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ANTLINE-BLACK A N D ALLIED COMPOUNDS. PART 11. 1117


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CXV1I.-Aniline-black and Allied Compounds. Part 11.


By ARTHUR GREENand ARTHUR
GEORGE EDMUND
WOODHEAD.
IN a former communication (Trans., 1910, 97, 2388) we have
described and characterised a series of quinonoid derivatives of
the colourles base leuco-emeraldine, which constitute the inter-
mediate stages in the production of aniline-black. These primary
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1118 GREEN AND WOODHEAD:

products, two of which, namely, emeraldine and nigraniline, when


formed on the fibre have long been known t o technologists, are
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readily interconvertible by oxidation or reduction, and the results


obtained by the quantitative determination of the oxygen or
hydrogen consumed in passing from one stage to the other support
the following constitutional formulze for the respective compounds :
L eucoe m eraldine :
NH NH NH NH
/\/\A /\/\/\ /\/\/\ /\/\/\
I I I I I I I I ,I I I I I I 1 IN&
\f \./\kH\/ Vv&\/ \/%/ \/

Colourless, amorphous base. Nearly insoluble in all solvents,


including 80 per cent. acetic acid. High melting point. On
exposure t o ' air in the damp state is slowly oxidised t o proto-
emeraldine, more rapidly when warm.
Protoemeraldine (monoquinonoid stage *) :
NH NH NH NH

NH NH
Violet base, forming yellowish-green salts. Soluble in 80 per
cent. acetic acid with a grass-green colour.
b'meraldine (diquinonoid stage) :
NH NH N N

Violet-blue base, forming green salts. Soluble in 80 per cent.


acetic acid and in 60 per cent. formic acid with a pure green
colour. Dissolves in pyridine with a bright blue colour. Dissolves
in pure concentrated sulphuric acid with a purplish-brown colour,
and on dilution with water gives a bright green precipitate. The
salts are stable, but t.he base is slowly oxidised by air to nigraniline
base.
Nigrnniline (triquinonoid stage) :

, ,
NH
I/\/\/\I p/L\
I I I
/\/\,/\
I I I I
N
I
N
/>/?/)
\/ v\NG\/ v\N/\/\AN/\/ \qH
Dark blue base, forming blue salts. Soluble in 80 per cent.
acetic acid and in 60 per cent. formic acid with a pure blue colour,
which on heating becomes green through reduction t o emeraldine.
Dissolves in pyridine with a bright blue colour. Dissolves in
* In these formule, the position of the quinonoid groups is not yet established.
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ANILINE-BLACK AND ALLIED COMPOUNDS. PART 11. 1119

concentrated sulphuric acid with a violet colour, and on dilutior


with water gives a bright green precipitate of emeraldine sulphate
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The base is stable, but the salts are very unstable.


Pernigraniline (tetraquinonoid stage) :
N N N N
/\A/\ /\A/ /\/\/\ /\/\/\
I I I I I I
\/ \A/\/
I\
\/\p I I I I
\AN/\/
I I I I
\/NNH
Purple base, forming purple salts. Soluble in 80 per cent. acetic
acid with a violet colour. Both the base and its salts are very
unstable, quickly undergoing degradation t o the lower quinonoid
stages with simultaneous production of decomposition products.
I n our view, none of the above compounds can be regarded as
aniline-black, but tK0y constitute, in fact, indamine-like inter-
mediate stages in its formation. Apart from their colour, they
differ from aniline-black in their greater instability, and give on
reduction leuco-emeraldine, not easily oxidised by air, instead of a
readily re-oxidisable leuco-black.
On the other hand, Willstatter and Dorogi (Ber., 1909, 42,
2147, 4118) have prepared a series of products which they term
aniline-blacks, by making use of methods not differing substan-
tially from those employed by us to obtain emeraldine and
nigraniline, except that the products formed were afterwards
subjected to it prolonged treatment with dilute sulphuric acid with
the object of removing mineral impurities. By extraction with
80 per cent. acetic acid we have been able t o show that these
blacks are, in fact, mixtures of emeraldine or nigraniline with

polymerisation or decomposition products formed by the action of


the acid used in the purification process. This conclusion was
further confirmed by Green and Wolff (Ber., 1911, 44, 2570), who
showed that by oxidising aniline with dichromate according t o
Willstaitter and Dorogis method, but without subjecting the
product to subsequent purification with sulphuric acid, a
compound was obtained entirely identical with our emeraldine,
and completely soluble in 80 per cent. acetic acid, giving a bright
green solution. After the acid treatment, however, the product
(Wilistatter and Dorogis bichromate-black ) is only partly
soluble in this solvent, and differs considerably from pure
emeraldine.
To their so-calIed aniline-blacks, Willstiitter and Dorogi assign
formulz which are the same as those given by us to nigraniline and
pernigraniline, although the main constituent of their products
must be emeraldine or nigraniline respectively. The high state
of oxidation assumed by these authors for their preparations is,
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1120 GREEN AND WOODHEAD:

moreover, opposed to the fact ascertained by us that under the


influence of dilute acids the higher quinonoid stages readily
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become degraded to the lower stagea, a fact which, although


capable of ready demonstration, is also disputed by Willstiitter.
The conclusions of Willstiitter and Dorogi have received apparent
verification from a series of analytical results published in a later
communication by Willstiitter and Cramer (Ber., 1910, 45, 2976),
in which is described a new method for the estimation of quinonoid
groups based on reduction with phenylhydrazine and the measure-
ment of the nitrogen evohed. Green and Wolff (Eoc. cit.) have,
however, shown t h a t the results obtained by this method are only
trustworthy provided the temperature required for reduction to the
leuco-compound does not exceed 80-90, for above this tempera-
ture auto-decomposition of the phenylhydrazine is liable to occur,
and rapidly increases as the temperature is raised. Contrary to the
statement of Willsthtter and Cramer it was found t h a t emeraldine
and nigraniline are completely reduced to leucoemeraldine a t tem-
peratures considerably below 80 (even in the cold), and t h a t the
nitrogen evolved thereby corresponds with the formula= previously
assigned by us. A t 150, however, which is the final temperature
employed by Willstiitter and Cramer, the evolution of nitrogen
becomes nearly continuous, and consequently the conclusions which
these authors base on their results are invalidated.
I n a subsequent communication (Ber., 1911, 44, 2162), Will-
stiitter and Cramer have published the results of a repetition of
our reduction experiments with titanium trichloride, obtaining
figures which are in close accord with those previously obtained by
us. As, however, these results do not agree with their own theo-
retical views or with their phenylhydrazine determinations, they
fall back on the assumption that the end-product of the reduction
with titanium trichloride in the cold or with phenylhydrazine
below 150 is not the true leucoemeraldine, but the monoquinonoid
stage, so t h a t all the stages are thus raised by one. The extreme
improbability of this w u m p t i o n is apparent when it is considered
that the raduction product is perfectly stable in presence of a large
excess of the strong reducing agent, and further t h a t the substance
is almost colourless (brownish-white to greyish-white). The only
experimental evidence advanced in its favour is the determination
of the nitrogen evolved when the reduction product is heated
with phenylhydrazine at 150, which owing to the a&o-decomposi-
tion of phenylhydrazine at this temperature must be considered
invalid.
I n order to place- the matter beyond doubt, it seemed desirable
t 3 carry out quantitative reductions with boiling titanium
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ANILINE-BLACK AND ALLIED COMPOUNDS. PART 11. 1121

trichloride on leucoemeraldine prepared from emeraldine by the


action of phenylhydrazine a t a low temperature. I f this product
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is actually a monoquiuonoid one, it would certainly undergo further


reduction under these conditions, with a corresponding consump-
tion of titanium trichloride. The results obtained justify the view
that no reduction occurs, for the small consumption of hydrogen
is not more than that accountable to aerial oxidation of the
leuco-compound and to experimental error,

EXPERIMENTAL.
Emeraldine.
The preparation of the emeraldine employed was carried out
substantially as previously described, b u t with some modifications
in detail, which lead to a purer product. Aniline (144 gram) is
suspended in water (3 litres), and carefully neutralised with hydro-
chloric acid (about 160 C.C. of 30 per cent. HCI). A n excem of
hydrochloric acid (93 c.c.j is further added, together with syrupy
vanadium chloride (25 drops). When cold, the solution is mixed
with a, cold solution of sodium chlorate (84 grams) in water
(600 c.c.), and the whole is kept in a refrigerator a t a temperature
of from 0" to 5" for about forty hours. The emeraldine hydro-
chloride formed is then collected, thoroughly washed with water,
stirred with an excess of dilute ammonia in order to basify it,
and again collected, and repeatedly washed with water. The
emeraldine base thus obtained is free from nigraniline, and in
the form of paste dissolves readily in 80 per cent. acetic acid,
giving an almost clear, bright green solution. After drying a t
looo it is less soluble, and becomes more insoluble at a higher
temperature. I f the base is exposed to air for a few days in the
damp state, i t becomes completely oxidised to nigraniline, and
then gives a clear, blue solution in 80 per cent. acetic &d. The
failure of Willstatter and Dorogi to obtain anything more than
suspensions in this solvent is obviously due to the want of purity
of their products, and this is further supported by their statement
(Bey., 1911, 44, 2166) that the preparation obtained by them
contained about 0.8 per cent. of ash before treatment with acid,
whilst the ash i n the emeraldine base prepared as above was less
than 0.1 per cent. The presence of small quantities of acids or
of salts prevents complete solubility, or causes the formation of a
fine colloidal precipitate.
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1122 GREEN AND WOODHEAD :

