 67
68 31-81 26-71 28-14 32-06 26-96 28-41 68
69 32-28 27-10 28-58 32-53 27-35 28-85 69
70 32-75 27-50 29-02 33-00 27-75 29-29 70
71 33-22 27-89 29-46 33-47 28-15 29-73 71

72 33-69 2828 29-90 33-94 28-54 30-17 72
73 34-15 28-67 30-34 34-41 28-94 30-61 73
74 34-62 29-07 30-78 34-89 29-34 31-06 74
75 35-09 29-46 31-22 35-36 29-73 31-50 75
76 35-56 29-85 31-66 35-83 30-13 31-95 76
77 36-03 30-25 32-10 36-30 30-53 32-40 77
78 36-49 30-64 32-54 36-77 30-92 32-84 78
79 36-96 31-03 32-98 37-24 31-31 33-29 79
80 37-43 31-43 33-43 37-71 31-71 33-74 80
81 3790 31-82 33-87 38-19 32-11 34-19 81

82 38-37 32-21 34-32 38-66 32-50 34-64 82
83 38-84 32-60 34-77 39-13 32-90 35-09 83
84 39-30 33-00 35-22 39-60 33-30 35-54 84
85 39-77 33-39 35-66 40-07 33-69 35-99 85
86 40-24 33-78 36-11 40-54 34-09 36-44 86
87 40-70 34-18 36-56 41-01 34-49 36-90 87
88 41-17 34-57 37-01 41-49 34-88 37-35 88
89 41-64 34-96 37-46 41-96 35-28 37-80 89
90 42-11 35-36 37-92 42-43 35-68 38-26 90
91 42-57 35-75 38-37 42-90 36-08 38-71 91

92 43-04 36-14 38-82 43-37 36-47 39-17 92
93 43-51 36-53 39-27 43-84 36-87 39-63 93
94 43-98 36-92 39-73 44-31 | 37-26 40-09 94
95 44-45 37*32 40-18 44-79 ! 37-66 40-55 95
96 44-92 37-71 40-64 45-26 1 38-05 41*01 96
97 45-39 38-10 41-10 45-73 j 38-45 41-47 97
98 45-85 38-50 41-55 46-20 | 38-85 41-93 98
99 46-32 38-89 42-01 46-67 39-24 42-39 99
100 46-79 39-29 42-47 47-14 ! 39-64 42-86 100
TABLE II. > (continued).

C^HÔ. C^HÔ.
Per Cent. Per Cent.
Cent. Per Cent. Alcohol Ester
Ester Per Cent. Per Cent.
Number. Acetate. Alcohol. Alcohol in the Per
Acetate. Alcohol. in the Number.
Original Oil. Original Oil.
101 47-26 39-68 42-93 47*61 40-04 43-32 101

102 47-72 40-07 43-39 48-09 40-43 43-78 102
103 48-19 40-46 43-85 48-56 40-83 44-24 103
104 48-66 40-85 44-32 49-03 41-23 44-71 104
105 49-13 41-25 44-78 49-50 41-63 45-18 105
106 49-59 41-64 45-24 49-97 42-02 45-65 106
107 50-06 42-04 45-70 50-44 42-42 46-12 107
108 50-53 42-43 46-16 £0-91 42-81 46-59 108
109 51-00 42-82 46-63 51-39 43-21 47-06 109
110 51-46 43-21 47-10 51-86 43-61 47-53 110
111 51-93 43-60 47-57 52-33 44-00 48-00 111

112 52-40 44-00 48-04 52-80 44-40 48-47 112
113 52-87 44-39 48-50 53-27 44-80 1 48-94 113
114 53-34 44-78 48-97 53-74 45-19 49-42 114
115 53-81 45-17 49-44 54-21 45-59 49-89 115
116 54-28 45-57 49-91 54-69 45-99 50-86 116
117 54-74 45-96 50-39 55-16 46-38 50-84 117
118 55-21 46-35 50-86 55-63 46-78 51-32 118
119 55-68 46-74 51-33 56-10 47-18 51*80 119
120 56-14 47-14 51-81 56-57 47-57 ! 52-28 120
121 56-61 47-53 52-28 57-04 47-97 52-76 121

122 57-08 47-92 52-76 57-51 48-36 53-24 122
123 57-55 48-32 53-23 57-99 48-76 53-72 123
124 58-01 48-71 53-71 58-46 49-16 54-20 124
125 58-48 49-10 54-18 58-93 49-55 54-68 125
> 126 58-95 49-50 54-66 59-40 49-95 55-17 126
127 59-42 49-89 55-14 59-87 50-35 55-65 127
128 59-89 £0-28 55-62 60'34 50-74 56-18 128
129 60-36 50-67 56-11 60-81 51-14 56-62 129
130 60-82 51-07 56-59 61-28 51-54 57-10 130
131 61-29 51-46 57-07 61-75 51-93 57-59 131

132 61-76 51-85 57*55 62-22' 52-33 5808 132
133 62-23 52-25 58-03 62-70 52-73 58-57 133
134 62-70 52-64 58-52 63-17 53-12 59-06 134
135 63-16 53-03 59-00 63-64 53-52 59-55 135
136 63-63 53*42 59-49 64-11 53-92 60-04 136
137 64-10 53-82 59-98 64-59 54-31 60-53 137
138 64-57 54-21 60-47 65-06 54-71 61-02 138
139 65-04 54-60 60-96 65-53 55-11 6151 139
140 65-50 55-00 61-45 66-00 55-50 62-01 140
141 65-97 55-39 61-94 66-47 55*90 6250 141

142 66-44 55-78 6243 66-94 56-30 63-00 142
143 66-90 56-18 62-93 67-41 56-69 63-50 148
144 67-37 56-57 63-42 67-89 57-09 64-00 144
145 67-84 56-96 63-92 68-36 57-49 64-50 145
146 68-31 57-35 64-41 63-83 57-88 65-00 146
147 68-78 57-75 64-91 69-30 58-28 65-50 147
148 69-25 58-14 65-40 69-77 58-68 66-00 148
149 69-72 58-53 65-90 70-24 59-07 66-50 149
150 70-18 58-93 66-40 70-71 59-46 67-00 150
C]5H240. C15H260.
Ester Per Cent. Per Cent. Per Cent. Per Cent.

Number Acetate. Alcohol. Alcohol in the Per Cent. Per Cent. Alcohol
Acetate. Alcohol. in the Ester
Original Oil. Original Oil. Number.
151 70-65 59-32 66-90 71-19 59-86 67-51 151

152 71-12 59-71 67-40 71-66 60-26 68-01 152
153 71-58 J 60-10 67-90 72-13 60-65 68-52 153
154 72-05 60-50 68-40 72-60 61-05 69-02 154
155 72*52 60-89 68-90 73-07 61-45 69-53 155
156 72-99 61-28 69-41 73-54 61-84 70-04 156
157 73-46 61-68 69-91 74-01 62-24 70-55 157
158 73-92 62-07 70-42 74-49 ; 62-64 71-06 158
159 74-39 62-46 70-29 74-96 63-03 71-57 159
160 74-86 62-86 71-43 75-43 63-43 72-08 160
161 75-33 63-25 71-93 75-90 63-83 72-59 161

162 75-80 63-64 72-44 76-37 64-22 73-10 162
163 76-26 64-03 72-95 76-84 64-62 73-62 163
164 76-73 64-42 73-46 77-31 65-02 74-13 164
165 77-20 64-82 73-97 77-78 65-41 74-65 165
166 77-67 65-21 74-49 78-26 65-81 7516 166
167 78-14 65-60 75-00 78-73 66-21 75-68 167
168 78-60 66-00 75-52 79-20 66-60 76-20 168
169 79-07 66-39 76-03 79-67 67-00 76-72 169
170 79-54 66-79 76-55 80-14 67-39 77-24 170
171 80-01 67-18 77-06 80-61 67-79 77-76 171

172 80-48 67-57 77-58 81 -OS 68-19 78-28 172
173 80-94 67-96 78-10 81-56 68-58 78-81 173
174 81-41 68-35 78-62 82-03 68-98 79-33 174
175 81-88 68-75 79-14 82-50 69-38 79-85 175
176 82-35 69-14 79-66 82-97 69-77 80-38 176 ,
177 82-81 69-54 80-18 83-44 70-17 80'91 177
178 83-28 69-93 80-70 83-91 70-57 81-43 178
179 83-75 70-32 81-23 84-38 70-96 81-96 179
180 84-21 70-71 81-75 84-86 71-36 82-49 180
181 84-68 71-10 82-28 85-33 71-76 83-02 181

182 85-15 71-50 82-80 85-80 72-15 83-55 182
183 85-62 71-89 83-33 86-27 72-55 84-09 183
184 86-09 72-28 83-86 86-74 72-95 84-62 184
185 86-56 72-68 84-39 87-21 73*34 85-15 185
186 87-03 73-07 84-92 87-68 73-74 85-69 186
187 87-49 73-46 85-45 88-16 74-14 86-22 187
188 87-96 73-86 85-98 88-63 74-53 86-76 188
189 88-43 74-25 86-51 89-10 74-93 87-30 189
190 88-89 74-64 87-05 89-57 75-32 87*84 190
191 89-36 75-03 87-58 90*04 75-72 88-38 191

192 89-83 75-42 88-12 90-51 76-12 88-92 192
193 90-30 75-82 8865 90-98 76-51 89-46 193
194 90-77 76-21 89-19 91-46 76-91 90-09 194
195 91-24 76-60 89-73 91-93 77-31 90-54 195
196 91-70 77-00 90-27 92-40 77-70 91-09 196
197 92-17 77-39 90-81 92-87 78-10 91-64 197
198 92-64 77-78 91-35 93-34 78-50 92-18 198
199 93-11 78-17 91-89 93-81 78-89 92-73 199
200 93-57 78-57 92-44 94-28 79-29 93-28 200
THE ANALYSIS OF ESSENTIAL O.ILS 333

^15^24^' C15H2fiO.
[
Per Cent. Per Cent.
Ester Per Cent. Per Cent. Alcohol in the Per Cent. Per Cent. Alcohol in the Ester
Number. Acetate. Alcohol. Original Oil. Acetate. Alcohol. Original Oil. Number.
201 94-04 78-96 92-98 94-76 79-68 93-83 201

202 94-51 79-35 S3-53 95-23 80-08 94-38 202
203 94-98 79-75 94-07 95-70 80-48 94-93 203
204 95-44 80-14 94-62 96-17 80-87 95-48 204
205 9591 80-53 95-17 96-64 81-26 96-03 205
206 96-38 80-92 95-72 97-11 81-66 96-59 206
207 96-85 81-32 96-27 97-58 82-06 97*14 207
208 97-32 81-71 96-82 98-05 82-45 97-70 208
209 97-79 82-10 97-37 98-52 82-85 98-25 209
210 98-25 82-50 97*92 99-00 83-25 98-81 210
211 98-72 82-89 98-48 99-47 83-64 99-37 211

212 99-19 83-28 99-03 99-94 84-04 99-93 212
213 99-66 83-67 99-59 100-41 84-44 100-49 213
214 100-12 84-07 100-14 214
TABLE III.—GEBANYL TIGLINATE : C4H7CO2C10H17.
feJs
<g ^ -|
-4-3
£3 il
*-!'
||
•g u.
f1
el
|
|
Is sl p
1 § ?Jj l| f|
^1 |1 f_ ~X
fc £ £ 52; £ 525 £ fc £^
1 0-42 21 8-85 41 17-28 61 25-71 81 34-13
2 0-84 22 9-27 42 17-70 62 26-13 82 34-55
3 1-26 23 9-69 43 18-12 63 2655 83 34-98
4 1-69 24 10-11 44 18-54 64 26-97 84 35-40
5 2-11 25 10-54 45 18-96 65 27-39 85 35-82
6 2-53 26 10-96 46 19-38 66 27-81 86 36-24
7 2-95 27 11-38 47 19-80 67 28*23 87 36-66
8 3-37 28 11-80 48 20-23 68 28-65 88 37-09
9 3-79 29 12-22 49 20-65 69 29-08 89 37-51
10 4-21 30 12-64 50 21-07 70 29-50 90 37-93
11 4-63 31 13-06 51 21-49 71 29-92 91 38-35

