INDEX

SR. NO.
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2
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4
5
6
7

TITLE
INTRODUCTION OF TERPENOIDS
CLASSIFICATION OF TERPENOIDES
TETRACYCLIC TRITERPENOIDS
PENTACYCLIC TRITERPENOIDS
NEW SKELETON OF TRITERPENOIDS
STRUCTURE OF NEW SKELETON TRITERPENOIDS
REFERENCES

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1. INTRODUCTION
1.1 Definition 1-4
1

The term terpene was employed to describe a mixture of isomeric hydrocarbons

of the molecular formula C10H16 occurring in the turpentine and many essential oils which
are obtained from the sap and tissues of certain plants and trees. The oxygenated
derivatives like alcohols, aldehydes, ketones, etc, at that time were called camphors. 1
Both the terms terpenes and camphors were amalgamated into a single term called
terpenoids. The modern definition of this term is as follows:
It includes hydrocarbons of plant origin of the general formula (C 5H8) as well as
their oxygenated, hydrogenated and dehydrogenated derivatives
Another reason for rejecting the term terpene is that since the suffix ene
signifies unsaturated hydrocarbons.
As terpenoids are composed of isoprene units, these are sometimes called
isoprenoids. Not only the carbon skeletons of terpenoids are divisible into isoprene units
but the terpene hydrocarbons are usually exact multiplies of C 5H8. An example is
myrcene (C10H16) which has a carbon skeleton divisible into two isoprene units.2

1.2 Nomenclature 1-4

Many terpenoids are known by their trivial names because these were isolated and
described in the literature long before their structure was elucidated. Generally these
names are derived from their botanical origins. Foe example crystalline sesquiterpene
secondary alcohol belonging to the group was isolated from vetiver oil (Vetiveria
zizaniodides) and named khus oil in India. So its alcohol was called khusinol and
another crystalline alcohol which belonging to same group and isolated from the same
source was called khusol.
2

1.3 Occurrence 3
The simple mono and sesquiterpenoids are the chief constituents of the essential
oils. The di and triterpenoids which are not steam volatile are obtained from plant, tree,
gums and resin. The tetraterpenoids constitute a group of compounds called
carotenoids. This group includes carotenes, xanthophyllis and carotenoidic acids.
Rubber is the most important polyterpenoids.
1.4 General properties of Terpenoids 2
As far as physical properties of terpenoids are concerned, most of them are
colourless liquids which are lighter than water and boil between 150C and 180C. A few
are solids which are lighter than water, volatile in steam, usually highly refractive and
insoluble in water but soluble in organic solvents. Many of these are optically active.
The various general chemical properties of terpenoids are as follows: 2

They are unsaturated compounds (open chain or cyclic with one or more carbon
atom rings) having on or more double bonds. Consequently, terpenoids undergo
addition reactions with hydrogen, halogens, halogen acids, etc. some of them
form hydrates. They also form characteristic addition products with NO 2, NOCl
and NOBr. These addition products are founds to be useful in the identification of
terpenoids. A number of addition products have antiseptic properties.

They undergo polymerisation, also dehydrogenation in the ring.

As they have olefinic bonds, they are very easily oxidised nearly by all the
oxidising agents.

A number of terpenoids are labile and hence readily isomerised in the presence of
acids into more stable forms.

On thermal decomposition, most of the terpenoids yield isoprene as one of the

products.

1.5 Isolation is carried out in two steps follow: 2 Lets discuss it one by one.
I.

Isolation of essential oils: As plant having essential oil generally prosses

maximum concentration at some particular time, e.g. jasmin at sun set, its become
desirable to take the plant parts having essential oil at this particular time. In
general method based on different principle has been developed for the extraction
of oil. This method is as follows.

Expression method: This method the plant material is cut in to small pieces.
Then these pieces crushed to get the juice which is screened to remove the larger
particles. After screening the juice is centrifuged in a high speed centrifuge
machine when one-half of the oil is extracted oil remains with the residue. From
this residue, inferior quality of the oil is obtained by distillation.

Steam distillation method: This method is the one most widely used method. In
this plant materials are macerated and then steam distilled to get the essential oils
in to the distillate from which these are extracted by using pure organic solvent
like light petroleum and solvent is then removed by distillation under the reduced
pressure .

