1132 ABSTRACTS OF CHEMICAL PAPERS.

"When dinitrobenzoparatoluide is treated with sulphuretted hydro

gen, it yields amidonitrobenzoparatoluide—
C,HJMe(NOl)(NHJ).NH.COPh[l : 3 : 3 : 4],
crystallising in red needles (m. p. 138°), and on reduction with tin
and hydrochloric acid the dinitro-compound yields diamidobenzopa.ro-
toluide (m. p. 184°), which is soluble in alcohol and ether.
The sulphate, CuH„N3O.H2S04, hydrochloride, nitrate, and oxalate
are crystalline salts, soluble in water.
Anhydro-compounds from Xylidine.—The preparation of x-benzoyl-
tcylidide, a-monmiitrobenzoxylidide, and a.-anhydrodiamidobenzoxylene
from a-xylidine and of the corresponding /3-compounds from S-xyli-
dine, have been already described by F. Boyes (Ber., 10, 143, this
Journal, Abstr., 1878, 143). The a-anhydro-base—

C.HaMe< ^CPh,

crystallises in colourless needles (m. p. 195°), soluble in alcohol.

The hydrochloride, ClsHnNj,HCl, oxalate, nitrate, and sulphate form
needle-shaped crystals. All these salts, with the exception of the
sulphate, dissolve readily in alcohol and in water.
The corresponding /8-compound forms colourless needles (m. p.
215°), soluble in alcohol. The sulphate and hydrochloride also form
needle-shaped crystals which are easily soluble in water.
The properties and mode of preparation of paranitrobenzamido-
naphthalene (m. p. 224°), paramidobenzamidonaphthalene (m. p. 186°),
B-nitrorthobenzamidonaphthalene (m. p. 175°), anhydrobenzoyldiamido-
naphtlialeiie (m. p. 210°), dinitrobenzamidonaphthalene (m. p. 252°),
dinitramidonaphlhalene (m. p. 233°), and diamidobenzamidonaphthalene
have already been described by Ebell (Ber., 7, 1317; 8, 562).
From these facts the author concludes that it is only the ortho-
diamido-compounds which have the power of losing a molecule of
water and forming anhydro-bases, when subjected to the powerful
action of nascent hydrogen. W. C. W.

Dinitro- and Trinitro-resoreinol. By R. Benedikt and A. v.