12 5-05 32 13-49 52 21-91 72 30-34 92 38-77
13 5-47 33 13-91 53 22-33 73 30-76 93 39-19
14 5*90 34 14-38 54 22-75 74 31-18 94 39-62
15 6-32 35 14-75 55 23-18 75 31-61 95 40-04
16 6-74 36 15-17 56 23-60 76 32-03 96 40-46
17 7-16 37 15-59 57 24-02 77 32-45 97 40-88
18 7-58 38 16-01 58 24-44 78 32-87 98 41-30
19 8-01 39 16-44 59 24-87 79 33-29 99 41-72
20 8-43 40 16-86 60 25-29 80 33-71 100 42-14
The importance of strictly adhering to the conditions above set out

in the acetylation process has been emphasised by several analysts.
According to Durrans1 the anhydrous sodium acetate acts rather as a
. and E.O.R., 1912, 123.
334 THE. CHEMISTEY OF ESSENTIAL OILS
dehydrating agent than a catalytic agent, since increasing the proportion
results in higher values for the alcohol percentage. This was confirmed
by Umney and Bennett,1 who showed that with pure geraniol 109 per
cent, was indicated when the proportion of anhydrous sodium acetate
was increased to 5 grams, whilst with 2 grams the theoretical percentage
was obtained.
SEPARATE DETERMINATION OF CITRONELLOL IN PRESENCE OF
GERANIOL.
Several methods have been proposed for the separation of geraniol
and citronellol which occur together in otto of rose and in rose-geranium
oils. On treating the mixture with phosphorus trichloride in ethereal
solution, geraniol is partly converbed into hydrocarbons and partly into
geranyl chloride, whilst citronellol is converted into a chlorinated acid
ester of phosphorous acid which is soluble in alkalis and can thus be
separated. By heating a mixture of geraniol and citronellol with phthalic
anhydride to 200° the geraniol is destroyed and the citronellol converted
into a phthalic acid ester, the sodium salt of which is soluble in water
and can be saponified by alcoholic potash. Geraniol can also be de-
stroyed by heating with benzoyl chloride to 140° to 160°.
. The only practical method which appears to give good results depends
on the fact that when a mixture of geraniol and citronellol are heated
with strong formic acid (100 per cent.) the geraniol is decomposed and
the citronellol is converted into citronellyl formate. The estimation is
best carried out as follows : —
To 10 c.c. of the oil (otto of rose or rose-geranium oil) 10 c.c. of formic
acid 100 per cent, (specific gravity 1'22) is added, and the mixture gently
boiled under a reflux condenser for one hour. The mixture is cooled,
100 c.c. of water added, and the whole transferred to a separator. The
aqueous layer is rejected, and the oil washed with successive quantities of
water as in the acetylation process. The formylated oil is dried with
anhydrous sodium sulphate, and about 2 grams neutralised and saponi-
fied with alcoholic potash in the usual manner. The percentage of
citronellol is then calculated from the following formula : —-
,, , , x x 15'6
citronellol percentage = —
where x = the number of c.cs. of normal potash absorbed and W = the
weight of formylated oil taken.
Citronellal and geraniol occur together in citronella oils, and several .
methods have been proposed for the estimation of these two constituents.
The results are only approximate in each case. These are as follows : —
1. Phenylhydrazine method of Kleber.
2. Oximation method of Dupont and Labaune.
3. Sulphite —Bisulphite method of Boulez.
The Phenylhydrazine method is carried out as follows : —
One gram of Ceylon citronella oil or 0*5 grams of Java citronella oil
is mixed with 10 c.c. of a freshly prepared 2 per cent, alcoholic solution
of redistilled phenylhydrazine and allowed to stand for one to one and a
half hours in a flask of about 50 c.c. capacity closed with a glass stopper.
Twenty c.c. of decinormal hydrochloric acid is then added, thoroughly
1
P. and E.O.R., 1912, 250.
mixed, 10 c.c. of benzene is then added, and the mixture allowed to stand
in a separator after being well shaken. The acid layer which measures
30 c.c. is filtered through a small filter and 20 c.c. of the filtrate is titrated
with decinormal alcoholic potash, using ethyl orange as indicator. The
amount required for the whole 30 c.c. of filtrate is then calculated, and
the quantity deducted from the amount required in a blank experiment
without the oil. Each c.c. of decinormal potash shown by the difference
in titration represents 0*0154 grams citronellal. The results obtained
vary somewhat according to the excess of phenylhydrazine absorbed and
according to the time allowed for the reaction.
The Oximation process depends on the fact that citronellal oxime, pro-
duced by shaking in the cold with a solution of hydroxylamine, is con-
verted on heating with acetic anhydride into a nitrile which is not affected
by saponification with alcoholic potash. The difference between the
molecular weight of the nitrile formed and that of citronellal is so small
as to be negligible, and the calculation of the percentage of geraniol from
the saponitication value is made by the usual formula. The method of
procedure is as follows:—
Ten grams of hydroxylamine hydrochloride are dissolved in 25 c.c. of
water ; 10 grams of carbonate of potash, separately dissolved in 25 c.c. of
water, are then added and the mixture filtered. With this solution 10
grams of the oil are thoroughly shaken for two hours at 15° to 18° C. The
oil is then separated, dried with anhydrous sodium sulphate, and acetyl-
ated with twice its volume of acetic.anhydride and one-fifth of its weight
of anhydrous sodium acetate for two hours under a reflux condenser.
The oil is washed, dried, and neutralised, and a weighed quantity (about
2 grams) saponified with alcoholic potash in the usual manner.
A Java oil which showed 83 per cent, of total acetylisable constituents
gave 43 per cent, of geraniol and 40 per cent, of citronellal, whilst a
Ceylon oil containing 60*2 per cent, of total acetylisable constituents was
found to contain 43 per cent, of geraniol.
The Sulphite-Bisulphite method devised by Boulez is conducted as
follows :—
25 or 50 grams of the oil are shaken in an Erlenmeyer flask with 100
or 200 grams of solution of bisulphite of soda, saturated with neutral
sodium sulphite, and allowed to stand for two to three hours with oc-
casional agitation. 100 to 200 grams of water are then added and the
mixture heated for several hours under a reflux condenser, with frequent
shaking until a clear oily layer is obtained on standing. The mixture is
transferred to a separator and the oil separated and measured. The loss
is taken to represent the amount of aldehyde, but the separated bisulphite
solution retains a small quantity of oil which can be extracted with ether.1
The geraniol content is determined in the residual oil by acetylation. The
results obtained by this method compare favourably with those obtained
by the oximation process.
DETERMINATION OF ALDEHYDES AND KETONES.
These two classes of bodies are somewhat closely related in chemical
constitution, and similar processes are therefore available for their estima-
tion. Both contain the carbonyl group, "/CO, owing to the presence of
1
P. and E.O.R., 1912, 334.
which they are capable of forming various addition and condensation
products with certain inorganic and organic reagents, as, for example,
sodium bisulphite or sulphite, hydroxylamine, phenylhydrazine, and its
nitro-derivative, ^-nitrophenylhydrazine, cyanacetic acid, hydrocyanic
acid, and semioxamazide. Some of these compounds are soluble in
water, and thus allow of the separation of the aldehydes or ketones from
the other insoluble constituents of the essential oils; others, on the other
hand, are crystalline, and can be separated by filtration from the rest of
the oil; while in the remaining cases, the reagent is added in excess, and
the quantity absorbed by the aldehyde or ketone determined.
The processes depending on the use of sodium bisulphite or sulphite,
and in which the aldehyde or ketone compounds dissolve in the solution
of the reagent, are known as absorption processes, and are those most
commonly employed for oils containing a high proportion of aldehydes
and ketones, the use of sodium bisulphite being probably still the method
most usually adopted for aldehydes, though the use of neutral sodium
sulphite is the official process in the British Pharmacopoeia of 1914, and
is also that most suitable for the estimation of ketones.
Bisulphite Method.—This is based on the general reaction
/OH
E . CHO + NaHSO3 = R . CH<
\SO3Na
and many variations have been proposed for carrying it out, some favour-
ing the addition of acid, such as acetic, others the use of alkali, such as
sodium carbonate. The process, as now ordinarily employed, is carried
out as follows :—
From 5 to 10 c.c. of the oil are measured carefully into a flask capable
of holding about 150 to 200 c.c., having a long narrow neck graduated
into 1/10 c.c. About an equal volume of a hot nearly saturated solution
(35 per cent.) of sodium bisulphite is added, the whole well shaken for a
few minutes, and then introduced into a boiling water-bath. Successive
small quantities of the bisulphite solution are gradually added with
vigorous shaking, until the flask is nearly full, and the flask kept in the
boiling water-bath until the solid compound at first produced is com-
pletely dissolved, and the oily layer of unabsorbed residue rises to the
surface. More bisulphite salution is then run in until the unabsorbed
oil rises in the graduated neck of the flask, when its volume is read, after
cooling. Two precautions must here be taken. Firstly, the temperature
at which the oil is measured originally, and that at which the unabsorbed
residue is measured, must be identical. Secondly, it must be remembered
that the measurements only give the volume percentages, hence to de-
termine the percentage by weight it is necessary to know the specific
gravity of the oil and of the non-absorbable residue. Of course the latter
can be separated and weighed, but the advantages of this are more than
counterbalanced by the loss in weight experienced whilst removing the
last traces of water.
It is advisable, generally speaking, to take about an hour over the
addition of the bisulphite solution, and heating in a water-bath, but in the
case of cassia oils containing much resinous matter it is sometimes neces-
sary to prolong the heating in boiling water for three or four hours before
the unabsorbed oil separates as a clear oil on the top of the solution.
This method gives good results for the estimation of cinnamic aide-
hyde in cassia and cinnamon bark oils, citral in lemon-grass oil, benz-
aldehyde in bitter almond oil, citronellal in eucalyptus citriodora oil, and
anisic aldehyde in aubepine or crategine. It has, however, the disad-
vantages that it takes not less than one hour, and there is no definite
indication when all the aldehyde has been completely absorbed, as there
is with the Neutral Sulphite process.
This is based on an observation of Tiemann's that when citral is-
shaken with a neutral solution of sodium sulphite, a compound with the
citral is produced, with simultaneous liberation of sodium hydroxide.
The reaction which takes place has not been absolutely established.
Tiemann considered that it proceeded according to the equation—
C9H15CHO + 2Na2SO3 + 2H2O = C9H17(NaSO3)2. CHO + 2NaOH
in which case reaction would only occur with unsaturated aldehydes or
ketones, but Sadtler,1 as the result of an investigation of a large number
of aldehydes and ketones was at first led to conclude that the reaction
was a general one for saturated and unsaturated aldehydes of both the
aliphatic and aromatic series, and that it should be represented by the
following equations for aldehydes and ketones respectively :—
B. CHO + 2Na2SO3 + 2H2O = E . CH : (NaSO3) + 2NaOH + H2O.
E . CO . E'. + 2Na2SO3 + 2H2O = EE'. C : (NaSO3) + 2NaOH + H2O;
though with ketones the reaction was not so general, carvone and
pulegone readily entering into combination with the sodium sulphite,,
whereas thujone did not do so. Based on the above equations, the
amount of alkali liberated is proportional 2to the quantity of aldehyde or
ketone entering into reaction, and Sadtler proposed this as a method for
determining the percentage of these substances in an essential oil, titrat-
ing the liberated alkali with semi-normal hydrochloric acid, and using;
rosolic acid as indicator. Unfortunately the end point of this reaction is
not very definite, and Sadtler, moreover, as the result of fuller investi-
gation of the subject,8 found the reaction was neither so general nor so
definite for aldehydes and ketones as was at first supposed. Whilst citral,
cinnamic aldehyde, carvone, and pulegone combine with two molecules
of sodium sulphite, benzaldehyde and vanillin are found to react with
only one molecule, the reaction with benzaldehyde being represented by
the equation—
/OH
C6H5CHO + Na2S03 + H2O = C6H5CH<x . + NaOH.
SO3Na
Besides thujone, citronellal, camphor, menthone, and fenchone did
not react with the sodium sulphite at all.
Sadtler concluded finally that double bonds seem to aid in bringing
about reaction when close to the . CHO group, e.g., citral, cinnamic alde-
hyde, and that proximity of the benzene nucleus to -the . CHO group, as>
in the case of benzaldehyde and vanillin, was also probably a factor,
while the only active ketones were those containing double bonds near to
the . CO group.
The aldehyde and ketone compounds formed with the sodium sulphite
are readily soluble in water, and H. E. Burgess4 makes use of this fact
l
2
Amer. J. Pharm.,31904, 84, and Jour. Soc. Chem. Ind., 1904, 4 303.
Loc. cit. J. Amer. Chem. Soc., 1905,1325. Analyst, 1904, 78.
VOL. ii. 22
to employ the reaction as the basis for an absorption process, a measured
quantity of the oil being heated with a neutral solution of sodium sulphite,
and the reduction in volume due to the solution of the aldehyde or ketone
compound, indicating the proportion of aldehyde or ketone present in the
oil. The alkaii liberated as the result of the reaction must be neutralised
as* fast as produced, and the absence of any further production of alkali
serves to denote the completion of the process. The estimation as de-
vised by Burgess is carried out as follows :—
Five c.c. of the oil are introduced into a 200 c.c, flask having a neck
graduated to 5 c.c. in 1/10 of a c.c., with a side tubulus reaching to the
bottom of the flask for introducing the oil, reagents, and water. To the
measured oil i$ added a saturated solution of neutral sulphite of soda and
two drops of ordinary phenolphthalein solution ; it is then placed in a
water-bath and thoroughly shaken, when a red colour is quickly produced.
It is carefully neutralised with 1 to 10 solution of acetic acid until, after
the addition of a few drops of acid, no further cojour is produced. The
oil is then run up into the graduated neck, and when cold carefully read.
The difference between 5 c.c. and the reading will give the amount of oil
absorbed, and this multiplied by 20 the percentage of aldehyde or ketone.
It will be noticed that Burgess recommends a special and rather more
complicated absorption flask than that used in the bisulphite process, but
this is not necessary, and offers no advantage over the Ordinary absorp-
tion flask already described (p. 336).
Burgess has applied this process to many aldehydes and ketones, and
finds it to give good results with anisic aldehyde, benzaldehyde, cinnamic
aldehyde, citral, carvone, pulegone, and the oils of bitter almonds, cara-
way, cassia, cinnamon, cumin, dill, lemon-grass, pennyroyal, and spear-
mint. Contrary to Sadtler, citronellal is found to react, but it forms a
milky solution, and at first is very frothy, so that care is necessary to
prevent loss. The reaction takes considerable time and heating for com-
pletion, but good results were obtained. Cumic aldehyde at first forms a
solid compound, but this goes into solution on heating with addition of
acetic acid. Litmus is a better indicator than phenolphthalein in the
case of this aldehyde, and should also be used for the oils of cumin and
pennyroyal. Considerable time and heating are required to complete
the reaction with nonyl and decyl aldehydes, but satisfactory results may
be obtained.
Mention has already been made of the fact that thujone and fenchone
do not react with sodium sulphite ; consequently the method is useless
for tansy, thuja, wormseed, and fennel oils.
The determination of citral in letnon-grass oil by the neutral sulphite
absorption process gives results some 4 per cent, lower than those obtained
by the bisulphite method, but the latter is that usually adopted in com-
merce, though, as alreadv stated, the former is official in the new British
Pharmacopoeia.
Labb6l recommends a slight modification of the above process, by
whieh he claims that the separation of crystals at the junction between
the unabsorbed oil and the sulphite liquor is prevented, and greater
accuracy in reading off the percentage therefore attained. He employs a
stoppered bulb, prolonged at the bottom into a graduated cylindrical
closed tube, and into this are introduced 5 c.c. of the oil, together with
1
Journ. de la Pmf. Francaise, 1913, 37.
about 60 c.c. of a cold saturated solution of sodium bicarbonate and
neutral sodium sulphite. After shaking vigorously for half a minute, the
apparatus is almost filled with the sulphite solution, the whole again
shaken for a few minutes, and the apparatus inverted when the unab-
sorbed oil rises cleanly into the graduated tube, and its volume may be
read off.
In all the foregoing cases, the percentage of aldehyde or ketone is so
high that the estimation by the above processes can be sufficiently ac-
curately carried out on the original oil. With such oils as lemon, orange,
hand-pressed lime, and citron or cedrat, however, the proportion of
aldehydes is so small that it is not possible to satisfactorily determine it
directly on the oil itself by absorption processes, and a preliminary con-
centration of the aldehydes in the oils by carefully fractionating out the
hydrocarbons in vacuo has therefore been proposed by Burgess and Child
who recommend the operation to be carried out as follows:—
One hundred c.c. of the oil to be examined are put into a distilling
flask having three bulbs blown* in the neck, and fitted with cork and
thermometer. This is connected to a condenser with a suitable receiver,
iiaving two vessels graduated at 10 c.c. and 80 c.c. respectively. A
JBruhl's apparatus answers the purpose very well. The whole is ex-
hausted, and a pressure of,not more than 15 mm. should be obtained.
The flask is now gently heated by means of an oil-bath, and 10 c.c.
distilled into the first tube. The next vessel is then put into position and
the distillation continued until 80 c.c. have distilled over. The pressure
is now relieved, and the residual oil in the flask distilled over with steam,
when the terpeneless oil, or aldehydes and other oxygenated constituents
-are obtained. The volume of this fraction is carefully noted, and the
•optical rotations and refractive indices of all three fractions determined,
after which the proportion of aldehyde is estimated on a known volume
of the third fraction by either the bisulphite or the neutral sulphite
method described above. For example, supposing 7 c.c. of oil were
obtained for the third fraction of a sample of lemon oil, and that of the
5 c.c., 2*1 c.c. were absorbed in the aldehyde determination, the percentage
2*1 x 20 x 7
of citral in the original lemon oil would be ^-^ = 2*9 per cent.
JLUU
IBy this process lemon oils are found to contain some 2-5 to 3 per cent,
aldehydes, hand-pressed lime oil 8 per cent., citron or cedrat oil 4 per
cent., and orange oil 0*75 to 1 per cent, but more recent work has shown
that these results are somewhat too low, due probably in part to some
of the aldehydes distilling over with the terpenes, and for oils containing
only a small percentage of aldehydes, a volumetric method, such as the
hydroxylamine jwocess, as modified by A. H. Bennetl is much to be
preferred, as being both simpler and more rapid to carry out, and also
more accurate.
For the estimation of benzaldehyde, Eipper 2 proposed a volumetric
•modification of the bisulphite process, the aldehyde being shaken with
a measured volume of a standard solution of bisulphite, and the excess
of bisulphite titrated back with iodine solution at a low temperaturer
Dodge8 found this give fairly accurate results, and recommends the
iollowmg method of carrying out the determination. About 0*15 gram
1 2
Analyst, 31909,U. Monats. f. Ghem., 1900, 1079.
Int. Congress of Applied Chem., 1912, xvii. 15.
bitter almond oil is weighed into a flask containing exactly 25 c.c. N/5
bisulphite solution, and the mixture gently shaken. The flask is then
closed, immersed in an ice-bath for one and a half to two hours, and the
cold solution titrated with N/10 iodine solution, using starch as indicator.
A blank test is made in a similar manner, and from the bisulphite used
up, the benzaldehyde may be calculated, 1 c.c. N/10 iodine solution being
equivalent to O0053 gram benzaldehyde. Feinberg1 also finds this
method very suitable for the estimation of benzaldehyde.
Hydroxylamine Method.—The use of hydroxylamine for the estimation
of citral in lemon oil was first proposed by J. Walther 2 who dissolved
the oil in alcohol, and boiled the solution under a reflux condenser, with
excess of a 5 per cent, solution of hydroxylamine hydrochloride, the
hydroxylamine being liberated from the hydrochloride by addition of 0*5
to 1 gram of sodium bicarbonate. , The resulting evolution of carbon
dioxide has been found, however, to carry off hydroxylamine with it, the
error thus produced varying with the time and rate of boiling and other
conditions, while a further objection to ihe process is that oils containing
different percentages of aldehydes and ketones require different treatment,
with regard to the quantity of hydroxylamine and bicarbonate of soda
necessary, and no definite instructions for its use, which will apply to all
oils, can therefore be given.
The reaction is a general one for aldehydes and ketones, aldoximes-
and ketoximes respectively being produced, according to the equations:—
E. CHO + H9NOH = ECH . NOH + H90
EE'. CO + H2NOH EE'C . NOH + H90
and the following are some results which have been obtained with
various aldehydes and carvone under different conditions as to quantities
of hydroxylamine and sodium bicarbonate, and as to time of boiling:—
Hydrox-
Bicar- Mol. ylamine Hydrox- time of
Weight bonate Per-
Substance. Bicar- taken
taken. Soda. bonate. ylamine Heating centage.
— rt p
C
N
~ °- - TIT
used. (minutes).
NaOH.
Benzaldehyde 1-034 0-4 0-5 124 91 30 93-3