Extraction by means of volatile solvents: This method is widely used in

perfume industry. This method is generally used in such plants which yield an oil
and gave low quantities of oil on steam distillation due to decomposition of
essential oil such cases, the plant materials is directly treated with light petrol at
50C. Under this condition the oil is taken up by the solvent along with the soluble
colouring materials. The essential oils from the extract are separated by removing
the solvent by distillation under reduced pressure.

Adsorption in purified fats: This method is known as enflurage method and is

widely used in France. By this method yield is high and used to extract out the
large number of the essential oil e.g. rose and jasmine.
In this method, the fats are warmed to 50 C on glass plates. Then, the surface of
the fats is converted with essential oils. Then, the old petals are replaced by the
fresh petals and this process is repeated. After removing the petals, the fats are
digested by ethyl alcohol when all the oils present in fats are dissolving in
alcohol. Some quantity of fat is dissolve in alcohol. This can be removed by
colling the alcohol extract to 20C, when the fats separates out. The alcoholic
distillate is then finally fractionally distilled under reduced pressure to remove the
solvent.
Recently, the fats has been replaced by coconut charcoal due to its great stability
and higher absorptive capacity. After keeping the charcoal with the petals for a
number of a day, the charcoal is submitted to steam distillation to get a essential
oil.

II.

Separation of terpenoids from essential oils: The essential oils obtained from
step 1 generally contain number of terpenoids and these are separated by various
physical and chemical method.
a. Chemical method:

When essential oil containing terpenoids hydrocarbons are treated with

nitrosyl chloride in chloroform, crystalline adducts of hydrocarbon having a
sharp melting points are obtained. These are decomposed in to their
corresponding hydrocarbons.

When essential oils containing alcohols are treated with the phthalic anhydride
to form diesters. The primary alcohol react with pthalic anhydride readily and
tertiary alcohol do not react at all.After extracting with sodium bicarbonate,
diesters are decomposed by alkali to perent triterpenoid alcohol.

Terpenoids alcohol and ketones are separated from essential oils by forming
their adducts with common carbonyl reagent like NaHSO3, 2-4-dinitro phenyl
5

hydrazine, semicarbazine. After the separation, these are decomposed to

regenerated aldehydes and ketones.
b. Physical method:

Fractional distillation method: The various terpenoids present in

essential oils are separated by fractional distillation method. The
terpenoid-hydrocarbons distil over first, followed by the oxygenated
derivatives. Distillation of the residue under reduced pressure yields
the sesquiterpenoids and these are separated by fractional distillation.
On an industrial scale, especially designed stills are employed and an
efficient condensing system is necessary to minimise loss of more
volatile hydrocarbons. Many times, the fractional distillation has to be
carried out under reduced pressure and in the presence of an inert gas.
These conditions are essential because many terpenes are sensitive to
heat and atmospheric oxygen.

Chromatography: In adsorption chromatography, the essential oil is

made to flow through a particular adsorbent when the different types
of rerpenoids are adsorbed at different places on the adsorbent to
form different chromato g rams. Then, the various chromatograms are
eluted by different solvent systems to get different eluates.Each
ehuate is then subjected separately to adsorption chromatography
when different bands due to the various terpenoids present in eluate
are obtained which are then eluted to yield different terpenoids. In
adsorption chromatographic method, alumina and silica gel are
generally

used

as

adsinbents

for

separating

the

terpenoids.

particularly triterpenoids. Other chromatographic techniques such as

vapour phase chromato g raphy. partition chromatography and countercurrent separation method have been used for the separation of
terpenoids. Gas chromatography has been particularly useful for
isolating pure configurational forms of a given terpenoid from
mixtures produced by synthesis.
6

2. CLASSIFICATION OF TERPENOIDS
The terpenoids have a general formula (C 5H8)n and have of n is used as a basis of
classification:3
Table no. 1
Class
1) Hemiterpene
2) Monoterpenes
3) Sesquiterpenes
4) Diterpenes
5) Triterpenes
6) Tetraterpenes
7) Polyterpenes

Classification of tepenoides

No. of Isoprene units

1
2
3
4
6
8
n

Molecular formula
C5 H8
C10 H16
C15 H24
C20 H32
C30 H48
C40 H64
(C 5H8 )n

The sesterterpenoids have been discovered recently. The example of this class
called solanesol, an acyclic unsaturated alcohol was discovered in 1956. In addition to the
hydrocarbons in each class given in Table, oxygenated compounds like alcohols,
aldehydes, ketones are also known which occur in nature.
Each class of terpenoids has been further subdivided into subclasses according to
the number of rings present in the molecule.
(1)

Acyclic terpenoids. These contain an open-chain structure.

