Manufacture of Colouring Matters Containing Sulphur.
Year: 1895

page_text: [Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIERES
COLORANTES ET PRODUITS CHIMIQUES DE ST. DENIS, of 105 Rue
Lafayette, Paris, France.]
Manufacture of Colouring Matters Containing Sulphur.
I, JOHN IMRAY of No. 28 Southampton Buildings in the County of Londen,
Consulting Engineer and Chartered Patent Agent, do hereby declare the nature of
this invention to be as follows:-
17
It is known that, by the action of sulphur alone, or of sulphur and caustic
alkalies on simple or complex organic substances, a certain number of colouring
matters are obtained.
Amongst them, the colouring matters of the English
Specification No. 1489 of 1873, denoted by the generic name "Cachou de Laval '
are obtained by causing sulphur and caustic soda to react on organic bodies of
simple or complex character such as sawdust, bran, wool, pyrozallol and certain
organic acids. Kopp has obtained (see Berichte VII, 1746) colouring matters of
the same nature by heating dry acetate of soda with sulphur to a very high
temperature.
In the English Specifications Vidal No. 19880 of 1893 and Vidal and La Societe
des Matières Colorantes No. 9443 of 1894, there are the same use of sulphur and
caustic soda, the same conditions of reaction, but applied to aromatic combinations
of known properties such as dioxybenzols, paradiamines, or ainidophenols. The
coloring matters obtained in those three cases have the saine reactions, the same
characters, and are capable of the same applications; they differ only in the tints
which they produce ou vegetable fibres; whilst Cachou de Laval dyes grey brown,
the colouring matters of the Specifications No. 19880 of 1893 and No. 9443 of 1894
dye black and blue.
Further, it is known that if sulphur alone is heated with aromatic monamines
such as paratoluidine or a meta xylidine in which there is a group CH³ para in
relation to the amido group, basic matters are obtained capable of dyeing unmor-
danted cotton yellow tints (sec Berichte XXII, 330-422-968). These bodies;
the nature of which is now well settled, are termed primulines, dehydro-thio-
toluidine, dehydro-thio,-xylidine & c.
Finally, it is also known that by heating, under certain conditions, hydrosulphate
of ammonia with substituted aromatic diamines, such as paraphenylenediamine
dimethylated, a blue colouring matter, "methylene blue has been obtained
according to the German Patent No. 18579.
On the other hand, my foreign correspondents have found that, by making
sulphur, or preferably sulphur and caustic soda or alkaline sulphides react on
these same paradiamines simple or acetylated, under special conditions as to
fusion and the state of the reagents which are together, there are obtained new
colouring matters very different from those above referred to, in respect not only
of their chemical properties but also of the tints which they produce on fibres.
They dye unmordanted cotton in tints varying from yellow to brown or red yellow,
having remarkable lustre, and fast against various chemical agents.

page_text: use.
There are heated to about 300° C. for 3 to 4 hours 100 kilos. diacetyldiazobenzi-
dine, 100 kilos. dry sodium sulphide, and 200 kilos. sulphur. When the reaction
is complete the material is allowed to cool, and can in this condition be applied to
The colouring matter, which is readily soluble in water, dyes cotton yellow.
Analogous colouring matters may be prepared by heating under like conditions
acetyl-para-nitraniline, the nitro-toluidines and nitro-a-naphthylamine, acetylated,
or the corresponding amido derivatives. All these colouring matters have the
same properties. They are soluble in water, in alkaline sulphides, sulphites and
bisulphites, insoluble in acids.
It is known, on the other hand, that the primulines and dehydro-thio-toluidines
or xylidines are basic bodies insoluble in alkalies:
The combination of the new products with alkaline bisulphites has little stability
and even at 100° C. it reproduces the primary material. The solutions in alkaline
sulphides are brown, thus differing essentially from Cachou de Laval and also from
the colouring matters of the Specifications No. 19880 of 1893 and No. 9443 of 1894
which possess the common property of dissolving in sodium sulphide with charac-
teristic bottle-green colour.
The ordinary reducing agents do not attack the new colouring matters; it is only
at boiling point that zinc powder discolours the alkaline solutions by oxidation or
reproduces the primary colouring matter.
Finally, as has been shewn, vegetable fibres are dyed directly in fast tints, yellow,
brown and red yellow. It is necessary to pass the material through an oxidising
bath (bichromate, iron perchloride, or alkaline hypochlorite) in order to brighten
the tints and definitely fix the dyes.
"
The colouring matters obtained as above set forth and which may be termed
"thiocatechines' are products insoluble in acids, soluble only in alkalies and
alkaline sulphides. On precipitating them from their solution in soda or sodium
sulphide by dilute acid there is obtained a paste which, in contact with alkaline
sulphites or bisulphites, becomes soluble, and may be used in this condition or after
drying, directly for dyeing or, with addition of thickener, for printing.
EXAMPLE.
The colouring matter obtained by heating amidoacetanilide with sodium
sulphide and sulphur is dissolved in hot water and precipitated by dilute
hydrochloric acid. The precipitated colouring matter is filtered and washed with
a little acidulated water. To the paste are then added 4 parts crystallised sulphite
of soda for each 1 part of the dry product, and the whole is intimately mixed.
This mixture is heated to 30° to 40° C. for 2 or 3 days, until the whole becomes
quite soluble. It may be dried and applied for use. For the sulphite of soda an
equivalent quantity of bisulphite may be substituted.
.
Dated this 16th day of February 1895.
ABEL & IMRAY,
Agents for the Applicant.