>} 1-039 0-8 1-0 124 94 30 95-9
» 1-037 0-8 1-0 378 85 60 86-9
>» 0-935 1-1 1-5 378 . 79 30 89-6
>» 0-900 1-0 1-5 150 75 60 88-3
Carvone . 1-411 0-8 1-0 378 90 30 95-7
»» 1-410 0-8 10 378 83 60 88-9
1-408 1-1 1-3 378 89 30 94-8
» 1-346 1-0 1-3 150 80 60 89-2
Caraway oil 2-135 1-0 150 '78 60 54-8
Citronellal 1-276 0-35 —
0-5 124 40 30 48-3
19 1-308 0-7 1-0 124 61 30 71-8
>» 1-320 1-1 1-5 378 50 30 58-3
Cuminic aldehyde 1-442 0-4 0-5 124 91 30 93-4
11 1-459 0-8 1-0 124 93 30 94-3
1
2
Int.
Congress of Applied Chem., i. 187.
Pharm. Ctntralb., 40, 1899, 621.
As regards the use of hydroxylamine for the estimation of ketones, it was
recommended by Kremers in 19011 for the estimation of carvone in
spearmint oil, the ketoxime being formed by treating the oil with
hydroxylamine, and the remainder of the oil removed by steam distilla-
tion, the crystalline ketoxime which is left being separated, dried, and
weighed.
E. K. Nelson 2 has applied a slight modification of Walther's process,
especially to the determination of ketones. He heats from 1 to 2 grams
in a water-bath under a reflux condenser, with 35 c.c. of a hydroxylamine
solution, prepared by dissolving 20 grams hydroxylamine hydrochloride
in 30 c.c. water and adding 125 c.c. alcohol free from aldehyde, and 2
grams sodium bicarbonate. The mixture is cooled, rendered acid by
addition of 6 c.c. concentrated hydrochloric acid through the condenser,
and the whole diluted to 500 c.c. with water. The solution is then
filtered and an aliquot part neutralised with N/2 NaOH solution to methyl
orange, and finally the excess of hydroxylamine titrated with N/10 NaOH
to phenolphthalein. This method is found to give fairly accurate results
for the estimation of carvone in spearmint, thujone in tansy and worm-
wood oils, pulegone in pennyroyal oil, and camphor in rosemary oil, but
proved less satisfactory for the estimation of fenchone.
The process has been much improved by A. H. Bennett3 who sub-
stitutes N/2 alcoholic potash for sodium bicarbonate in order to liberate
the hydroxylamine, and this modification is now adopted in the British
Pharmacopoeia as the official method for the estimation of citral in lemon
oil, and is also the process in general use in this country for the purpose.
It is carried out by taking 20 c.c. of oil, adding 20 c.c. of N/2 alcoholic
hydroxylamine hydrochloride solution (in 80 per cent, alcohol), and 8 c.c.
of N/l alcoholic potash, together with 20 c.c. strong alcohol, and gently
boiling the mixture, under a reflux condenser for half an hour, after
which it is cooled, the condenser carefully washed down with distilled
water, and the whole diluted with distilled water to about 250 c.c., the
undecomposed hydroxylamine hydrochloride being then neutralised to
phenolphthalein with N/2 alcoholic potash, and the hydroxylamine re-
maining unabsorbed by the aldehyde then titrated with N/2 sulphuric
acid, using methyl orange as indicator. A blank test is made in exactly
the same manner, omitting only the oil, and the difference between the
number of c.c. of N/2 acid required in the two cases in the final titration
represents the number of c.cs. of N/2 acid which will neutralise the
hydroxylamine absorbed by the aldehyde or ketone, and this, in the case
of lemon oil, multiplied by 0*076 gives the grams of citral in 20 c.c. of
the oil, and from a knowledge of the specific gravity of the oil, the per-
centage of citral by weight can thence be readily calculated. The process
gives slightly too low results, some 5 to 10 per cent, below the true
aldehyde content, but in the case of oils containing only a comparatively
small quantity of aldehyde or ketone, as with lemon or lime oil, this is
unimportant, and concordant results by different observers are readily
obtained.4 In the case of oils containing a large proportion of aldehyde
or ketone, however, the error wou],d be of considerable importance, and
the process is therefore not suitable in such cases.
Phenylhydrazine Methods.—In addition to the general reaction between
almost all aldehydes and ketones and hydroxylamine, there is another
2
Joum. Soc. Chem. Ind.t 1901, 16. J. Ind. Eng. Chem., 1911, 588.
-Loc. cit. * P. and E.O.R., 1913, 269.
'equally characteristic reaction between both these classes of compounds
and phenylhydrazine, the condensation products formed being usually
crystalline, and sparingly soluble compounds, termed phenylhydrazones,
or simply hydrazones. The reactions taking place may be represented
by the following equations:—
C6H5CHO + C6H5NH . NH2 = C6H5CH : N . NH . C6H5.
Benzaldehyde. Phenylhydrazine.
CH8. C9HW. CO + C6H5NH . NH2 ., CH3. C9H19. C : N . NH . C6H6.
Methyl nonyl kefeone. Phenylhydrazine.
Several processes for the estimation of aldehydes and ketones have
been based on these reactions, some depending on the separation and
weighing of the insoluble hydrazone, others on treatment of the substance
with an excess of phenylhydrazine, and estimation of the unused reagent.
Among the earliest to suggest this method for the estimation of
aldehydes and ketones were Benedikt and Strache,1 who treated the
aldehyde or ketone with an excess of phenylhydrazine, filtered off the
hydrazone produced, and oxidised the uncombined phenylhydrazine with
Fehling's solution, measuring the nitrogen thereby evolved. The process,
which .really measures the—CO contained by the bodies, has been slightly
modified by Watson Smith, junior,2 who uses a current of carbon dioxide
instead of steam for driving off the nitrogen. Each c.c. of nitrogen cor-
responds to 1*252 mgs.—GO, and the process gives good results with
benzaldehyde, cuminic aldehyde, and methyl nonyl ketone (rue oil), but
with other aldehydes is unsatisfactory.
P. B. Bother has proposed to estimate the excess of phenylhydrazine
by adding to it an excess of standard N/10 iodine solution and titrating
back with N/10 thiosulphate solution, 0*1 gram phenylhydrazine cor-
responding to 37 c.c. N/10 iodine solution. Prom 0'5 to 1 gram of oil
(or in the case of lemon oil, 10 grams) is dissolved in a 250 c.c. flask in
about 30 c.c. alcohol, and enough of a 1 per cent, phenylhydrazine solu-
tion added to give 1 molecule for each molecule of aldehyde. The mixture
is well shaken, and allowed to stand for fifteen hours in the dark with
occasional shaking. It is then diluted with water and filtered through a
plaited paper into a litre'flask containing about 500 c.c. water and 10 to>
20 c.c. N/10 iodine solution. The filter is well washed with water, and
the filtrate titrated back with N/10 thiosulphate solution, using starch as
indicator. The method gives good results with oils rich in aldehydes,
but for lemon oil is not nearly so accurate as the Kleber modification
described below.
The gravimetric method which is specially suitable for the determina-3
tion of small quantities of benzaldehyde is recommended both by H^rissey,
Denis, and Dunbar.4 The former adds 1 c.c freshly-distilled phenyl-
hydrazine and 0*5 c.c. glacial acetic acid to so much of the benzaldehyde
as will yield 0*1 to 0'2 gram hydrazone, heats for twenty to thirty minutes
in a boiling-water bath, and after twelve hours, filters on a Gooch crucible,
washes with 20 c.c. water, and dries in the vacuum desiccator. Denis and
Dunbar, whose process is suggested for the examination of extracts of
almonds, mix 10 c.c. of the extract with 10 to 15 c.c. of a freshly prepared
10 per cent, phenylhydrazine solution, shake thoroughly, and allow to
1 2
3
Monats. f. Chem., Ig93, 273- Clum. News, 1906, 83.
4
Jown. de Pharm. et Chem., 1906,60.
Journ. Ind. and Eng. Chtm., 1909, 256.
stand in dark for twelve hours, at the end of which 200 c.o. cold water
are addel, and the mixture filtered through a Gooch crucible. The pre-
cipitate is washed first with cold water and afterwards with 10 c.c. of 10
per cent, alcohol, dried for three hours in vacua at 70° to 80° C., and
weighed. The weight obtained multiplied by 5408 gives grams henz-
aldehyde in 100 c.c. of the solution.
The most important application of the phenylhydrazine reaction to
essential oil analysis is the process devised by Kleber tor the determina-
tion of citral in lemon oill in which the excess of phenylhydrazine is
titrated 'with standard acid to diethyl orange as indicator. Kleber re-
commends the process to be carried put as follows: About 10 grams
lemon oil are accurately weighed into a flask, 20 c.c. of freshly prepared
5 per cent, alcoholic phenylhydrazine solution added, the flask closed,
and allowed to stand about thirty minutes, after which sufficient N/2
hydrochloric acid is added to exactly neutralise the phenylhydrazine
solution, this quantity being previously determined by a blank test with
the phenylhydrazine only. The neutralised mixture is transferred to a
separator, the flask being rinsed with 20 o.c. water, and the whole vigor-
ously shaken, when on standing two layers separate, the lower one of
whieh is drawn off into a flask, the residue in the separator washed with
5 0.0. water, and the washing added to the liquor previously withdrawn,
this being then titrated with N/2 soda, using diethyl orange as indicator,
and titrating to a brownish tint which precedes the pink coloration.
Each c.c. of N/2 soda required corresponds to 0*076 gram citral. Kleber
found this process satisfactory for the estimation of citral in lemon oil
and citropellal in citronella oils, and considered it capable of general
application for the estimation of aldehydes and ketones. The accuracy
of the method for the examination of lemon oil has been confirmed by
several American chemists* and also by Schimmel,2 who recommend the
following modification: About 2 c.c. of lemon oil are accurately weighed
into a 50 c.c. glass-stoppered bottle, mixed with 10 c.c. of a freshly pre-
pared 2 per cent, phenylhydrazine solution, and allowed to stand for one
hour; 20 c.e, N/10 HG1 are then added, together with 10 c.c. benzene,
the mixture thoroughly shaken, and transferred to a separating funnel.
After standing, an acid layer amounting to about 30 c.c. separates to the
bottom. This is filtered off, and 20 c.c. of the filtrate titrated with N/10
KOH, using 10 drops of a 1 in 2000 diethyl orange solution, as indicator,
and adding potash until a distinct yellow colour appears. A blank test
without oil is made in a similar manner, and from the difference in the
amount of potash required by the two tests, the quantity of citral in the
oil can be calculated. The phenylhydrazine solution rapidly deteriorates.
and should be prepared fresh each time; it should never be used more
than twenty-foux hours old. Schimmel has also proved the value of this
proeess io the estimation of cuminic aldehyde, benzaldehyde, and methyl
nooftyl ketone, but find it useless for fenchone, thujone, camphor, and
menthone.
Phenylhydrazine Derivatives.—The use of w-nitrophenylhydrazimand
j9-bromphenylhydrazine has been proposed by Hanus for the determina-
tion of vanillin, and Van Ekenstein and J. J. Blanksma in 1905 sug-
gested the use of jo-nitrophenylhydrazine as a reagent for aldehydes and
ketones generally, in all three cases the precipitated hydrazone being
1 2
Amer. Perfumer, 1912, 284. Semi-annual Report, April, 1912, 77.
filtered off, washed, dried, and weighed. Feinberg,1 experimenting with
the two latter reagents, finds both to give good results with vanillin and
anisic aldehyde. The last-named is also satisfactory for the estimation
of benzaldehyde, but jp-bromphenylhydrazine gives too low results.
Colorimetric Processes.—Various colorimetric methods have been pro-
posed for the estimation2 of aldehydes, one of the most important being
that of E. McK. Chace, which is based on the well-known reaction of
aldehydes with a fuchsine solution decolorised by means of sulphur
dioxide, the colour produced when this reagent is added to a known
quantity of the oil being matched by a standard solution of the pure
aldehyde. The fuchsine reagent is prepared by dissolving 0-5 gram,
fuchsine in 100 c.c. of water, adding a solution containing 16 grams
sulphur dioxide, and allowing it to stand until colourless, when the
solution is made up to 1 litre. In carrying out the estimation, 2 grams
of the lemon oil are diluted to 100 c.c. with aldehyde free alcohol, pre-
pared by allowing to stand over alkali for several days, distilling, boiling,
the distillate for several hours under a reflux condenser with 25 grams
per litre of m-phenylenediamine hydrochloride, and redistilling. Four
c.c. of this solution are then diluted with 20 c.c. aldehyde free alcohol,
20 c.c. of the fuchsine solution added, and the total volume made up to
50 c.c. with the alcohol. The colour thus produced is compared with
standards prepared in the same way, but with known quantities of a 2
per cent, alcoholic solution of pure citral in place of the solution of oil,
all the solutions being left for ten minutes in a water-bath at a tempera-
ture not exceeding 15° C., and the colours compared either directly or by
means of a colorimeter. The method gives good results with lemon
extracts or mixtures of citral with limonene, but with lemon oil itself a
satisfactory degree of accuracy is not attainable owing to slight turbidity
of the solution due to certain wax-like constituents of the oil, and results
differing by as much as 1*25 per cent, citral on the oil may be easily
obtained, so that this process, though useful for lemon essences, cannot
be regarded as suitable for3the analysis of lemon oil.
Woodman and Lyford recommend a very slight modification of the
above process for the determination of benzaldehyde in extracts of bitter
almonds, the aldehyde free alcohol being prepared by treating it first with
silver oxide, tben with m-phenylenediamine hydrochloride, passing a
strong current of air through it for three hours, and then distilling,
rejecting the first 100 c.c. of distillate.
Another colorimetric method for the estimation of citral is that due to
R. S. Hiltner,4 who substitutes a 1 per cent, solution of m-phenylenedi-
amine hydrochloride in 50 per cent, alcohol for the fuchsine solution em-
ployed by Chace, but otherwise the process is similar, the yellow colour
produced by the m-phenylenediamine and the oil being matched by
means of a standard alcoholic solution of citral. The reaction is more
distinct than in Chace's process, and the results are claimed to be more
accurate, as acetaldehyde and citronellal give no coloration under the ex-
perimental conditions, with m-phenylenediamine. Old lemon oils which
have become oxidised give a yellow-green to blue-green coloration, accord-
ing to the degree of oxidation, and this renders the process useless for
old oils. The estimation is carried out by weighing out 1*5 to 2 grams
1
Eighth Inter. Congress Applied Chem., 1912, 1, 187.
2
4
J. Amer. Chem. Soc., 1906, 1472. »IWd.f 1908, 1607. -
e7". Ind. Etig. Chem., 1909, 798.
lemon oil, diluting to 50 c.c. with 90 to 95 per cent, alcohol and to 2 c.c.
»of this solution, adding 10 c.c. of the m-phenylenediamine solution. The
onixture is diluted to a given volume, and the colour produced matched
by means of a 0*1 per cent, solution of citral in 50 per cent, alcohol.
A modification of the Hiltner method of estimating citral is de-
.-scribed in the Journal of Industrial and Engineering Chemistry1 by
»C. E. Parker and-B. S. Hiltner. In the determination of citral by the
i metaphenylene-diamine method it not infrequently occurs that lemon
iand orange oils and extracts produce blue or green colours instead of
yellow. This abnormal behaviour has somewhat restricted the applica-
bility of the method. Experiments have shown that substances such as
^Fuller's earth, animal charcoal, talcum, pumice, zinc powder, platinised
asbestos, eponite, and kaolin, employed for decolorising the reagent
.affect the metaphenylene-diamine in some obscure way, rendering it
imore responsive to the action of a citrus oil which has the property of
producing the blue colour. Further experiments favour the presumption
that oxidation of the terpene is in part responsible for the production of
:the blue colour. Stannous chloride was found to prevent the formation
-of the blue colour, whether added in solid form or in aqueous or alcoholic
solution. The addition of a proper amount of oxalic acid to the original
Hiltner reagent was found to accomplish the desired object in the most
simple and convenient way, and was finally adopted for the proposed
method. If the various samples are mixed with the reagent at the same
rtime, as many as a dozen can be compared with a single standard within
an hour without any substantial error, but in order to do this it is de-
sirable to employ always a fixed amount of citral in solution. The
^details of the improved method are as follows: Reagents.—Alcohol of 94
.to 95 per cent, strength, practically colourless, may be employed. Citral
.Standard Solutions.—0*5 gram of citral is dissolved in alcohol (94
per cent.) and made up to 50 c.c. Of this 1 per cent, solution, 10 c.c. are
•diluted to 100 c.c. Each c.c. of this contains O'OOl gram citral.
These solutions may be kept in a refrigerator, but should be measured at
room temperature, Metaphenylene diamine Hydrochloride : Oxalic. Acid
.Solution.—Dissolve 1 gram metaphenylene-diamine hydrochloride and
1 gram -of crystallised oxalic acid, each in about 45 c.c. of 80 per cent.
;alcohol. Mix in a stoppered 100 c.c. graduated flask or cylinder, and
jmake up to the mark with 80 per cent, alcohol. Add 2 or 3 grams
Fuller's earth, shake well, allow to settle, and decant through a double
.filter. When most of the liquid has run through, add the turbid residue
to the liquid in the filter. Colorimeter.—Any form of colorimeter may
be used. Manipulation.—Weigh into a 50 c.c. graduated flask about
>0'5 gram lemon oil, or about 4 grams orange oil, or 10 grams lemon
extract, or 50 c.c. orange extract respectively; make up to the mark with
94 per cent, alcohol, stopper and mix the contents. Pipette 5 c.c. of
these first dilutions into 50 c.c. graduated flasks. Pipette also 4 c.c. of
the standard 0-1 per cent, citral solution into a 100 c.c. flask. As nearly
as possible at the same time add from a small'graduated cylinder to the
-50 c.c. tiasks 10-c.c., and to the 100 c.c. flask 20 c.c. of the metaphenylene-
diamine reagent; make all up to the mark with 95 per cent, alcohol,
-stopper the flask and mix well. Empty the 100 c.c. flask of citral dilu-
tion into the plunger tube* of the colorimeter, and a 50 c.c. flask of the
-1 August, 1918, p. 608 (through P. and E.O.R. (1918), 256).