(2)

Monocyclic terpenoids. These have one ring in the molecule.

(3)

Bicyclic terpenoids. These contain two rings in the molecule.

(4)

Tricyclic terpenoids. These contain three rings in the molecule.

(5)

Tetracyclic terpenoids. These contain four rings in the molecule.

(6)

Pentacyclic terpenoids. These contain five rings in the molecule.

Now we will more concentrate on triterpenoides.

3. TETRACYCLIC TRITERPENOIDS (STEROIDAL) SAPONINS

Mainly triterpenoids are in the form of the tetracyclic triterpenoids and
7

pentacyclic triterpenoids.

The steroidal saponins are less widely distributed in nature than the pentacyclic
tritetpenoid type. Phytochemical surveys have shown their presence in many
monocotyledonous families, particularly the Dioscoreaceae (e.g. Dioscorea spp.),
Amaryllidaceae (e.g. Agave spp.) and Liliaceae (e.g. Yucca and Trillium spp.). In the
dicotyledons the occurrence of diosgenin in fenugreek (Leguminosae) and of steroidal
alkaloids in Solanum (Solanaceae) is of potential importance. Some species of
Strophanthus and Digitalis contain both steroidal saponins and cardiac glycosides.
Examples of saponins and their constituent sugars are sarsaponin, digitonin, gitonin,
dioscin.
Steroidal saponins are of at pharmaceutical importance because of their
relationship to compounds such as the sex hormones, cortisone, diuretic steroids, vitamin D
and the cardiac glycosides. Some are used as starting materials for the synthesis of
these compounds. Diosgenin is the principal sapogenin used by industry but most
yams, from which it is isolated, contain a mixture of sapogenins in the glycosidic
form.
As with cardiac glycosides. The stereochemistry of the molecule is of some
importance, although not so much so for cortisone manufacture. Natural sapogenins differ
only in their configuration at carbon atoms 3, 5 and 25, and in the spirostane series the
orientation at C-22 need not be specified (steroidal alkaloids). Mixtures of the C-25
epimers e.g. diosgenin (4 5, 25-spirosten-30-ol) and yamogenin (25-spirosten-30-ol) are
8

of normal occurrence and their ratio, one to the other, is dependent upon factors such as
morphological part and stage of development of the plant. In some instances in the
plant, the side-chain which forms ring F of the sapogenin is kept open by glycoside
formation as in the bisdesmosidic saponin sarsaparilloside of Smilax aristolochiaefolia.
3.1 Biogenesis of steroidal saponins5
Steroidal saponins arise via the mevalonic acid pathway. A scheme for the
R

subsequent cyclization of squalene to give cholesterol is illustrated in Fig.

Figure no.1: Possible route for the formation of the cholesterol

Figure no 2: Some plant metabolites of cholesterol

3.2 Dioscorea species6
Tubers of many of the dioscoreas (yams) have long been used for food, as they are
rich in starch. In addition to starch, some species contain steroidal saponins and others
alkaloids. From a suitable source the sapogenins are isolated by acid hydrolysis of the
saponin. Previous fermentation of the material for some 4-10 days often gives a better
yield. The water-insoluble sapagenin is extracted with a suitable organic solvent. Both
wild and cultivated plants are used. Cultivation requires attention to correct soil and
drainage, support for the vines and freedom from weeds, Virus, fungus and insect attack.
According to the species, the tubers reach maturity in 3-5 years and on average yield 1 to
8% of total sepogenin.
Until 1970 diosgenin isolated from the Mexican yam wars the s ole s ou rc e for
steroidal contraceplive manufacture. With the nationalization of the Mexican industry,
however, prices were increased to such an extent that manufacturers switched to
10

hecogenin for corticosteroids, to other sources of diosgenin and to the use of the steroidal
alkaloids of Solanum species Total synthesis also became economically feasible and is
now much used. Recently, the economics of steroid production have again changed in that
China is now exporting large quantities of diosgenin; it is of high quality (although the
fact is of no significance commercially, it is free of the 25 isomer yamogenin) and is
reasonably priced. Three of the many Dioscorea spp. found in China and used
commercially are given in Table no.1, the tubers of these yield 2% of diosgenin, with the
average content of diosgenin for the main areas of production being l%.