L euco emeraldine.
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The leucoemeraldine was prepared by the reduction of emeraldine


in the undried condition a t the ordinary temperature. The
emeraldine paste obtained as above described was incorporated
with an excess of phenylhydrazine in a mortar, the colour thereby
changing from deep violet through slate-blue to a dirty white. For
experiments with titanium trichloride the product was freed from
excess of phenylhydrazine by washing with ether, and dried quickly
on a porous plate. It still contained 49.42 per cent. of water.
The percentage of chlorine in the dry product was found to
be 0.73.
For ultimate analysis the base was completely freed from water
by further washing with anhydrous ether, and then dried under
diminished pressure a t 50-70. It fornied a greyish-white powder,
which became blue after a few hours' exposure to air, but could
be kept unchanged in toluene containing a trace of phenyl-
hydrazine. The following results were obtained on analysis * :
(=(mean of three determinations) = 79-06 ;H(mean of three deter-
minations) = 5.58 ; N(mean of two determinations) = 15.44.
C,,H,,N8 requires C = 78-91; H =5-75; N = 15.34 per cent.

A t t e m p t e d Reduction w i t h Titanium Trichloride.


A measured quantity of the standard titanium trichloride solu-
tion was run into a flask previously filled with carbon dioxide, and
was heated to boiling. A weighed quantity of the moist leuco-
emeraldine (containing 50.58 per cent. of dry base) was then
added, and the whole W ~ Sboiled for five minutes. The contents
of the flask were then iapidly cooled by immersion in iced water,
and filtered when cold. All these operations were performed
with a stream of csrbon dioxide passing through the apparatus.
An aliquot portion of the filtrate was then titrated with a
N / 10-solution of ferric ammonium sulphate. I n two blank experi-
ments made under these conditions 45 C.C. of the titanium
trichloride solution required 24-12 C.C.of the N / 10-ferric solution.
I. 1.0222 Grams of moist leucoemeraldine (containing 50.58 per
cent. of dry base) and 45 C.C. of titanium trichloride required
20.5 C.C. N/lO-ferric solution. The difference between this figure
and the blank experiment is 3-5 c.c., which represents a consump-
tion of hydroger, of 0.00035 gram for the amount of leuco-
emeraldine taken, or of 0*00@59gram for 1 gram of dry leuco-
emeraldine.
* The numbers are corrected for chlorine (0.73 per cent.).
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ANILINE-BLACK AND ALLIED COMPOUNDS. PART 11. 1123

11. 1.0795 Grams of moist lewxemeraldine (50.58 per cent.)


and 46 C.C. of titanium trichloride required 19.8 C.C. of the
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N/lO-ferric solution. The difference between this figure and the


blank experiment is 4.32 c.c., which represents a consumption of
hydrogen of O.OGO43 gram for the amount of leucoemeraldine
taken, o r of 0*00077 gram for 1 gram of dry leucoemeraldine.
111. 1.7270 Grams oi moist leucoemeraldine (50.58 per cent.)
and 45 C.C. of titanium trichloridc required 16-92 C.C. of N/lO-ferric
solution. The difference between this figure and the blank experi-
ment is 7.2 c.c., which represents a consumption of hydrogen of
0.00072 gram for the amount of leucoemeraldine taken, or of
0*00083 gram for 1 gram of dry leucoemeraldine.
The increasing value of the hydrogen consumption for each
successive experiment is due to the progressive oxidation of the
leucoemeraldine by exposure to air between the experiments.
The hydrogen consumption required by theory for a mono-
quinonoid compound is 0*00275 gram for 1 gram of substance, that
is, more than three times the highest figure obtained.
Taken in conjunction with our previous results, the following
conclusions are arrived a t :
(I) The product formed by reduction of emeraldine or nigr-
aniline with titanium trichloride or phenylhydrazine in the cold
is leucoemeraldine, C48H42N8, a colourless base devoid of quinonoid
groups.
(2) Protoemeraldine is the monoquinonoid stage.
(3) Emeraldine is the diquinonoid stage.
(4) Nigraniline is the triquinonoid stage.
(5) Pernigran ilins is the tetraquinonoid stage.
(6) The blacks of Willstatter and his pupils are not true
aniline-blacks, but are mixtures of erneraldine or nigraniline
with products of their decomposition or polymerisation. They
should therefore be removed from the literature as chemical
individuals.

Our thanks are due to Mr. S. Wolff for the preparation of the
emeraldine employed in these experiments.
DEPARTMENT
OF TINCTORIAL
CHEMISTRY,
THE UNIVERSITY,
LEEDS.