unknown dilution into a comparison tube. Both comparison tubes;
should be graduated in millimetres. Adjust the plunger until both
halves of the field have the same intensity of colour, and note the heights-
of the columns compared. Calculate the average of five or more ob-
servations. From these preliminary results compute the amount of the
first dilution of the unknown, which should be used in making the
second dilution to produce the same colour as the standard in the same
height of column of liquid. Eepeat the determination, preparing at the
same time fresh dilutions of the standard and unknown until columns,
of liquid of equal intensity of colour differ in length not more than 5 or
10 per cent.
Calculation—
(a) = gram of citral (0*002) in 50 c.c. of diluted standard used for
comparison.
(b) — grams of oil or extract weighed.
(c) = volume in c.c. (50) of first dilution of unknown.
(d) —• volume in c.c. of same used for second dilution.
(e) = height of column (mm.) of standard used for comparison.
(/*) = height of column (mm.) of unknown used for comparison.
m, a x c x e x 100 , ., . . ., . . .
Then ^ -j — = rper cent, citral in oil or extract.
b x a x /7
For the estimation of vanillin, T. von Fallenburgl proposes to make*
use of the colour produced by treating a dilute aqueous solution with-
isobutyl alcohol and concentrated sulphuric acid. Five c.c. of the solution
are mixed with 5 c.c. of a 1 per cent, isobutyl alcohol solution in 95 per
cent, alcohol, and 25 c.c. concentrated sulphuric acid, the colour produced
being compared after forty-five minutes with that given by known amounts
of vanillin.
The following processes have been recommended for the determina-
tion of aldehydes and ketones :—
Semioxamazide.—A gravimetric method for the estimation of cinnamic
aldehyde ia cassia and cinnamon oils, but which appears to apply only
to this aldehyde, has been devised by Hanus2 based on the formation of
a crystalline semioxamazone when cinnamic aldehyde is treated with seini-
oxamazide, the reaction being—
CONH. NH2 CONH . N : CH . CH : CH . C6H5
| + C8H7. CHO | + H80-
CONH2 CONH2
The process is carried out by accurately weighing 0*15 to 0*2 gram-
cinnamon or cassia oil in a 250 c.c. conical flask, adding 85 c.c. water,
and shaking thoroughly, after which about 1-J- times the quantity of
semioxamazide, dissolved in hot water, is added, the mixture well shaken
for five minutes, and then allowed to stand for twenty-four hours with-
occasional shaking, especially during the first three hours. The semi-^
oxamazone separates in the form of small flakes, which are filtered through
a Gooch tile, washed with cold water, dried at 105° C. till constant, and
weighed. The process gives accurate results for the estimation of em-
namic aldehyde not only in cassia and cinnamon oils but also in cinnamon
bark, and is for this latter purpose particularly suitable, the oil from 5 to*
1 2
Chem. Zentr., 1916, 391. Zeit&. Untera. Nahr. Gen. Mittel, 1903, 817.
8 grams bark being steam distilled, the distillate extracted with ether, the
ether evaporated off, and the aldehyde estimated as above described.
Cyanacetic Acid, Hydrocyanic Acid.—When an aldehyde is treated
with cyanacetic acid in the presence of potassium -hydroxide, condensation
takes place according to the general equation—
/ON
K . CHO + CH2CN . COOH _ ECH : C< + H2O.
X3OOH
The condensation product is soluble, and it has been proposed to make
use of this reaction as an absorption process for the determination of citral
in lemon oil, but owing to a very indistinct separation between the un-
absorbed oil and the absorbing solution, it has been found practically im-
possible to get satisfactory results and the process has been abandoned in
practice.
A general property of aldehydes and ketones is that when heated with
hydrocyanic acid, additive compounds, termed nitriles or cyanohydrins,
are produced, according to the general equations—
B . CHO + HCN - E . CH(OH)CN
BE'. CO + HCN - BE'. C(OH)CN
On this reaction F. de Myttenaere has endeavoured to base a process,
for the estimation of aldehydes and ketones, adding sufficient of a dilute
(0*4: per cent.) aqueous or faintly alkaline solution of hydrocyanic acid to
give about 4 molecules hydrocyanic acid per molecule of aldehyde or
ketone, and measuring the total and free hydrocyanic acid after first
heating the mixture for seventy-five minutes in the water-bath in a sealed
flask, and then allowing to stand for twelve hours at room temperature.
The total hydrocyanic acid is estimated by adding exactly 6 c.c. of the
solution to be tested to 75 c.c, water, followed by 10 drops of 40 per
cent, soda solution, 10 c.c. 17 per cent, ammonia solution, and a few drops
of 10 per cent, potassium iodide solution, and then titrating with N/100
silver nitrate. The free hydrocyanic acid the author determines by add-
ing 3 c.c. of the solution to be tested to 50 c.c. N/100 silver nitrate in a
100 c.c. flask, diluting to 100 c.c. with water, filtering, and' titrating the
excess of silver nitrate in 50 c.c. filtrate by means of N/100 ammonium
thiocyanate, using iron alum as indicator. The author has obtained good
results with this process in the estimation of benzaldehyde, but it failed
with citral and vanillin, and also with ketones.
Sodium Salicylate,—When an aldehyde is shaken with a saturated
solution of sodium salicylate, there seems to be evidence of the formation
of a weak molecular compound, and with cinnamic aldehyde well-defined
crystals have been obtained which give on analysis :—
Found. Theoretical.
Sodium . . . . . . . . 7*3 per cent. 7-9 per cent.