Table no.2 list of plant containing triterpenoid sapogenin

Sapogenin
Diosgenin

Hecogenin
Sarsapogenin
Sarmentogenin

Species
Dioscorea sylvatica
D. mexicana, D.composita
D. tokora
D. deltoidea
Agave sisalana
A. rigida
Yucca saponin
Strophanthus saponin

Location
Transvaal and Natal
Mexico and Center America
Japan
India
America and Kenya
Mexico
Center Anerica
africa

3.3 Sisal: Hecogenin is obtained commercially as the acetate in about 0.01% yield from
sisal leaves (Agave sisalana). In East Africa, from leaf 'waste' stripped from the leaves
11

during removal of the fibre. A hecogeonin containing 'sisal concentrate' is produced. From
this the 'juice' is separated and allowed to ferment for 7 days. The sludge produced
contains about 80% of the hecogenin originally present in the leaves; steam at 1380 kPa
pressure is employed to complete the hydrolysis of the original glycosides. By filtration
and drying a concentrate containing about l2% hecogenin and varying amounts of other
sapogenins is produced.7-9

3.4 Fenugreek seeds: A spice cultivated in many parts of the world and derived from
Trigonella foenum-graecum (Leguminosae). Different commercial samples vary according
to their geographic origin. The seeds may be irregularly rhomboidal, oblong or square in
outline, and yellow, olive-green or yellow-brown to dark brown in colour. The Indian
and Moroccan varieties are quoted on the London Drug Market. They are of
pharmaceutical interest as they contain a number of steroidal sapogenin, particularly
diosgenin, which is contained in the oily embryo 11. Fazli and Hardman investigated a
number of commercial samples of seed as possible commercial sources of diosgenin
and reported contents of 0.8-2.2% expressed on a moisture-free basis.
3.5 Solanum species: This large genus (over 1000 spp.) is noted for the production of
C27 steroidal alkaloids in many species. Some of these alkaloids are the nitrogen
analogues of the C 27 sapogenins (e.g. solasodine and diosgenin). Another series of C27,
compounds contain a tertiary nitrogen in a condensed ring system (e.g. solanidine). These
compounds can also be employed in the partial synthesis of steroidal drugs, and a
number of companies have devoted considerable attention to commercial production.
Species so exploited are Solanum laciniatum, S. khasianum and S. aviculare; trials on the
production of S. marginatum have been conducted in South America.
12

3.6 Soya bean sterols: The soya (soy, soja) plant, Glyrine max (G. soya) (Leguminosae)
is extensively cultivated for its seeds, which are rich in oil and protein. The seeds also
contain appreciable quantities of the phytosterols, stigmasterol and sitosterol. Although
not sapogenins, they are included here because they are now used extensively for
steroid synthesis. They are obtained as by products of soap-making, being components of
the unsaponifiable matter of the fixed oil. Pure stigmasterol, with its unsaturated sidechain is unable to chemical conversion to suitable starting material and can replace
diosgenin, but it was more recently than sitosterol, the saturated side chain of which
could not be removed chemically without fragmentation.

3.7 Sarsaparilla root: Sarsaparilla consist of the dried roots and rhizomes of species of
smilex( Liliaceae and Smilaceae ). Much chemical work

has been done on the

sarsaparilla without botanical identification of a material. Different species contain one or

more steroidal saponins. Two isomeric genus are known: smilagenin and sarsapogenin.
Two differ only there C-25 configuration and the reduced form of the diosgenin and
yamogenin. On the hydolysis of the sarsapogenin it gives three molecules of glucose and
one molecule of rhamnose.
13

3.8 Ginseng: The roots of the Panax ginseng (Araliaceae) have hold on the place
Chinese medicine. It is produced in a China, Korea, and Siberia, and considerable
quantity, derived from Panax quinquefolium . Panax quinquefolium (American ginseng
root) Ginseng that is produced in the United States and Canada is particularly prized in
Chinese societies and many ginseng packages are prominently colored red, white and
blue12-22.