page_text: Manufacture of Colouring Matters Containing Sulphur.
I, JOHN IMRAY, of No. 28 Southampton Buildings, 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:—
It is known that, by the action of sulphur alone, or of sulphur and caustic
alkalies on simple or complex organic substances, a certain number of colouring
matters are obtained. Amongst them, the colouring matters of the English
Specification No. 1489 of 1873, denoted by the generic names "Cachou de Laval "
are obtained by causing sulphur and caustic soda to react on organic bodies of
simple or complex character such as sawdust, bran, wool, pyrozallol and certain
organic acids.
Kopp has obtained (see Berichte VII, 1746) colouring matters of the
same nature by heating dry acetate of soda with sulphur to a very high
temperature.
In the English Specifications Vidal No. 19880 of 1893 and Vidal and La
Societe des Matieres Colorantes No. 9443 of 1894, there are described the same
use of sulphur and caustic soda, and the same conditions of reaction, but applied to
aromatic combinations of known properties such as dioxybenzols, paradiamines, or
amidophenols. The colouring matters obtained in those three cases have the same
reactions, the same characters, and are capable of the same applications, they differ
only in the tints which they produce on vegetable fibres; whilst Cachou de Laval
dyes grey brown, the colouring matters of the Specifications No. 19880 of 1893
and No. 9443 of 1894 dye black and blue.
Further, it is known that if sulphur alone is heated with aromatic monamines
such as paratoluidine or a meta xylidine in which there is a group CH³ para in
relation to the amido group, basic matters are obtained capable of dyeing unmor-
danted cotton yellow tints (see Berichte XXII, 330-422-968).
These bodies, the nature of which is now well settled, are termed primulines,
dehydro-thio-toluidine, dehydro-thio-xylidine etc.
Finally, it is also known that by heating, under certain conditions, hydrosulphate
of ammonia with substituted aromatic diamines, such as paraphenylenediamine
dimethylated, a blue colouring matter, methylene blue has been obtained
according to the German Patent No. 18579.
On the other hand, my foreign correspondents have found that, by making
sulphur, or preferably sulphur and caustic soda or alkaline sulphides react on these
same paradiamines simple or acetylated, under special conditions as to fusion and the
state of the reagents which are together, there are obtained new colouring matters
very different from those above referred to, in respect not only of their chemical
properties but also of the tints which they produce ou fibres. They dye unmor-
danted cotton in tints varying from yellow to brown or red yellow, having
remarkable lustre, and fast against various chemical agents.
The following examples illustrate the process for their preparation..
EXAMPLE I.
There are heated to 200°-250° C. for three hours 100 kilos. acetyl-para-
phenylenediamine and 200 kilos. sulphur.
There shortly occurs a violent reaction and evolution of sulphuretted hydrogen,
on the cessation of which the material is left to cool.
The colouring matter obtained is soluble in hot alkaline sulphides, and in this
condition directly dras cotton a brown collow

page_text: There are heated to about 300° C. for 3 to 4 hours 100 kilos. diacetyldinitro-
benzidine, 100 kilos. dry sodium sulphide, and 200 kilos. sulphur. When the
reaction is complete the material is allowed to cool, and can be used in this
condition. The colouring matter, which is readily soluble in water, dyes cotton
yellow.
Analogous colouring matters may be prepared by heating under like conditions
acetyl-para-nitraniline, the nitro-toludines and nitro-a-naphthylamine, acetylated,
or the corresponding amido derivatives.
All these colouring matters have the same properties. They are soluble in
water, in alkaline sulphides, sulphites and bisulphites, insoluble in acids.
It is known, on the other hand, that the primulines and dehydro-thio-toluidines
or xylidines are basic bodies insoluble in alkalies.
The combination of the new products with alkaline bisulphites has little stability
and even at 100° C. it reproduces the primary material.
The solutions in alkaline sulphides are brown, thus differing essentially from
Cachou de Laval and also from the colouring matters described in the
Specifications No. 19880 of 1893 and No. 9443 of 1894 which possess the
common property of dissolving in sodium sulphide with characteristic bottle-
green colour.
The ordinary reducing agents do not attack the new colouring matters; it is
only at boiling point that zine powder discolours the alkaline solutions by oxidation
or reproduces the primary colouring matter.
Finally, as has been shewn, vegetable fibres are dyed directly in fast tints,
yellow, brown and red yellow.
It is necessary to pass the material through an oxidising bath (bichromate, iron
perchloride, or alkaline hypochlorite) in order to brighten the tints and definitely
fix the dyes.
23
The colouring matters obtained as above set forth and which may be termed
"thiocatechines are products insoluble in acids, soluble only in alkalies and
alkaline sulphides. On precipitating them from their solution in soda or sodium
sulphide by dilute acid there is obtained a paste which, in contact with alkaline
sulphites or bisulphites, becomes soluble, and may be used in this condition or after
drying, directly for dyeing or, with addition of thickener, for printing.
EXAMPLE.
The colouring matter obtained by heating amidoacetanilide with sodium
sulphide and sulphur is dissolved in hot water and precipitated by dilute
hydrochloric acid. The precipitated colouring matter is filtered and washed
with a little acidulated water. To the paste is then added 4 parts crystallised
sulphite of soda for each one part of the dry product, and the whole is intimately
mixed. This mixture is heated to 30° to 40° C. for 2 or 3 days, until the whole
becomes quite soluble. It may be dried and applied for use.
For the sulphite of soda an equivalent quantity of bisulphite may be
substituted.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed declare that what I
claim is
1. The herein described manufacture of colouring matters containing sulphur by
causing sulphur or sulphur and alkaline sulphides to act on acetylated diamines or
on corresponding acetylnitramines.
2. The transformation of the colouring matters manufactured as above set forth

page_text: by treatment with alkaline sulphites or bisulphites into soluble compounds applicable.
for dyeing or printing.
3. The colouring matters produced as above set forth.
Dated this 22nd der of October 1905
ABEL & IMRAY,
Agents for the Applicant.