,, salicylate 53-5 54-8
This process, though referred to by Burgess,1 never seems to have-

been very seriously investigated.
. 79.
.348 THE CHEMISTKY OF ESSENTIAL OILS
Acetylation.—Citronellal may be quantitatively estimated by the
ordinary acetylation process1 when the aldehyde is quantitatively con-
verted into isopulegyl acetate, which is then determined by saponification
with potash in the ordinary way. Dupont and Labaume2 have attempted
•to base a method for the separation of geraniol from citronellal in citron-
ella oils on the fact that the citronellal oxime formed by shaking with
hydroxylamine solution at the ordinary temperature is not converted
into an ester by subsequent acetylation, but into the nitrile of citronellic
acid which is stable towards' alkali during the saponifi cation process.
Cannizzaro's Reaction.—On this reaction, which may be represented
thus—
2C6H5CHO + KOH = C6H5COOK + C6H5CH2OH,
3
Dodge has based a process for the determination of benzaldehyde. A
strong (2'5 N) alcoholic potash solution is required for the estimation,
which is performed .by allowing a mixture of 10 c.c. of this solution with
1 to 2 grams benzaldehyde to stand at the ordinary temperature for
twenty-four hours, after which the unabsorbed potash is titrated back
with N/2 hydrochloric acid. A blank test is also made, and from the
amount of potash entering into reaction, the percentage of aldehyde can
be calculated. The process breaks down in the assay of natural oil of
bitter almonds, probably due to the presence of benzaldehyde cyanhydrin.
THE DETERMINATION OF PHENOLS.
The usual method for the determination of phenols is based on the
solubility of these compounds in solutions of caustic alkali. Such ab-
sorption methods are not strictly accurate, since a small portion of con-
stituents other than phenols are dissolved by the alkali. So long,
however, as the conditions are kept constant, useful comparative results
are obtained. The process is best carried out as follows :—
Five to 10 c.c. of the oil are shaken in a Hirschsohn flask, as used
for cassia oil analysis, with a 5 per cent, solution of caustic soda, until
absorption is complete, and the unabsorbed oil driven into the neck of
the flask by more of the solution and its volume read off. The difference
between the original amount of oil used and the unabsorbed portion may
be taken as phenols. Strictly speaking, this method gives a volume
percentage, which can be converted into a weight percentage if the specific
gravities of the two portions of the oil be known.
Schryver 4 has recommended the use of sodamide for the determina-
tion of phenols; the hydrogen of the phenolic hydroxyl replaces the sodium
with the formation of an equivalent quantity of ammonia,
NaNH2 + HO. B' = NaOK' + NHS.
About 1 gram of sodamide in fine powder is washed several times with
benzene and placed in a 200 c.c. flask. About 50 c.c. of benzene, free
from thiophene, is added, and the flask, attached to a condenser, warmed
-on the water-bath, and traces of ammonia are removed by a stream of
carbon dioxide. From 1 to 2 grams of the phenol-containing oil is then
.admitted to the flask through a stoppered funnel inserted through the
1
2
Determination of Alcohols, p. 297.
3
Roure-Bertrand's Report, April, 1912, 3.
4
Eighth Inter. Congress of Applied Chem., 1912, xvii. 15.
Jour. Soc. Chem. Ind., 18 (1899), 553.
cork, the last traces being washed through with benzene. The contents-
of the flask are again heafced and a current of air driverj through until
all the ammonia generated is carried over and absorbed in a given volume
(about 20 c.c.) of normal sulphuric acid in a suitable collecting vessel.
The amount of phenol is calculated on the basis of the equation given
above.
Kremers recommends the following method of estimating thymol:—
Five c.c. of the oil to be examined are weighed and brought into a
glass-stoppered burette graduated to -^ c.c., and is diluted with about
an equal volume of petroleum ether; a 5 per cent, potassium hydroxide
solution is added, and the mixture shaken for a short time, then the
liquid is left standing until separation is complete. Then the alkaline
solution is allowed to run into a 100 c.c. graduated flask. This opera-
tion is repeated until no further decrease in the volume of the oil takes-
place.
The alkaline solution of thymol is made up to 100 or 200 c.c. as the
case may require, using a 5 per cent, soda solution. To 10 c.c. of this-
solution in a graduated 500 c.c. flask is added a ~j normal iodine solu-
tion in slight excess, whereupon the thymol is precipitated as a dark
reddish-brown iodine compound. In order to ascertain whether a suf-
ficient quantity of iodine has been added, a few drops are transferred
into a test tube and a few drops of dilute hydrochloric acid are added.
When enough iodine is present, the brown colour of the solution indi-
cates the presence of iodine, otherwise the liquid appears milky by the
separation of thymol. If an excess of iodine is present, the solution is
slightly acidified with dilute hydrochloric acid and diluted to 500 c.c.
From this 100 c.c. are filtered,off, and the excess of iodine determined by
titration with ^ normal solution of sodium thiosulphate. For calcula-
tion, the numbej of cubic centimetres required is deducted from the
number of cubic centimetres of -f^ normal iodine solution added and
the resultant figure multiplied by 5, which gives the number of cubic,
centimetres of iodine required by the thymol.
Every cubic centimetre of y^ normal iodine solution equals 0'003753
gram of thymol. Knowing the quantity of thymol in the alkaline solu-
tion, the percentage in the original oil is readily found.
The reaction taking place is represented by the equation—
C10H14O + 41 + 2NaOH = C10H12I2O + 2NaI + 2H2O
In the estimation of carvacrol a slight modification of this method
must be made, because carvacrol is thrown down as a finely divided
white precipitate, giving the solution a milky appearance. In order to
form a precipitate the liquid is vigorously shaken after the addition of
iodine solution, and is subsequently filtered. Then the liquid is acidu-
lated with hydrochloric acid, and subsequently the same procedure is
followed as was described for thymol. The calculation is also the same.
Eedman, Weith, and Brock l have modified the above-described
method, by using sodium bicarbonate instead of sodium hydroxide..
They proceed as follows :—
About 50 c.c. of n-sodium bicarbonate solution is placed in a glass-
stoppered bottle of 500 c.c. capacity and diluted with 100 c.c. water. To.
this is added from a burette 15 c.c. of a solution containing as much of
the phenol under examination as corresponds to about a decinormal
1
Jour. Ind. Eng. Chem., 5 (1913), 831.
.-solution. To this is added -£$ normal iodine solution in excess until a
permanent brown colour is obtained. The excess of iodine should
;amount to 20 c.c. The mixture is now vigorously shaken for one minute,
^diluted with 50 c.c. of n-sulphuric acid, and the excess of iodine titrated
back with decinormal thiosulphate solution, 5 c.c. of a 20 per cent, potas-
sium iodide solution being added. Starch is used as an indicator. The
^temperature should be from 20° to 25°.
In order that the reaction may proceed rapidly it is important to
shake the mixture thoroughly after adding the iodine solution. When
this is done the iodine compound is formed completely within one minute.
With thymol it affords thymol di-iodide. In order to make sure that any
iodine which may have entered into the hydroxyl-group is again liberated,
care should be taken that a little hydriodic acid is always present ; hence
the addition of the potassium iodide solution before the excess of iodine
is titrated back with thiosulphate. Tit rat ion can only be regarded as
•complete when the blue coloration does not return in 10 minutes.
For the determination of eugenol Thorns has elaborated the follow-
ing method, the results of which are fairly accurate : —
About 5 grams of the oil are weighed into a beaker of about 150 c.c.
capacity, 20 grams of ^15 per cent, sodium hydroxide solution added, and
then b grams benzoyl chloride. On stirring, the solid mass of eugenol
sodium salt at first formed goes into solution again as it is converted
into benzoic ester, with evolution of much heat. In the course of a few
minutes the reaction ends, and on cooling a solid crystalline mass of
benzoyl eugenol is obtained. To this 50 c.c. water is added, and the whole
warmed on a water-bath until the ester is completely melted to an oil,
well stirred, cooled, and the clear supernatant aqueous solution filtered
off. The crystalline mass is again washed with two successive quan-
tities of 50 c.c. water, and the resulting impure benzoyl eugenol is re-
crystallised from alcohol, due allowance being made for its solubility in
that medium. 25 c.c. of hot alcohol (90 per cent, by weight strength)
are poured through the filter employed in the previous washing opera-
tions, in order to dissolve any adherent crystals, into the beaker, and
the whole warmed upon the water-bath until complete solution is effected.
The solution is then cooled to 17° C., and the crystalline precipitate
thrown upon a small weighed filter paper, filtered into a 25 c.c. cylinder,
and washed with 90 per cent, alcohol until the filtrate exactly measures
25 c.c. The filter and crystals are then removed to a weighing bottle,
dried at 100° C. until constant, and then weighed. From the total
weight the weights of the filter paper and of the weighing bottle are
deducted, from which the benzoyl eugenol is calculated. To th« latter
weight 0*55 gram are added, being the weight of pure benzoyl eugenol
•dissolved by 25 c.c. 90 per cent, alcohol at 17° C. as determined by ex-
periment.
This final quantity gives the amount of benzoyl eugenol, from which
the amount of eugenol is easily calculated, eugenol having the formula
C10H12O2, and benzoyl eugenol C17H16O3, so that xgg- x 100 •* the per-
centage of eugenol if x equals the weight of benzoyl eugenol obtained,
and y the weight of oil used in the estimation, under these circum-
stances the eugenol -content should not fall below 75 per cent., or if
estimated by absorption with potash not below 82 per cent., usually from
85 to 90 per cent.
THE ANALYSIS OP ESSENTIAL OILS 351
Thorn has recognised that the foregoing process is only approximately
.-accurate and now recommends the following modification, This consists
in heating 5 grams of the oil in a water-hath with 20 c.c, of a 15 per
•cent, soda solution for thirty minutes. After allowing the hydrocarbons
to separate, the eugenol soda solution is run off, and the hydrocarbons
washed with dilute soda solution twice, the washings being added to the
original soda solution. The reaction is now effected at water-bath tem-
perature with 6 grams of benzoyl chloride. The whole is allowed to cool,
and the crystalline mass transferred to a beaker with 55 c.c. of water. It
is heated in order to melt the crystals, and well agitated with the water
to wash the benzoyl eugenol. This washing is repeated. twice. The
•crystalline mass is then transferred to a beaker with 25 c.c. of 90 per
<sent. alcohol, and warmed till complete solution takes place. The solu-
tion is allowed to stand till the bulk of the crystals have separated out,
and is cooled to 17° and filtered through a paper 9 cm. in diameter,
previously dried and tarred. The filtrate measures about 20 c.c. and the
•crystals are washed with more alcohol until it measures 25 c.c. The
•paper and crystals are then dried in a weighing-glass and weighed, the
temperature of drying being not more than 101° C. The solubility allow-
ance for 25 c.c. «of alcohol is 0*55 gram. The total eugenol is calculated,
from the formmla
* °'55
676
where P is the percentage, a the weight of benzoyl eugenol obtained,
cand b is the weight of clove oil used.
Verley and Bolsing propose the following method. It depends on the
iact that acetic and other anhydrides react with phenols in excess of
pyridine. Eugenol reacts readily forming eugenol acetate and acetic
acid, the latter combining with pyridine to form pyridine acetate. This
-compound reacts towards indicators such as phenol-phthalein in the same
way as acetic acid, and therefore a titration is possible. Yerley and
.Bolsing use from 1 to 2 grams of the oil, which js placed in a 200 c.c. flask,
and 25 c.c. of a mixture of acetic anhydride (15 parts) and pyridine (100
parts). The mixture is heated for thirty minutes on a water-bath, the
liquid cooled, and 25 c.c. of water added. The mixture is well shaken
-and titrated with normal potash, using phenolphthalein as indicator. A
blank experiment is carried out without the eugenol, and the difference
between the titration figures in c.c. of normal alkali, multiplied by 0*582,
.gives the amoaint of eugenol in the sample taken.
DBTBBMINATION OF THE METHYL NUMBER.