Wild ginseng

Red ginseng

Ginseng that has been heated, either through steaming or sun-drying. It is

frequently marinated in an herbal brew which results in the root becoming extremely
brittle. This version of ginseng is traditionally associated with stimulating sexual function
and increasing energy. Red ginseng is always produced from cultivated roots, usually
from either China or South Korea.
Wild ginseng is ginseng that has not been planted and cultivated domestically,
rather it is that which grows naturally and is harvested from wherever it is found to be
growing. It is considered to be superior to field farmed ginseng by various authorities and
it has been shown to contain higher levels of ginsenoside. Wild ginseng is relatively rare
and even increasingly endangered, due in large part to high demand for the product in
recent years, which has led to the wild plants being sought out and harvested faster than
new ones can grow (it requires years for a ginseng root to reach maturity). Wild ginseng
can be either Asian or American and can be processed to be red ginseng.

14

Ginseng alternatives

Gynostemma pentaphyllum (Southern ginseng, Aka Jiaogulan)

Eleutherococcus senticosus (Siberian ginseng)

Pseudostellaria heterophylla (Prince ginseng)

Withania somnifera (Indian ginseng, Aka Ashwagandha)

Pfaffia paniculata (Brazilian ginseng, Aka Suma)

Lepidium meyenii (Peruvian ginseng, Aka Maca)

Constituents: P. ginseng roots have been thoroughly studied by morden methods of

analysis and, the many compounds isolated, the medicinal activity appears to reside in a
number of saponins termed ginsenosides by Japanese workers and panaxosides by
Russian workers. However, two series of compounds do not appear to be absolutely
identical with respect to the sugar moieties. Around 30 ginsenosidcs (e.g. ginsenosidcs
Re, Rs, Rb1,Rb2
etc.) have been
described

and

designated
according

to

their Rf values in
a
system.

particular
The

panaxosides are
termed
panaxoside A, B,
C etc.

15

On hydrolysis the panaxosides yield principally oleanolic acid, panaxadiol and

panaxatriol. The natural glycoside possesses an open side-chain (e.g. 20-Sprotopanaxadiol). Ginseng root, therefore, contains a mixture of both steroids and
pentacyclic triterpenaid saponins. Two other groups of compounds present in the root
which have known therapeutic activity are high molecular weight polysaccharides
(glycans) and acetylenic compounds. The glycans of P. ginseng have been named
panaxans and those of P. quinquefolium, quinquefolans (A. B and C). Panaxans A and B
have been shown to be coristituicd mainly of -(16) linked o-glucopyranose units with
C-3 branching and a small component of peptide. Those glycans tested have
hrpoglycacmic, antiulcer and immunological properties.A considerable number of mainly
C17, but also C14, polyacetylenic alcohols have been isolated from the roots in recent years
and are typified by panaxynol and panaxydol. These compounds have been shown to
have antitumour properties and Japanese patents exist for their isolation and
derivatization. The cytotoxic activity of the C17 polyacetylenes against leukaemia cells has
been shown to be almost 20 times greater than that for the C14-compounds.

Other constituents include sesquiterpenes (-elemene, panasinsanol A and B,

ginsenol etc.)

16

Panax pseudoginseng ssp. himalaicus var. augusttfolius (Himalayan ginseng).

The roots contain active saponins and ginsenosides R 0 and Rb1, chikusetsusaponins IVa
and VI have been recorded. Pseudoginsenoside-RI2 which consists of oleanolic acid,
phthatic acid, glucuronic acid and xylose moieties arranged as below

Panax notoginseng roots (Sanchi-ginseng) contain several dammarane saponins.

identical a similar to those of ginseng, and a polysaccharide (sanchinan-A) having a
branched structure with a galactose backbone and side-chains containing arahinose and
galactose this glycan contains a small amount of protein and possesses
reticuloendothelial activating properties.
Panax japonicumr and P. japanicum var. major contain chikusetsusaponins.
ginsenosides and glycans.
Panax vietnamensis (Vietnamese ginseng). The roots are a secret remedy of the
Sedang ethnic minority and contain a number of known and new ginsenosides .

