Manufacture of New Bases Containing Sulphur, of their Sulpho- acids, and of Colouring-matters Derived therefrom.
Year: 1894

page_text: Date of Application, 12th Feb., 1894
Complete Specification Left, 5th Nov., 1894-Accepted; 8th Dec., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR ANILIN
FABRIKATION, of Berlin, in the Empire of Germany, Chemical Manu-
facturers.]
Manufacture of New Bases Containing Sulphur, of their Sulpho-
acids, and of Colouring-matters Derived therefrom.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention to be as follows:-
This invention relates to the production of new bases containing sulphur, derived
from aromatic diamines, of their sulpho acids and of colouring matters derived
therefrom.
It is known that sulphuretted bases have been derived from aniline, p. toluidine
and sulphur, but diamines have not hitherto been subjected to an analogous
process.
My foreign correspondents have now discovered, that aromatic diamines, such as
benzidine, heated with p. toluidine and sulphur, yield new valuable bases.
According to the quantity of sulphur and p. toluidine, reacting upon one
molecule of benzidine, two different bases may be prepared, having constitutions
which are probably represented by the following formulæ :
The production of these bases is effected by heating a mixture of benzidine,
p. toluidine and sulphur with or without the addition of a suitable medium-such as
naphthalene until the formation of sulphuretted hydrogen ceases.
The sulphates of the bases thus produced may be isolated by dissolving the
reaction product in sulphuric acid of 50 per cent., and precipitating by means of
water.
My foreign correspondents have further found that the diazotised bodies, obtained
from these bases, yield valuable dyestuffs when combined with the sulpho-acids of
phenols, amines or amido-phenols. According to the sulpho- or carbo-acids
employed, the colouring matters obtained dye unmordanted cotton and wool tints
varying from yellow to red and violet.
My foreign correspondents have further discovered that the above mentioned
bases may be sulphonated by means of fuming sulphuric acid.

page_text: The sulpho-acids thus obtained may be diazotised and combined with phenols
and amines and their sulpho- and carbo-acids, forming in this way colouring
matters which dye unmordanted cotton.
These colouring matters may also be produced on the fibre itself by first fixing
the sulpho acids on unmordanted cotton in an alkaline bath, then diazotising and
developing with phenols, amines and the like.
Moreover, the new bases and their sulpho-acids may be subjected to the processes
and reactions to which primuline, dihydrotoluidine, their sulpho acids and similar
bodies can be subjected.
Dated this 12th day of February 1894
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New Bases Containing Sulphur, of their Sulpho-
acids, and of Colouring-matters Derived therefrom.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and 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 the production of new bases containing sulphur, derived
from aromatic diamines, of their sulpho acids and of colouring matters derived
therefrom.
It is known that sulphuretted bases have been derived from aniline, p.-toluidine
and sulphur, but diàmines have not hitherto been subjected to an analogous
process.
My foreign correspondents have now discovered, that aromatic diamines, such as
benzidine, heated with p.-toluidine and sulphur yield new valuable bases.
According to the quantity of sulphur and p-toluidine reacting upon one
molecule of benzidine, two different bases-called herein Base I and Base II may be
prepared having constitutions which are probably represented by the following
formulæ.