Benedikt and Griissner1 have proposed the determination of the
methyl number in the analysis of essential oils. Whilst this process may
have some value in the examination of the constitution of a compound,
it is very rarely necessary to use it in the analysis of essential oils. The
methyl number (which is a somewhat fallacious term as it includes other
;alkyl radicles) is understood as the number of milligrams of methyl
yielded by the gram of the substance when heated with hydriodic aoid.
From 0*2 to 0*3 gram of the oil is heated with hydriodic acid of specific
^gravity 1*7 and the methyl iodide formed collected in a suitable receiver,
1
Chem. Zeit.t 13 (1899), 872,1087.
free iodine being absorbed by phosphorus. The methyl (or alkyl) iodide-
is decomposed by alcoholic solution of silver nitrate, and the silver iodide
weighed, from which the amount of alkyl radicle, calculated as CH3 i&
found.
THE DETECTION OF CHLOBINE IN ESSENTIAL OILS.
A few essential oils contain substances which can be easily synthesised.
by processes in which the use of chlorine is involved. Such oils are*
frequently adulterated with the synthetic product. If this contains
chlorine—which is very frequently the case, on account of the difficulty
in removing the last traces of this body—its detection becomes of im-
portance, as the presence of a trace of chlorine is evidence of the presence-
of the artificial compound.
The Determination of Chlorine.—Many methods ha,ve been suggested
for the detection and determination of chlorine, but most of them are
merely qualitative. Of these the following are useful:—
(a) By simple combustion. This method depends on the fact that on
combustion a portion of the chlorine present in the organic compounds-
existing as impurities forms hydrochloric acid, which can be detected by
means of silver nitrate.
A piece of filtering paper about 2 inches by 1 inch, and rolled in the
shape of a spill, is saturated with the oil, the excess of oil is thrown off"
and the paper is placed in a small porcelain dish which in its turn re-
poses in a larger dish, measuring about 8 inches in diameter. The paper
is ignited, and a beaker, of a capacity of about 2 litres, moistened inside
with distilled water, is quickly placed over the paper. The sizes of the
dishes used must be such that the rim of the larger dish must stand out
well all round from the beaker. After the flame is extinguished the
beaker should be left in position for about one minute, after which the
products of combustion which have been deposited against the moist
sides of the beaker are rinsed out with a little distilled water, and filtered.
The filterate, acidulated with a drop of nitric acid, must remain clear when
silver nitrate solution is added.
Care must be taken that the filter paper is free from chlorine. Thig
should be determined by a blank experiment. This process has been
strongly recommended by Schimmel & Co., but there is considerable
doubt whether it will detect minute quantities of chlorine.
(b) The sodium test is distinctly more delicate, and is carried out as-
follows:—
A piece of pure metallic sodium about half the size of a pea is dropped,
into 0*5 c.c. of the oil in a dry test tube, and heated until all chemical
action has ceased. The test tube and contents are immersed whilst still
hot in 10 c.c. of distilled water in a porcelain dish. The solution i&
filtered, acidulated with nitric acid, and silver nitrate solution added.
Any turbidity or opalescence indicates the presence of chlorine compounds.
A blank test should be performed to ensure the absence of chlorine in
the materials employed.
(c) The lime combustion method gives good results as a qualitative
test, although it will often fail to detect very minute traces, say below
0*08\ per cent. It is carried out as follows :—
A mixture of 1 c.c. of benzaldehyde and 5 grams of lime are placed in
the bottom cf a platinum crucible about 3 ins. in depth, a layer of lime
placed on the top and the crucible covered and gently heated; a con-
siderable escape of benzaldehyde takes place, so that it is obvious that
the results can have no quantitative value.
The temperature is then gradually increased until no further vapours
are driven off. The mixture is then dissolved in dilute nitric acid, filtered
and tested in the usual manner with silver nitrate.
The method of Carius for the determination of chlorine in organic
compounds is, of course, absolutely quantitative, but is very tedious, and
is scarcely suitable for the detection of very small traces of chlorine, as
the weight of oil taken in a Carius determination never exceeds 0*5 grams.
Salamon has recommended the following method, and appended are
the results obtained compared with those yielded by the Carius' method
and the obviously inadequate lime method.
About 2 grams of benzaldehyde are heated in a retort with 40 c.c. of
concentrated sulphuric acid, the fumes collected in a solution of silver
nitrate, and the heating continued until no further precipitate insoluble
in hot dilute nitric acid is obtained in the silver nitrate solution. This
takes about three hours.
The solution of silver nitrate is acidified with dilute nitric acid, boiled
so as to decompose any silver sulphite that might have been formed,
and the precipitate filtered, washed, etc.
A slight modification consists in using a mixture of 40 c.c. concen-
trated sulphuric acid and 5 c.c. concentrated nitric acid, the nitric acid
being added last to the mixture of sulphuric acid and benzaldehyde.
The hydrochloric acid was evolved more rapidly, and slightly higher
results were obtained in certain cases, due probably to better oxidation.
By using this modification, a test can be easily carried out in one hour.
In using this method the heating must be very gradual, the mixture
should not be allowed to froth until the end of the operation, and a blank
should be carried out on the reagents used.
In cases where the amount of chlorine is very small such as *005 per
cent., it is advisable to carry out, say, distillations on 5 separate quantities
of about 2 grams each, collecting them all in the same receiver.
By this means an appreciable amount of precipitate can be obtained,
and definitely identified.
Lime Method, Sulphuric Acid Nitro-sulphuric Carius Method,

No. Chlorine, per Cent. Method, per Cent. Acid Method, per per Cent.
Cent.
1 •19 1-83 2-14 2-2

2 Not weighable. 0-13 0-13 0-15
3 •20 1-8 1-9 2-0
4 •19 1-7 1-7 1-9
5 nil. trace trace trace
G •17 1-63
7 •28 — 2-66
8 •17 1-42 —
—
—
THE DETERMINATION OF HYDROCARBONS.

The determination of hydrocarbons is not often required, but is a
matter of some importance in the case of the so-called terpeneless and
sesquiterpeneless oils, especially those of lemon, many commercial
samples of which contain appreciable quantities of hydrocarbons.
VOL. n. 23
Booker l has elaborated the following method for the determination
of the hydrocarbons present in concentrated oils of lemon :—
Citral is first estimated in 10 c.c. of oil by the sulphite method. When
the oil which has not entered into reaction is less than 6 c.c., the estima-
tion is repeated with another 5 or 10 c.c. The oil left over from these
tests is bulked, and 5 c.c. of this citral-free oil is placed in a 600 to
700 c.c. separator, into which, immediately previously, 500 c.c. of alcohol
of precisely 51 per cent, by volume, cooled down to from 0 to — 2° C.,
has been introduced. The separator is closed with a cork and the con-
tents are repeatedly shaken, when the aromatic bodies of the oil are dis-
solved by the alcohol, while the hydrocarbons are left behind almost
quantitatively. The separator is then placed in a cooling-bath at 0° C.,
cork downwards, for six to ten hours. It is then taken out of the freez-
ing mixture, carefully turned back to its proper position, and placed in a
stand. When the alcoholic solution has cleared to ,a point at which only
a slight film remains (which in certain conditions may take up to two
days) it is drawn off to about 10 c.c., any oil-drops which may still adhere
to the sides of the funnel being rinsed down with ice-cold 51 per cent,
alcohol, so that all the oil which has remained undissolved is brought
together. When the mixture has become perfectly clear, the oil, being
freed as far as possible from the last traces of alcoholic solution, is trans-
ferred to a measuring tube calibrated to y1^ c.c., and the vessel rinsed out
with a little more ice-cold 51 per cent, alcohol. It is advisable to use a
separating funnel of which the lower part ends in a narrow graduated
tube. As soon as the oil is completely cleared (when the froth is very
persistent a few drops of dilute acetic acid should be added), the volume
is read off and calculated to the original oil.
The method may be completed by estimating not only the quantity
but also the character of the hydrocarbons. Thus, from 100 to 200 c.c.
of oil is fractionally distilled in vacuo. The distillation is only continued
up to the point where the separate fractions of about 10 c.c. each still
show dextro-rotation. These fractions are put together as the " terpene-
containing portion " of the oil, the rest constituting the " sesquiterpene-
containing portion ". Each of these portions is then freed from citral
by means of Na2SO3, and in both cases the residue is treated with 100
times its quantity of ice-cold 51 per cent, alcohol, as described above, a
large glass fla^k being, if necessary, substituted for the separator. The
alcohol solution is separated by means of a siphon from the portion which
has remained undissolved. The oils which have been separated are
estimated quantitatively, and from the values thus obtained the per-
centage of terpenes and sesquiterpenes in the original oil is calculated.
For purposes of further identification the rotation is estimated, and, if
necessary, the characteristic derivatives are prepared. The terpenes,
of which the principal constituent is d-limonene, are characterised by a
pronounced dextro-rotation; they yield a liberal proportion of limonene
tetrabromide, whereas the sesquiterpenes, which consist chiefly of
bisabolene, are laevo-rotatory and may be identified from the bisabolene
trihydrochloride.
1
Jour. Prakt. Chem. (1914), 89, 199.
THE HYDROGEN NUMBER OF ESSENTIAL OILS.

A new method for the examination of certain oils has recently been
described by Allan E. Albright.1
Some unsaturated compounds are capable of quantitative hydrogena-
ifcion in a solution of colloidal palladium. It has been found that a
^hydrogen number" corresponding to the iodine number of fatty oils
may be ascribed to some ethereal oils.
The colloidal palladium solution is prepared as follows : A solution
of a palladium silt is added to a solution of an alkali salt of an acid of high
molecular weight, the sodium salt of protalbinic acid being suitable. An
excess of alkali dissolves the precipitate formed, and the solution contains
tihe palladium in the form of a hydrosol of its hydroxide. The solution
is purified by dialysis, and the hydroxide reduced with hydrazine hydrate.
On further dialysis and evaporation to dryness a water-soluble product
is obtained, consisting of colloidal palladium and sodium protalbinate, the
latter acting as a protective colloid.
A substitute may be prepared thus: 0'05 gram palladous chloride is
placed in a special shaking flask with 50 c.c. of 50 per cent, alcohol and
1 or 2 c c. of 1 per cent, aqueous solution of gum-arabic, the weight of
gum being about one-fourth the weight of the palladous chloride. On
shaking this mixture in an atmosphere of hydrogen the chloride is re-
duced with formation of a black solution of colloidal platinum, which is
rendered stable by the small quantity of gum present.
The apparatus used is somewhat complicated, and consists of shaking
baskets containing the absorption flasks, which are connected with a gas
•burette and a hydrogen supply, the latter being purified by passing
"through a wash bottle containing alkaline permanganate, and afterwards
-washing with water. Arrangements are made to correct errors due to
absorption of hydrogen by the catalyser, the solubility of the gas in the
-solvent, and the consumption of hydrogen by oxygen dissolved in the
-solvent. The weight of the substance taken is adjusted so that 100 c.c.
•or less of hydrogen is absorbed.
Every essential oil contains at least small quantities of unsaturated
substances, such as terpenes (limonene phellandrene, etc.), but not all
»bonds are hydrogenated with equal ease. For instance, limonene is first
reduced to carvomenthene, citral to citronellal, carvoxime to carvotan-
;acetoxime, the second bond in each case requiring a considerably longer
treatment for complete saturation. For such substances a quantitative
determination is unsatisfactory. Some oils, however, contain substances
which are completely arid rapidly reduced, notably those containing the
.allyl or propenyl group. Safrol, anethol, and eugenol are the chief sub-
stances which have been studied, and these are reduced to dihydro-safrol,
dihydro-anethol, and dihydro-eugenol. The pure substances have been
-compared with the natural oils of sassafras, anise, fennel, clove, and
pimento, and with imitation oils made up of the active constituent and
limonene.
The hydrogen number is defined as the number of c.c. of hydrogen
•corrected to normal temperature and pressure absorbed by 1 gram of the
material during the period of rapid absorption. This number gives a
measure of the proportion of active constituent present, but the results
l
Jour. Amer. Chem. Soc., 1914, 2188; through P. and E.O.R.
are generally too high because of the absorption of hydrogen by other
constituents.
The results obtained are summarised in the following table:—
Hydrogen Equivalent per Theoretical per

Substance. Number. Cent, of Active Cent, of Active
Constituent. Constituent.
Safrol 135-6 98-3 100-0

Limonene . . . . . — ! —
Imitation sassafras oil 111-9 81-1 80-0
Authentic „ ,, . 103-1 74-8
102-0 74-0
Anethol 150-5 99-6 —
100-0
Imitation anise oil . 125-1 82-4 80-0
127-0 83-7 80-0
Commercial anise oil . 125-8 82-9
127-3 83-9
„ fennel oil 101-3 66-8 —
102-7 I 67-7 —
Eugenol . . . . . 134-4 98-3 —
100-0
Imitation clove oil . 113-2 82*8 80-0
113-3 82-8 80-0
Commercial clove oil . 114-6 83-8 —
114-0 83-3 —
„ pimento oil 97-8 71-5
97-8 71-5 —
~~
THE DETECTION OF SOME COMMON ADULTERANTS.1