4. PENTACYCLIC TRITERPENOIDS SAPONIN

17

Unlike the steroidal saponins, the pentacyclic triterpenoid saponins are rare in
monocotyledons. They are abundant in many dicotyledonous families, particularly the
Caryophyllaceae, Sapindaceae, PolygaIaceae and Sapotaceae. Among the many other
dicotyledonous families in which they have been found are the Phytolaccaceae,
Chenopodiaceae, Ranunculaeeae, Berberidaceae, Papaveraceae, Linaceae, Rutaceae.
Zygophyllaceae, Mynaceae, Cucurbitaceac, Araliaceac, Umbelliferae. Primulaceae,
Oleaceae, Lobeliaceae, Campanulaceae, Rubiaceae and Compositae.
In these saponins the sapogenin is attached to a chain of sugar or uronic acid
units, or both, often in the 3-position, as in the examples above.
4.1 Biosynthesis: As with the steroids, involves ring-closure of squalene and is
illustrated in Figure.

Triterpenoid saponins may be classified into three groups represented by amyrin, -amyrin and lupeol, The related triterpenoid acids are formed from these by
replacement of a methyl group by a carboxyl group in positions 4, 17 or 20.

18

4.2 Plant containing Pentacyclic triterpenoids saponin

Saponin
Aescin

Genin
Aescigenin

Sugar components
2 glucose, 1 glucoronic acid,

Aralin
Calendula-

Aralidin
Oleanolic acid

tiglic acid
hippocastanum
2 arabinose, 1 glucuronic acid Aralia japonica
2 glucose, 1 galactose,
Calendula

Glycyrrhetinic acid
Noroleanolic acid

1 glucoronic acid
2 Glucoronic acid
1 Rhamnose, 1 glucose,

officinals
Glycyrrhiza spp.
Guaiacum spp.

Hederagenin

1 arabinose
1 glucose, 1 arabinose

Hedera helix and

saponin A
Glycyrrinic acid
Guaianin
Hederacoside A

Occurrence
Aesculus

Symphytoxide

Hedergenin

1 Arabinose, 2 glucose

Araliaceae
Symphytum

Primula saponin

Quillaliac acid

1 rhamnose, 1 glucose,

officinale roots
Primula spp.

Saikosaponin

Saikogenin F

1 galactose, 1 glucoronic acid

1 glucose, 1 fructose
Bupleurum spp.

A.

Quillaia Bark: Quillaia bark (Soap Bark, Panama Wood, Quillaia) is the dried
inner bark of Quillalia saponarica and of other species of Quillalia (Rosaceae). 23,
24

19

Constituents: The bark contains a mixture of saponin which on hydrolysis

yields the principle sapogenin quillaic acid (hydroxygypsogenin) and gypsogenin
together with sugars, uronic acids and acyl moieties have shown that quillaia
saponin is a mixture of acylated triterpanoids oligoglycosides. Mild alkaline
hydrolysis gives two deacyl saponin (Quillalic acid 3,28-O- bisglycosides)
together with the less polar compound. The structure of the one compounds is
given below; the other lacks the terminal glucose. Quillalia contains about 10%
of saponin, ethanol (45%) , soluble extractive are not less than 22% and also
sugar , starch and calcium oxalate.

Fig: Component of the quillalia saponin

B.

Liquorice root: Liquorice consists of the dried unpeeled roots and stolen of the
Glycerrhiza glabra (Leguminosae). Liquorice owes most its sweet taste to
glycyrrhizinic, potassium and calcium salt of the glycyrryzinic acid is the
diglucopyranosiduronic acid of glycyrrhizinic acid which have a triterpenoid
structure. Other hydroxyl and deoxy triterpenoids acids related to glycyrrhetic
acid have been isolated; the C-20 epimer of glycyrrhetic acid is named liquiritic
acid. The other constituents of it are liquiritin, isoliquiritin, liquiritigenin,
isoliquiritigenin. Spanish spp. contain 5-10%, Russian spp. contain 10%, Persian
spp. contain 7.5% of glycyrrhizin. 26

20

Fig: Triterpenoids saponin and flavanois of glycerrhiza glabra

C.

Senega root: Senega consists of the dried root of Polygala senega L.