page_text: The mode of carrying out the invention may be understood from the following
example.
PREPARATION OF THE BASE I.
18.4 kilos. of benzidine, 10.7 kilos. of paratoluidine, 12.8 kilos. of sulphur and
30 kilos. of naphthalene are heated until the formation of sulphuretted hydrogen
ceases. The sulphates of the bases thus produced may be isolated by dissolving
the reaction product in sulphuric acid of 50 per cent., and precipitating by means of
cold water; the sulphate forms in humid state a precipitate of a yellow colour.
PREPARATION OF THE BASE II.
The process for the preparation of this base is analogous to the above, the only
difference being that 18.4 kilos. of benzidine, 31.4 kilos. of para-toluidine,.
21-6 kilos. of sulphur and 40 kilos. of naphthalene are used.
The free bases, separated from the sulphates shew a great resemblance in
their general properties, they are soluble in alcohol and ether; the solutions.
have a yellow-green fluorescence, the solutions in benzene have a blue-green
fluorescence.
In the above mentioned examples the quantities may be varied, thus obtaining
mixtures of the two bases, which are also suitable for the production of sulpho
acids and of colouring matters.
By the action of nitrous acid on the salts of the Bases I and II diazo bodies are.
formed the salts of which are soluble in water with a yellow colour.
The diazo bodies obtained from these bases yield valuable dye stuffs when.
combined with the sulpho- or carbo acids of phenols, amines or amidophenoles.
impurities.
The solution is added to a solution of 25 kilos. of the ẞ-naphthol-a-sulpho acid.
EXAMPLE II.
The corresponding quantity of the Base II is diazotised in the same manner..
The diazo body is added to a solution of 32 kilos. of 1.8-amidonaphthol-disulpho
acid (English Patent No. 2984 of 1893) and 60 kilos. of sodium-carbonate.
The colouring matter precipitated by means of common salt, filtered off, pressed
It dyes unmordanted cotton violet tints.
and dried.
By substituting for the ẞ-naphthol-a-sulpho acid and the 1.8-amidonaphthol-
disulpho acid other sulpho or carbo acids of amines or phenols, many colouring
matters are obtained dyeing unmordanted cotton in tints, varying from yellow to
brown, to red and violet, and being moreover capable of dyeing wool in a neutral or
acidulated bath.
Generally the colouring matters derived from the two bases combined with the
same component greatly resemble each other, in most cases those derived from
Base II yield more yellowish tints.
My foreign correspondents have further discovered that the above mentioned
bases may be sulphonated by means of fuming sulphuric acid.

page_text: VAAMILE.
1 part of the Base I is dissolved in 3 parts of fuming sulphuric acid (23% anhy-
dride) and heated on the water bath until a test-sample dissolves easily in a
solution of sodium carbonate. The reaction product is poured into water, filtered
off, washed and dried.
In the same manner the sulpho acids of the Base II or of the mixture of the two
bases is prepared. They have a great resemblance to the sulpho acid of the
Base I. The free acids are insoluble in water, but the sodium salts are readily
soluble with a faint yellow colour.
They dye unmordanted cotton in an alkaline or neutral bath in yellow tints
which are not of remarkable intensity.
The sulpho acids thus obtained may be diazotised and combined with phenols
and amines and their sulpho- and carbo-acids, forming in this way colouring matters
which dye unmordanted cotton.
EXAMPLE:
40 kilos. of the sulpho acid of the Base I are dissolved in water by means of
6 kilos. of sodium carbonate, 14 kilos. of sodium nitrite are added. The solution
well cooled is poured into water acidulated with 40 kilos. of hydrochloric
acid (20° B.). The diazo-body separates in the shape of a yellow brown precipitate.
The diazo body added to a cold solution of 29 kilos. of ẞ-naphthol dissolved in
an excess of caustic alkali. After stirring for some time, the solution is gently
heated and the colouring matter is precipitated by means of common salt in the
shape of a red powder, filtered off, pressed and dried. It dyes unmordanted cotton
and wool in red tints.
These colouring matters may also be produced on the fibre itself by first fixing
the sulpho acids on unmordanted cotton in an alkaline bath, then diazotising and
developing with phenols, amines and the like.
Moreover the new bases and their sulpho acids may be subjected to the processes
and reactions to which primuline, dihydrotoluidine, their sulpho acids and similar
bodies can be subjected.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what
I claim is :-
1. The herein described manufacture of new bases containing sulphur or mixtures
of these bases, by heating benzidine with paratoluidine and sulphur, with or
without the addition of a suitable medium.
2. The transformation of the bases above referred to into sulpho acids by means
of fuming sulphuric acid.
3. The manufacture of colouring matters by combining the diazo compounds of
the bases above referred to or their sulpho acids with phenols, amines, amidophenols
or their sulpho or carbo acids.
4. As new products of manufacture, the bases, their sulpho acids and the
colouring matters produced as set forth in the preceding claims.
Dated this 5th day of November 1894.
ABEL & IMRAY,
Agents for the Applicant.