Turpentine Oil.—This is readily recognised in oils which contain no
pinene, as this is the main constituent of turpentine oil. It is usually
found in the first distillates, and generally reduces the specific gravity
and effects the solubility and optical rotation. Its presence is proved by
the formation of pinene hydrochloride (melting-point 125°) and the nitro-
sochloride (melting-point 103°). If pinene is a constituent of the oil
itself, the addition of turpentine can only be proved by comparison with
an authentic sample.
Cedarwood, Copaiba and Gurjun Balsam Oils.—These adulterants are
usually found in the last fractions owing to their high boiling-points.
They have a high specific gravity (*900 to *950) and high refractive index,
and are only soluble in strong alcohol. Copaiba oil rotates - 7" to - 35°
(African up to + 20°), cedarwood - 25° to - 45°, and gurjun balsam
- 35° to - 130°. No definite characteristic derivatives can be obtained.
Gurjun balsam oil gives an intense violet colour when a few drops of
nitric acid are added to a solution of the oil in glacial acetic acid.
Fatty Oils may be detected by leaving an oily stain on blotting paper
after evaporation by gentle heat. With the exception of castor oil they
are insoluble in alcohol. Castor oil dissolves in a small quantity of
petroleum ether, but on further dilution with petroleum ether, it separates.
Fatty oils usually increase the ester value of an oil, and a greater propor-
tion of non-volatile residue is found on evaporation over a water-bath.
Some volatile oils leave a residue on evaporation, e.g. bergamot, lemon,
orange, nutmeg, ylang-ylang, and cassia oils. The fatty oils do not distil
J
P. and E.O.R. (June, 1915), 148.
without decomposition, and their presence may be proved by the acrolein
test (heating with potassium bisulphate). Cocoanut oil may be detected
by freezing.
Fatty acids may readily be detected by the increase in acid value.
Petroleum or mineral oil (kerosene, etc.) are less soluble in alcohol
than most oils. They have a low specific gravity and refractive index,
and are not saponified by alcoholic potash. The lower boiling fractions
can usually be detected by their odour, and the higher boiling fractions
remain in the residue on fractional distillation. They are unaffected by
fuming nitric acid.
Alcohol and acetone maybe detected by their low boiling-point and by
the iodoform test. Oils containing alcohol form milky mixtures with
water. It may be extracted by washing with water, when the refractive
index of the washed oil is found to be distinctly higher than that of the
original oil.
Chloroform is readily recognised by its odour and by the phenyl iso-
nitrile test. It is found in the first fractions distilled.
Besin is frequently found in cassia oil. It interferes with the accurate
determination of the aldehyde by making it difficult to read off the un-
combined oil. It may be detected by adding a solution of lead acetate in
70 per cent, alcohol to a solution of the oil in alcohol of the same strength.
The presence of resin increases the amount of non-volatile residue, and
also increases the acid value of the oil.
The proportion of resin can be determined by weighing the precipitate
formed with solution of lead acetate in 70 per cent, alcohol.1
Terpenes are commonly employed for diluting lemon, orange, and
bergamot oils. The addition lowers the specific gravity, increases the
optical rotation, and lowers the proportion of oxygenated constituents.
Terpinolene, a by-product in the manufacture of terpineol, has been de-
tected in some oils, notably citronella and spike, lavender. It can be
detected by its odour in the fractionated oils.
1
P. and E.O.B., 1914, 264.
THE END.
INDEX.
ACETEUGENOL, 263. Aromatophores, 28.
Acetic acid, 295. Aronsohn, on odour, 33.
— aldehyde, 180. Artemisia absinthium, oil of, 12, 18.
Acetine, 313. Asarone, 266.
Acetone, 212, 357. Asarylic aldehyde, 207.
Acetophenone, 244. Ascaridol, 285.
Acetovanillone, 247. Atractylene, 93.
Acids, 294. Atractylol, 160.
Alantoic acid, 298. Aubepine, 197.
Alantolactone, 274. Austerweil and Cochin on odour, 33.
Alcohol as adulterant, 357. Australol, 264.
Alcohols, 104. Azulene. 103.
— determination of, 321.
Aldehydes, 177. BACKMAN on odour, 27.
— aliphatic, 180. Baker and Smith on leaf venation, 22, 24.
— compounds of, 178, 179, 180. Basil oil, development of, 12.
— determination of, 335 (and vide Ke- Benzaldehyde, 15, 190.
tones). Benzoic acid, 296.
Allo-ocimene, 79. Benzophenone, 246.
Allyl cyanide, 291. Benzyl acetate, 170.
— guaiacol, 270. — alcohol, 126.
— isothiocyanate, 293. — benzoate, 170.
— isothujone, 237. — cinnamate, 171.
— methoxy - methylene-dioxy - benzene, — cyanide, 291.
267. — esters, 170.
— propyldisulphide, 293. — ethyl-car binol, 128.
— pyrocatechol, 261. — isothiocyanate, 294.
— tetramethoxy-benzene, 268. — menthol, 144.
— trimethoxybenzene, 267. Benzylidene-acetone, 246.
Almonds, oil of, 15. Bergamot oil, development of, 16.
Amygdalin, 15. Bergaptene, 275.
Amyl acetate, 167. Betulol, 159.
— benzoate, 167. Bisabolene, 81.
— heptylate, 167. . Blondel on development of essential oils,
— salicylate, 167. 15.
— valerianate, 167. Boiling-points, determination of, 310.
Amyrol, 152. Bonnier on development of essential oils,
Analysis of essential oils, 299. 6, 20.
Androl, 123. Borneol, 145.
Anethol, 259. tso-Borneol, 146, 147.
Angelic acid, 296. Bornyl acetate, 146, 171.
Angelica lactone, 284. — butyrate, 146, 172.
Anisic acid, 298. — esters 146, 171.
— alcohol, 129. — formate, 146.
— aldehyde, 197. — isovalerianate, 172.
— ketone, 217. — propionate, 146, 172.
Anthranilic acid, 298. — valerianate, 146.
Apiol, 269. iso-Bornyl formate, 147.
Aplotaxene, 103. Bornylene, 53.
Apopinol, 150. Bromostyrolene, 39.
Aromadendral, 209. Bupleurol, 123.
Aromadendrene, 99. Butyl isothiocyanate, 293.
(359)
Butyric acid, 295. Citronellal, 118, 121, 188, 189.
— aldehyde, 180. — determination of, 334, 335.
Citronellic acid, 296.
CADINENE, 83. Citronellol, 33, 118.
Cadinol, 154. — determination of, 334.
Calamene, 99. Citronellyl acetate, 173.
Camphene, 50. — esters, 172.
— hydrate, 148. — formate, 173.
Camphor, 241. Citroptene, 276.
— homologues, 243. Civet ketone, 249.
Cannabis sesquiterpene, 101. Closed chain alcohols, 126.
Cannibene, 102. Clove sesquiterpene alcohol, 156.
Cantharene, 79. Clovene, 97.
Caparrapene, 93. Cohn on odour, 29.
Caparrapiol, 160. Common adulterants, detection of, 356.
Caproic acid, 296. Copaene, 95.
Carene, 75. Copaiba oil, as adulterant, 356.
Carlina oxide, 284. Costene, 100.
Carone, 67. iso-Costene, 100.
Carvacrol, 257. Costic acid, 298.
GarveneDe, 72. Costol, 156.
Carvertrene, 65, 66. Costus lactone, 284.
— synthesis of, 67. Coumarin, 272.
Carvomenthol, 231. Creosol, 260.
Carvone, 66, 230. Cresol compounds, 250.
Carvotanacetone, 71, 231, 236. m-Cresol, 250, 251.
Carylamine, 67. ^-Cresol, 250, 251.
Caryophyllene, 84, 89. jw-Cresol methyl ether, 251.
a-Caryophyllene, 84, 89. Crithmene, 75.
/8-Caryophyllene, 84. Crotonyl isothiocyanate, 294.
*y-Caryophyllene, 84. Cryptal, 209.
iso-Caryophyllene, 88. Cumic aldehyde, 195.
Urn-Caryophyllene, 85. Cuminic alcohol, 129.
terjj-Caryophyllene, 85. Cyclocitral, 33.
Cedarwood oil, as adulterant, 356. Cyclogeraniolene, 32.
Cedrene, 95, 153, 154. ^-Cymene, 254.
Cedrenol, 153. Cypressene, 93.
Cedrol, 97, 153.
pseudo-Cefaol, 97, 153. DACRYDENE, 76.
Cedrone, 96. van Dam on odour, 25.
Charabot, on development of essential Damascenine, 290.
oils, 3, 5, 6, 11, 13, 15, 16, 20, 21, 22. Decyl alcohol, 107.
Chavibetol, 270. — aldehyde, 181.
Chavicol, 257. Diacetine, 313.
Chinese pine sesquiterpene, 102. Diacetyl, 215.
Chlorine, detection of, 14, 352. Diallyl sulphide, 293.
Chloroform, as an adulterant, 357. — thujone, 237.
Chlorophyll, functions of, 20. — trisuphide, 293.
Chlorostyrolene, 39. Dicitronell-oxide, 284.
Cineol, 45, 276, 278. Dihydrocarveol, 66, 139.
Cinnamic acid, 297. Dihydrocarvone, 67, 232.
— alcohol, 129. Dihydrocedrene, 96, 97.
— aldehyde, 193. Dihydroionone, 223.
Cinnamyl butyrate, 173. Dihydroisocedrol, 96.
— cinnamate, 173. Dihydrolinalol, 117.
— esters, 173. Dihydromyrcene, 117.
— propionate, 173. Dihydropseudoionone, 124, 125.
Citral, 111, 182. Dihydroverbenol, 227.
— determination of (see Aldehydes). Dihydroverbenone, 227.
a-Citral, 113, 182, 184. Dihydrovetivenol, 155.
/8-Citral, 113, 182, 184. Dillapiol, 269.
c?/cZo-Citral, 33, 185. iso-Dillapiol, 270.
€no/-Citral, 111. Dimethyl-heptenone, 33.
iso-Citral, 185. -isothujone, 237.
Citronella sesquiterpene, 101. phloro-acetophenone, 245.
INDEX 361
Dimethyl sulphide, 292. Patty oils as adulterants, 356.
— -thujone, 237. Fenchene, 48, 53.
Dinitro-butyl-m-cresol methyl ether, 290. a-Fenchene, 54, 55.
Diorphenol, 248. 0-Fenchene, 54, 56.
Dipentene, 59, 62, 63. •y-Fenchene, 56.
Diphenyl methane, 39, Fenchone, 234.
Diphenyl oxide, 39, 250. Fenchyl alcohol, 140, 234,
Distillation, fractional, 310. iso-Fenchyl alcohol, 234.
Duodecyl alcohol, 107, 108. Ferulene, 100.
Duodecylic aldehyde, 181. Firpene, 49.
Durand on odour, 26. Fliickiger on development of essential
Durrans on odour, 35, 36. oils, 25.
Formic acid, 294.
ELEMENE, 100. — aldehyde, 180.
Elemicin, 262. Fournie on odour, 25.
Elemol, 157. Fractional distillation, 310.
Elsholtzione, 244. — saponification, 314.
Enfleurage, 14.
Enosmophore, 29. GALIPOL, 160.
Erdmann on odour, 25. Geranaldehyde, 182.
Esters, 161. Geraniol, 17, 34, 108, 113.
— artificial detection of, 312. — development of, 17.
— determination of, 311. — dioxide, 110.
Estragol, 258. — rose odour of, 34.
iso-Estragol, 259. iso-Geraniol, 111, 112.
Essential oils, analysis of, 299. Geranium oil, artificial, 39.
in the plant, 1. development of, 17.
origin of, 3. Geranyl acetate, 168.
Ethyl acetate, 165. — butyrate, 169.
— alcohol, 105. — esters, 168.
— amyl-carbinol, 106. — ethyl ether, 110.
ketone, 213. — formate, 166.
— anisate, 165. — isobutyrate, 169.
— anthranilate, 165. — isovalerianate, 169.
— benzoate, 166. — tiglate, saponification values of, 333.
— butyrate, 166. Globulol, 158.
— caprylate, 166. Glucosides in essential oil formation, 13.
— cinnamate, 166. Glyceryl acetate, detection of, 315.
— citrate, 313. Gonostylene, 102, 159.
— heptoate, 166. Gonostylol, 159.
— laurinate, 166, 313. Guaiacol, 251.
— malonate, 166. Guaiene, 93.
— -menthol, 144. Guaiol, 155.
menthyl acetate, 144. Gurjunene, 94.
— myristinate, 166. Gurjun ketone, 249.
— nonylate, 166. — oil as adulterant, 356.
— octylate, 166.
— oleate, 313. HALUER on odour, 28.
— phenyl-acetate, 167. Helinin, 274.
— phthalate, 313. Heliotropin, 206, 265.
— salicylate, 167. Heller on odour, 26.
— succinate, 313. Henning on odour, 26.
— valerianate, 166. Heptane, 38.
Eucalyptol, 23, 45, 276. Heptyl alcohol, 106.
— determination of, 278. — aldehyde, 181.
— leaf venation of, 23. — heptoate, 167.
Eudesmene, 102. Herabolene, 99.
Eudesmic acid, 298. Hexahydro-^-cymene, 39.
Eudesmol, 158, 159. Hexyl acetate, 167.
Eugenol, 261. — alcohol, 105.
— determination of, 350. — aldehyde, 181.
iso-Eugenol, 262. — butyrate, 168.
Hexylenic aldehyde, 182.
:FARNESAL, 124, 212. Higher aliphatic alcohols, 106.
Fame sol, 124. Homoanisic acid, 258.
Homolinalyl acetate, 173. Lim-caryophyllene, 85.
Humulene, 88. Limene, 81.
Hydrocarbons, 38. Limonene, 40, 59, 63, ISO.
— determination of, 353. —- synthesis of, 63.
Hydrocinnamic acid, £97. ortf/z-o-Liriionene, 63.
— aldehyde, 196. #s$wdo-Limonene, 63.
Hydrocyanic acid, 291. Linalol, 110, 114.
Hydrogen number of essential oils, 353. — dioxide, 117.
Hydropinene, 49. — monoxide, 117.
Hydroquinone methyl ether, 259. Linalyl acetate, 169.
Hydroxypaeonol, 247. — butyrate, 170.
— esters, 169.
INDOL, 14, 292. — formate, 169.
a-Ionane, 223. — propionate, 170.
/8-Ionane, 223, Longifolene, 103.
lonone, 32, 215. Lysigenous structures, 1.
o-Ionone, 216, 217, 218.
£-Ionone, 216, 217, 218. MAALI sesquiterpene, 101, 160.
pseudo-Ionone, 216. alcohol, 160.
Irone, 32, 215. Matico camphor, 159.
Isoamyl alcohol, 105. Mehrling and Welde on odour, 32, 33-
— -menthol, 144. Melting-points, determination of, 309.
Isoanethol, 258. Menthadiene, 40.
Isoborneol, 146, 147. Menthane, 39.
Isobornyl formate, 147. Menthene, 40.
Isobutyl alcohol, 105. Menthenol, 40.
Isocanenone, 72. Menthenone, 241.
Isocaryophyllene, 85. Mentho-citronellol, 122.
Isocostene, 100. Menthonyl alcohol, 122.
Isodillapiol, 270. Menthol, 142.
Isoestragol, 259. wô-Menthol, 144.
Isoeugenol, 262. Menthone, 189-239.
Isofenchyl alcohol, 234. Menthyl acetate, 144, 176.
Isogeraniol, 111, 112. — benzoate, 144.
Isohexyl alcohol, 106. esters, 176.
Isopinene, 40, 47, 48, 55. — isovalerianate, 176.
Isopropyl-o-cresol, 257. — propionate, 144.
Isopulegol, 141, 189. Mesnard on development of essential oils..
Isosafrol, 266. 15.
Isosantalene, 92. Methoxy-cinnamic aldehyde, 196.
Iso-sylvestrene, 65. Methyl acetophenone, 245.
Isothujene, 58. — alcohol, 105.
Isothujone, 236. — -amyl-ketone, 213.
Isothujylamine, 58. — anisate, 163.
Isovalerianic aldehyde, 180. — anthranilate, 14, 163.
Isozingiberene, 82. — anthranilic acid, 298.
— benzoate, 164.
JASMIN, oil of, 14, 126, 248. — caprinate, 163.
Jasmone, 248. — caprylate, 163.
Juniperol, 158. — cinnamate, 164.
— chavicol, 258.
— cyclohexanol, 142.
KAEMPFEEIA ketone, 249. — ethyl-propyl alcohol, 106.
Kakosmophores, 29. — eugenol, 263.
Kessyl alcohol, 150. — heptenol, 122, 214.
Ketone musk, 290. — heptenone, 214.
Ketones, 212. — heptoate, 163.
— determination of, 335-346. — heptyl ketone, 213.
Klimont on odour, 28. — heptylene carbinol, 122.
Kremer on odour, 27. — hexanone, 225.
— hydroxy-cinnamic aldehyde, 196.
LACTONES, 272. — -indol, 292.
Lavender oil, development of, 6, 17, 20. — laurinate, 163.
Ledum camphor, 156. — malonate, 164.
Librocedrene, 99. — menthol, 144.
INDEX 363:
Methyl menthyl acetate, 144. Oxybenzyl isothiocyanate, 294.