(Polygalaceae) or of closely-related species of Polygala or a mixture of these. 27
Constituents: Senega contains 6-12% of triterpenoid saponins. Earlier work
based on the hydrolysis of the crude saponin mixture (senegin) produced a variety
of products but during the 1970 Japanese workers characterised a number of
individual saponins had on the aglycone presenegenin with glucose at C-3 and a
number of sugars and a cinnamic acid derivative forming a branched chain at C28: the units compnsing the principal glycoside seneginin .
21

A number of oligosaccharide multi-esters have recently been identified in the

roots and named seaegoses A-I. rhamnoliquiritin, liqucoumarin, 6-acetyle-5hydroxy-4-methyle coumarin are the other constituents of the senega root.

D.

Quassia Wood: Quassia (Jamaica Quassia) is the stem wood of Picrasma

excelsa (Pic roena excelsa or Aeschrion excelsa) (Simarubaceae), which is
known in commerce as Jamaica quassia. 29
Constituents: Quassia contains the amaroid (terpenoid) compound quassin, an
intensely bitter lactonc; also neoquassin, 18-hydroxyquassin and scopoletin.
Quassia wood also contains alkaloids, as illustrated by cathine-6-one.

Other triterpenoids: 1-4

22

23

5. NEW SKELETONS OF TRITERPENOIDS

A number of triterpenoids possessing novel carbon frameworks have been
isolated from various sources. The structures of these triterpenoids are of much interest
from the point of view of their formation biogenetically.
1. Sipholane: The sipholane skeleton consists of a cis-octahydroazulene linked via
an ethylene bridge to a trans- decahydrobenzoxepine. The structure of the sipholane
skeleton was established by an X-ray diffraction analysis of one of the natural
compound derivatives. Eight new triterpenes possessing this skeleton have been isol ated from the Red Sea sponge Siphonochalina siphonella 35. The X-ray derived
structure of the major triterpene, sipholenol-A made possible. The NMR and Mass
spectral interpretations and the structure elucidation of the additional seven new
compounds. Of special interest is the suggested biogenesis of the sipholanes starting
from 2, 3:6, 7:18, and 19-triepoxysqualene. In contrast to the single cyclization process
that takes place in the biogenesis of tetra- and pentacyclic triterpenes, the suggested
route leading to the sipholanes involves two consecutive cyclizations. 35-39
2. Siphonellane: Siphonellinol, a triterpene, possessing the new carbocyclic
skeleton, siphonellane was also isolated from the marine sponge Siphonochalina
siphonella by Carmely et al 40 . The proposed biogenesis of this triterpene shows a
close relationship to that of the squalene derived sipholanes and differs only in cycliz ation of one half of the molecule. 40-44
3. Polypodane: A new oily triterpene hydrocarbon having a novel bicyclic carbon
skeleton, polypodane and named -polypodatetraene was isolated from the fresh leaves
of Polypodium fauriei and Lemmaphyllum microphyllum 46 . A related new
triterpene, -polypodatetraene, was isolated from leaves of Polystichum ovatopaleaceum and P. polyblephatum. A bicyclic diol possessing this polypodane skeleton
has also been isolated by Boar et al46. From gum mastic, the abundantly available
resin obtained from the Mediterranean shrub Pistacia lentiscus. The structure and
absolute stereochemistry of the bicyclic diol are fully consistent with its formation by
interception of the bicyclic carbocation postulated as an intermediate in the cyclization
of the chair-chair-boat conformation of (3S) squalene-2,3-epoxide 56. This bicyclic
24

triterpenoid retains all of the regio- and stereochemical features necessary for
continued cyclization. The isolation of these bicyclic triterpenoids supports the
postulation of van Tamelen and his co workers that the cyclization of squalene
precedes via a series of discrete conformationally rigid carbocationic intermediates. 4552, 56