Hubi, (Monatsh. Chem., 2, 323—330).— b'itz, who discovered dini-
troso-resorcinol (Ber., 1875, 631), did not succeed in converting it into
dinitro-resorcinol, but found that nitric acid, even when very dilute,
converts it at once into trinitroresorcinol, and that when heated
with potassium permanganate or ferricyanide, even in the cold, it is
completely oxidised and burnt. Weselsky and Benedikt however
have shown that nitroso-compounds can be oxidised to nitro-com-
pounds by exposing them suspended in ether to the action of nitrons
acid vapours (p. 726 of this volume), the vapour being passed through
the liquid for several hours, and the reaction being completed when
the nitroso-compound is entirely dissolved. The product must be
repeatedly shaken with water to remove oxides and acids of nitrogen
dissolved in the ether, and the ether may then be distilled off, but not
completely, as in that case, a small quantity of nitric acid which
 ORUANIC CHEMISTRY. 1133
remains behind in spite of the agitation with water, would indnce a
further nitration to trinitro-r&sorcinol. The product is then ponred
out into a small basin, the ether left to evaporate at ordinary tempera
tures, and the residue, after pulverisation, thoroughly washed with cold
water. It may then be crystallised from dilute alcohol without fear of
further nitration.
Dinitroresorcinol crystallises in pale yellow laminae, melts at 142°,
is partially snblimable, and detonates when strongly heated. When
heated with very dilute nitric acid (e.g., 1 : 10) it is completely con
verted into trinitro-resorcinol. Its potassium salt crystallises in
orange-yellow easily soluble prisms. The ammonium salt forms
reddish-yellow geodes having a satiny lustre. The normal barium salt,
CeH2(N02)202Ba, prepared by boiling dinitroresorcinol with barium
carbonate, crystallises on cooling in geodes of small yellow needles
nearly insoluble in cold water.
Nitro-amidoresorcinol, C«H2(N02)(NH2)(OH)2, is obtained as an
ammonium salt by passing hydrogen sulphide into a solution of
dinitroresorcinol (50 g.) in 356 c.c. absolute alcohol mixed with
150 c.c. aqueous ammonia and heated to about 70°. The yellow
pulpy ammonium salt which forms at first dissolves slowly to a clear
dark-red liquid, whereupon the stream of gas must be interrupted,
and the liquid left at rest for twelve hours. The ammonium salt then
separates in dark-coloured needles traversing the whole liquid ; and
on draining off the mother-liquor, dissolving the crystals in water,
filtering from sulphur, and cautiously adding dilute sulphuric acid as
long as a precipitate is formed, but no longer, free nitroamidoresorcinol
is obtained as a brown crystalline precipitate, which may be purified by
recrystallisation from weak spirit. It then forms black-brown crys
tals sparingly soluble in water, easily in alcohol and ether, melting at
about 1 70°. It dissolves easily in acids and in alkalis. The alkali
salts reduce ammoniacal silver solution, even at ordinary tempera
tures, and form with lead salts a red-brown flocculent precipitate ; with
barium salts, after a while, a black crystalline precipitate. The
ammonium salt, as already observed, separates on reduction of dinitro
resorcinol in alcoholic solution, in slender needles mixed with sulphur,
which may be easily removed by washing with carbon bisulphide, the
purified ammonium salt then forming dark violet crystals containing a
variable quantity of ammonia. The salt when recently prepared has
the normal composition C6Hs(N02)(NH2)(ONH4)2, but gives off part of
its ammonia on mere exposure to the air, aud after several days'
drying at 100° is completely reconverted into free nitroamidoresor
cinol. In aqueous solution, the ammoniacal salt is very unstable, and
is completely decomposed on heating, with formation of resinous pro
ducts.
.Nitramidoresorcinol sulphate, [C6H2(OH)2(N02)(NH2)]2S04H2) forms
brownish slender needle-shaped crystals easily soluble in water and
decomposing at 100°.
Dinitro-amidoresorcinol, C«H(OH)2(N02)2.NH2, or Styphnamie acid,
the analogue of picramic acid, is obtained on prolonged heating of
styphnic acid (trinitroresorcinol) dissolved in alcohol with ammonium
.sulphide, and purified by acidulating the resulting solution with acetic
1134 ABSTRACTS OF CHEMICAL PAPERS.
acid, repeatedly agitating it with ether, then distilling off the ether,
and recrystallising the crnde product from absolute alcohol.
Styphnamic acid forms copper-red shining laminae, nearly insoluble
in water, only slightly soluble in alcohol, but dissolving readily in
alkalis, and precipitated therefrom by dilute acids only at the boiling
heat. It dissolves easily in strong snlphuric acid, forming a colourless
liquid, from which it is precipitated by water in red laminee.
Dinitrodiazoresorcinol, C,H8N40« = HO.N I N.C.H j ^Nq'^.— The
potassium salt of this compound is obtained by dissolving 5 g. mono-
or di - nitramidoresorcinol in 155 c.c. sulphuric acid diluted with
5 volumes of water, adding an excess of potassium nitrite in aqueous
solution, and boiling till the liquid turns greenish-yellow. On cooling,
the entire liquid solidifies to a light-yellow crystalline mass of the
potassium salt, which may be purified by recrystallisation, and sepa
rated from very strong aqueous solutions, or from dilute sulphuric
acid, or on mixing its solution with alcohol, in long slender anhydrous
crystals, having a fine yellow colour without surface-shimmer. By