— methoxy-cinnamic acid, 297. Oxyphenetol, 259.
— methoxyrescorcylate, 176.
— methoxysalicylate, 176. PAEONOL, 247.
— methylanthranilate, 164. Para-methyl hydrocinnamic aldehyde,.
— nonyl-ketone, 213. 196.
— nonylate, 163. Parry on odour, 35.
— j^-oxyallylbenzene, 258. Patchonlene, 101.
— ^-oxypropenylbenzene, 259. Patchonli camphor, 159.
— phenyl-acetate, 164. Peppermint oil, development of, 3, 18.
— phenyl-propionate, 165. Perillic alcohol, 130, 207.
— phthalate, 313. Perkin on odour, 30, 34, 35.
— salicylate, 165. Petroleum as adulterant, 357.
Monoacetine, 313. Phellandral, 210.
Hosier on peppermint plants, 4. Phellandrenes, 68, 69.
Musk, artificial, 286. Phenols, 250, 348.
— aldehyde, 290. — determination of, 348.
— ambrette, 290. Phenyl-acetic acid, 128, 297.
— cyanide, 290. " aldehyde, 128, 194.
— ketone, 249, 290. — amyl alcohol, 129.
— xylene, 289. — butyl alcohol, 129.
Muskone, 249. — dimethyl carbinol, 128.
Myrcene, 77. — ether, 250.
Myrcenol, 78. — ethyl-alcohol, 122, 127.
Myristicin, 267. acetate, 175.
Myrtenal, ±08. carbinol, 128.
Myrtenol, 148. ether, 250.
esters, 175.
isothiocyanate, 294.
0-NAPHTHOL-butyl ether, 271. propionate, 175.
— -ethyl ether, 271. ethylene, 38.
— -methyl ether, 271. — heptyl alcohol, 129.
Neo-menthol, 144. — hexyl alcohol, 129.
Neral, 182. — methyl carbinol, 128.
Nerol, 112, 113. ether, 250.
Nerolidol, 125. — propionitrile, 291.
Nitro-benzene, 287. — propyl alcohol, 128.
Nitrogen compounds, 286. ciDnamate, 175.
Nonyl alcohol, 107. Phlorol ethers, 251.
— aldehyde, 181. Phloracetophenone dimethyl ether, 271*.
Nor-camphene, 79. Phyllocladene, 81.
— -tricycloeksantalal, 210. a-Pinene, 40, 47, 49.
— -tricycloeksantalane, 81. j3-Pinene, 40, 46.
8-Pinene, 40, 46.
OCIMEFE, 77, 78. iso-Pinene, 40, 47, 48, 49, 56.
Ocimenol, 79. Pinenol, 138.
Ocimum basilicum, 12. Pinenyl acetate, 175.
Octyl acetate, 168. Pinocamphene, 233.
— alcohol, 107. Pinocarveol, 138.
— aldehyde, 181. Pinoglycyl acetate, 175.
— butyrate, 168. — propionate, 175.
— heptylate, 168. 0-Pinolene, 48, 234.
Odour and chemical constitution, 25. Piperitol, 148.
Oleic aldehyde, 182. Piperitone, 228.
Olfactometers, 25. Piperonal, 206, 265.
Opoponax sesquiterpene, 100. Polarimetry, 305.
alcohol, 100. Propenyl-trimethoxy-benzene, 266.
Optical methods of analysis, 301. Propionic acid, 295.
Origanene, 74. Propyl-menthol, 144.
Origanol, 57. menthyl acetate, 144.
Osmoceptors, 28. Pseudo cedrol, 97, 153.
Osmophores, 28. ionone, 216.
Oxides, 272. selenine, 90.
Oxyacetophenone, 245. Pulegol, 142.
Oxyallylbenzene, 258. Pulegone, 142, 238.
-364 THE CHEMISTEY OF ESSENTIAL OILS
JPumilone, 215. Terp-caryophyllene, 85.
-Pyrogalloll dimethyl ether, 261. Terpene alcohols, 130.
Terpenes, 39.
REFRACTION, 301. — as adulterants, 357.
.Kefractive index, 301. Terpin, 45.
Eefractometer, 302. — hydrate, 137.
Residual affinity, theory of, 35. Terpinene, 57, 71.
. Resin as adulterant, 357. a-Terpinene, 71, 75.
Resinogeneschicht, 7. £-Terpinene, 71, 72.
Rhodinal, 188, 189, 190. 7-Terpinene, 71, 73.
Rhodinol, 118, 119, 120, 121. Terpinenol, 136.
Rose, evolution of perfume, 16. Terpineol, 57, 130.
— odours, Austerweil on, 33. a-Terpineol, 131, 132.
Roscol, 118. £-Terpineol, 131, 133.
Roure-Bertrand on peppermint plants, 6. 7-Terpineol, 131, 133.
Rupe and Majewski on odour, 28. Terpinolene, 74.
Ruzicka on odour, 28. Terpinyl acetate, 174, 314.
— cinnamate, 174.
SABINA ketone, 57, 225. — esters, 173.
Sabinene, 56, 59. — formate, 173.
Sabinol, 135. — propionate, 174.
Safrol, 265. Tetradecyl aldehyde, 182.
iso-Safrol, 266. Tetrahydrocarvone, 231.
-Salicylic acid, 297. Tetrahydroelemene, 157.
— aldehyde, 192. Tetrahydroelemol, 157.
Salvene, 76. Tetrahydroionone, 223.
Sandalwood oil, hydrocarbons from, 80. Teudt on odour, 35.
Santalal, 211. Thujenes, 57, 58.
Santalene, 92. Thujol, 18.
iso-Santalene, 92. Thujones, 235-237.
• Santalols, 151. Thujyl alcohol, 134.
Santalone, 248. wo-Thujyl alcohol, 134.
Santelol, 149. Thujylamine, 58.
Santene, 79. Thymol, 251, 349.
Santenone, 225. — methyl ether, 256.
Saponification, fractional, 314. Thymohydroquinone, 260.
— table of values, 323. — methyl ether, 260.
Schizogenous structures, 2. Thymomenthol, 144.
Sedanolide, 275. Thymoquinone, 260.
Sedanonic anhydride, 275. Tiglic acid, 296.
Selinene, 89. Tredecyl aldehyde, 18 >.
•0r£/&o-Selinene, 90. Triacetine, 313.
pseudo-Selineue, 90. Triallylthujone, 237.
Sesquicamphene, 95. Trimethyl-hexanone, 246.
Sesquicitronellene, 98. Trinitro-butyl-xylene, 289.
-Sesquiterpenes, 81. Tschirch on development of essential oils,
Skatol, 292. 7, 13.
Solidifying points, determination of, 309. Tuberose, oil of, 14.
Solubility of essential oils in water, 9, 10. Tunmann on development of essentia
water in essential oils, 11. oils, 8.
Specific gravity, 299. Turpentine as adulterant, 356.
Styrol, 38. Tyndall on odours, 27.
Styrolene, 38.
> Styrolyl acetate, 175.
— propionate, 175. UMBELLULONE, 232.
— valerianate, 175. Umney and Baker on solubility of es-
Suginene, 98. sential oils in water, 9.
Sulphur compounds, 292. Uncineol, 124.
Sylvestrene, 65. Undecylenic alcohol, 107.
iso-Sylvestrene, 65. — aldehyde, 182.
Undecylic alcohol, 107.
TANACETENE, 58. — aldehyde, 181.
Tasmanol, 264.
Teresantalic acid, 296. VALERIANIC acid, 295.
'Teresantalol, 139. — aldehyde, 181.
INDEX 365.
Valeryl-tetrahydrobenzoic acid, 275. WOKEB on odour, 30.
Vanilla, essence of, 203.
Vanillin, 198, 261. XANTHOTOXIN, 276.
Veratric acid, 298. Xylene musk, 289.
Verbenene, 45, 46.
Verbenol, 228.
Verbenone, 226. ZIBETHONE, 249.
Vestrylamiiie, 67. Zingiberene, 82.
Vetivene, 97. iso-zingiberene, 82.
Vetivenol, 98, 154. Zingiberol, 155.
Vinyl sulphide, 293. Zwaardemaker on odour, 25, 35.

Chemistry of Essential Oils and Perfumes Voll 1 &amp; 2

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Chemistry of Essential Oils and Perfumes Voll 1 &amp; 2

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VOLUME I.

ERNEST J. PARRY B.Sc. (LOND.), F.I.C, F.C.S.

FOURTH EDITION, REVISED AND ENLARGED

WITH FIFTY.TWO ILLUSTRATIONS

PRINTED IN GREAT BRITAIN

56A GREAT DOVER STREET,

The oil probably consists of sesquiterpenes or sesquiterpene alcohols.

It contains two sesquiterpene alcohols, C15H26O, one boiling at 265° and

Alicularia scalaris yields a lemon-yellow essential oil having the fol-

It appears to contain a sesquiterpene alcohol.

It forms an acetate of specific gravity 1-0168 at 20° and refractive index

C:CH G(OH).CH 2 C:CH

Pseudo-cediol is a saturated alcohol, boiling at 1473 to 152° at 10

It is soluble in 1 to 10 volumes of 90 per cent, alcohol. According

A sample examined by Messrs. Schimmel & Co. gave the following

A second sesquiterpene is present, which only yields liquid halogen

On fractional distillation the following constituents were separated:

They contain about 85 per cent, of J-a-pinene, 5 per cent, of rf-limonene,

FIG. 1.—Still of a *• Turpentine Farm " in the " Landes ".

F IG> 2.—Collection of the crude turpentine in the «* Landes ".

In the maritime pine forests of Bordeaux no tree is tapped lightly till it

m.p. b.p. d. nD. m.p. b.p. d. nD. m.p. b.p. d. nD.

•1) (2 (3) (4) (5)

As Hertz 1 has shown, the optical rotation of American oil of turpen-

Al P. heterophylla 7-0 1st year, normal depth - 20° 50'

OPTICAL KOTATION IN 100 MM. TUBE, 20° C.

Collection. Al. A2. A3. A4. A5. A6. 01.

Wood turpentine can, however, be so rectified as to distil at tempera-

1 . Optical Activity . . . . active usually none none none none s

TUKPENTINE FROM PlNUS PONDEROSA (LAWS).

Distillate. Specific Index of

°C. Per Cent. Per Cent.

Laevo-a-pinene, /2-pinene, and laevo-limonene were detected in the oil.

Distillate. dl5°. ND15°

°C. Per Cent. Per Cent.

a-Pinene, /3-pinene, and limonene were found in the oil.

°C. Per Cent. Per Cent.

This oil is very noteworthy, as it consists almost entirely of the hydro-

°C. Per Cent. Per Cent.

TURPENTINE FROM PINUS LAMBEKTIANA.

Distillate. d!5° ND15°

The oil contains a-pinene, /?-pinene, a very small amount of phellan-

TUEPENTINE FROM PlNUS EDULIS.

Distillate. 6/15° ND 15°

°C. Per Cent. Per Cent.

TURPENTINE FROM PINUS JEFFREYI.

Field of Oil. [«JD. Specific Gravity.

Pinus Sylvestris 15 to 16 per cent. + 22° to + 24° 0-867 at 15°

It yields sylvestrene hydrochloride when treated with hydrogen chloride

Two samples on fractionation by Eabak 2 and by Schimmel & Co.3

Austrian turpentine oil is derived principally from Pinus laricio. Its

FIG. 4.—Tree of Agathis robusta, Queensland.

IV,. 5.—Athrotaxis selaginoides. King William Pine. Athrotaxis selaginoides.

A small amount of a phenolic body was isolated from the higher

FIGL 6.—Araucaria Cunninghamii. Fasciation at top of a tree under cultivation at

pIG. 7_Araucaria Cunninghamii. Cultivated tree at Beecroft, New South Wales.

hydrocarbon C10H,0. which as a colourless liquid having a specific gravity

1 0-8596 @ 23 + 44-2 1-4809® 20 3-13 0-331

2 0-8591 @ 23 + 47-5 1 -4809 @ 19 3-8 0-26G

OIL FROM THE FRUITS.

0-8608 @ 22 + 0-3 1-4788® 19 1-78 0-44

Specific Rotation Refractive Ester, per Ester, per

No. Specific Gravity, Rotation Retractive Index, Ester, Yield,

Chemistry of Essential Oils and Perfumes Voll 1 & 2

Chemistry of Essential Oils and Perfumes Voll 1 & 2

properties : boiling-point 123° to 126° (105 mm.); d'^-0 09224 ; aD + 5°;