4. Spirosupinane: The structure of spirosupinanonediol, a new triterpenoid isolated

from Euphorbia supina has been established by spectral and X-ray analyses as
7(89) abeo-9SD: C-friedo-B: A'-neogammaceran-8-one-3S, 7S-diol 51-56 . With a
novel skeletal system for which the name spirosupinane has been proposed. This is the
first example of a triterpene possessing a Spiro skeleton. The probable biogenesis of
spirosupinanonediol involving an 8, 9-dihydroxyfernane derivative has been
rationalized.
5. Radermasinin: Radermasinin, a novel cytotoxic triterpene lactone isolated from
Radermachia sinica was shown to have structure 31 by spectral data and singlecrystal X-ray analysis of its monohydrate. It possesses a gem-dimethylvinyl group at C18 in addition to a spiro -hydroxy lactone moiety at C-17 and its possible biogenetic
path-way involving 21-hydroxy-18-olean-28-oic acid derivative as precursor has been
suggested55, 60-64 .
6 Baccharane: The structure of hosenkol-A, the first example of the natural baccharane
triterpenoid of the missing inter-mediate shionane and lupane , has been deter mined by
spectroscopic methods as well as by X-ray crystallographic analysis. The isolation of
hosenkol-A which has a unique spiro-ring strongly, supports the postulated biogenesis
of lupane and shionane via baccharane 58-62.
7. Rearranged lanostanes: Some new rearranged lanostanoids having novel carbon
skeletons, such as 17, 14-friedolanostane,17,13-friedolanostane and 8 (1413R) abeo17,13 friedolanostane , have been isolated from seeds of Abies mariesii. A. firma and A.
sibirica. The new rearranged lanostane skeletons have been considered to be
biosynthesized from the lanostane skeleton by enzymic dehydrogenation of H-17 or
dehydroxylation of OH-17 followed by successive 1,2-shifts of methyl groups) and a
ring bond66, 70-74.
25

A few triterpenoids possessing the novel 14(1312) abeo lanostane skeleton

have been isolated from Kadsura longipedunculata and K. heteroclita .
8. Degraded and rearranged lanostanes: Glycinoeclepin A, a natural hatching stimulus
for soyabean cyst nematode, has been isolated from the aqueous extract of roots of
kidney bean (Phaseolus vulgaris). Its novel structure was elucidated by spectroscopic
and X-ray crystallographic analyses. The structure is characterized by migration of two
methyl groups.77-82
Involved in the C and D rings and oxidative cleavage of the B-ring with loss of
one carbon atom, compared with those of cycloartanes (9, 19-cyclolanostane), and is
regarded as a pentanortriterpene. Two other new nortriterpenes, glycinoeclepins B and
C possessing a similar ring system to that of glycinoeclepin A, but with a non-degraded
side chain, have also been isolated from the same source .Javeroic acid and phellinic acid
having a novel degraded and rearranged lanostane skeleton were isolated from Phellinus
pomaceus and their structures were determined by a combination of chemical and
spectral analyses. The new carbon skeleton of these two triterpenes was confirmed by
X-ray crystallographic ana . lysis of the dimethyl ester of javeroic acid.
9. Carotenoid-like triterpenes: Ksebati and his co-workers have isolated five new
triterpene galactosides named pouosides A - E from Asteropus sp. a Pacific marine
sponge. The carbon skeleton 30 of the pouoside aglycones is new and parallels that of
the C.o-carotenoids, with its terminal cyclohexane rings linked by a symmetrical
acyclic chain 86-88, 90.
10. New skeleton

monocyclic

and

bic yclic triterpenoids: Three

new

triterpenoids, -irigermanal, -irigermanal and iridogermanal possessing novel

bicyclic and monocycltc carbon skeletons, have been isolated from rhizomes of Iris
yermanica. The compounds are closely related to ambreine. 90-91
11. Swertane: The structure and stereochemistry of swertanone, a triterpene ketone
with a novel skeleton, swertane isolated from Swertia chirata, have been established
from spectroscopic data and X-ray crystallographic analysis. A possible biogenetic
pathway for the formation of the swertane skeleton has been envisaged involving
cyclization of squalene-2.3-epoxide in the usual manner leading to the non-classical
26

carbocation followed by a 1, 3-hydride shift from C-17 to C-21. A series of 1, 2shifts and elimination of a proton from C-7. 91
12. Pfaffanes: Pfaffic acid, a novel hexacyclic nortriterpene possessing the pfaffane
skeleton was isolated from Pfaffia paniculata and its structure was established by X-ray
crystallographic analysis of its methyl ester. Subsequently, four new pfaffane-type
nortriterpenes were isolated from P. pulrerulenta together with pfaffic acid and its -Dglucuronopyranoside. 92

27

6. STRUCTURE NEW SKELETON OF TRITERPENOIDS

28

29

30

31

32

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38