slow crystallisation from dilute aqueous solution, it is obtained in com
pact brown prisms with blue surface-shimmer, having the composi
tion CjHN^bK + H,0. This salt is highly explosive, decomposing
with violent detonation when heated, struck, or pressed. It is very
soluble in hot, very sparingly in cold water. It does not appear
possible to introduce more than 1 atom of potassium into dinitrodiazo-
resorcinol, the monopotassic salt crystallising out unaltered from its
solution mixed with the calculated quantity of potassium carbonate.
Free dinitrodiazoresorcinol is obtained by dissolving the potassium
salt in dilute sulphuric acid, the colourless liquid, on exposure to the air,
depositing it in yellow triclinic crystals which detonate when heated.
Mononitrodiazoresorcinol is formed on mixing a solution of nitro-
amidoresorcinol in dilute sulphuric acid with the calculated quantity
of potassium nitrite in cold aqueous solution, and separates from the
liquid as a brown crystalline precipitate, which may be recrystallised
from alcohol.
Action of Potassium Hydroxide on Dinitrodiazoresorcinol.—When a
solution of the above-described potassium salt is boiled with potassium
hydroxide, its colour quickly changes from light yellow to red ; nitrogen
is abundantly evolved; and on acidulating the liquid, the greater part of
the product separates as a flocoulent precipitate, which, on recrystal
lisation from absolute alcohol, yields two bodies, one (A) the chief
product of the reaction, separating in granular shining crystals;
whilst the other (B) is deposited from the mother-liquors in light-
brown laminee. This latter body is the sole product obtained when
the reaction takes place in alcoholic instead of aqueous solution, and
may then be separated by diluting the alcoholic liquid with water,
acidulating with sulphuric acid, and purified by crystallisation from
strong alcohol.
The body A is slightly coloured, nearly insoluble in water, slightly
soluble in alcohol, easily in ether and strong acetic acid. It melts at
268°. Its analysis agrees nearlv with the formula of tetranitrodiresor-
cinol-, C13H,NtO„ = (OH),(N02),HC..C,H(NO,)i(OH)„ which is a
 ORGANIC CHEMISTKT. 1135
diphenyl-derivative, a view which is supported by its high melting
point, and by the circumstance that it is not susceptible of further
nitration, but crystallises unaltered from solution in boiling nitric
acid. It dissolves in potassium carbonate, the solution on cooling
depositing the acid potassinni salt, CuH4KvN40ij, in shining red
needles ; and by mixing the solution of this salt with potassium
hydroxide, the normal salt is obtained in needle-shaped crystals, having
a dark green colour and metallic lustre.
The body B, obtained by the action of alcoholic potash on dinitro-
diazoresorcinol, forms large light brown shining laminie, melts at 210°,
and is sublimable : it is very slightly soluble in boiling water, more
readily in alcohol. According to its analysis, it might be regarded as
a new dinitroresorcinol ; but this view is inconsistent with the fact
t hat it is completely unattacked by strong boiling nitric acid.
H. W.
Quinone Derivatives. ' By E. Sarauw (Annalen, 209, 93—131).—
Quinone when treated with hydrobromic acid yields a mixture of mono-
and di-bromoquinol, with the intermediate production of quinhydronc.
This reaction may be explained thus : at first quinhydrone is formed
with liberation of bromine ; the former is converted by excess of
hydrobromic acid into mouobromoqninol, whilst the latter reacts with
the unattacked quinone, forming monobromoquinone and hydrobromic
acid ; and finally the monobromoquinone combines with the hydro
bromic acid to form dibromoquinol. Wohler in the study of the
analogous action of concentrated hydrochloric acid (Annalen, 51, 155)
noticed the formation of a dark coloration in the earlier part of the
reaction, which he concluded to be due to an intermediate product of
the formula C«H24(OH)(OCl). The author, however, shows that the
actions of hydrochloric and hydrobromic acids are precisely similar,
and that the dark coloration is due to quinhydrone.
Monobromoquinol, C8H3Br(OH)j.—Owing to the difficulty of separa
ting the mono- and di-bromoquinol in the above reaction, the mono
bromoquinol is best prepared by the direct reaction of equal molecules
of bromine and quinol in chloroform solution (comp. Abstr., 1880, 385).
Monobromoquinol crystallises indelicate leaflets (m. p. 110°), soluble
in water, benzene, &c.; sparingly soluble in chloroform and petroleum.
Monobromoquinone, CjHsBrOa, is obtained by the oxidation of mono
bromoquinol with ferric chloride. It crystallises in tufts of needles
(m. p. 55—56°), easily soluble in chloroform, ether, alcohol, &c. ;
sparingly soluble in petroleum and in hot water. Monobromoquinone
dissolves in ammonia and in sodium hydroxide or carbonate, to form a
dark black solution ; it is probable that the bromine-atom is displaced
by the hydroxyl-group, and a body of formula, C,H3(OH)Os, is pro
duced.
Dibromoquinol, C«H2Bra(OH)a, is prepared either by the action of
hydrobromic acid on monobromoquinone, or of 2 tuols. bromine on
1 mol. quinol, or of 1 mol. bromine on 1 mol. quinone. It crystallises
in tablets (m. p. 186—187°) , soluble in alcohol and ether, sparingly
soluble in benzene, carbon bisulphide, &c.
An isomeric dibromoquinol of probable formula CeH3Br(OH)(0 Br),
is obtained in the preparation of ordinary dibromoquinol from quinone.