Improvements in the Manufacture and Production of Colouring Matters Containing Sulphur.
Year: 1898

page_text: Date of Application 25th
Oct
1000
Complete Specification Left, 25th July, 1899-Accepted, 26th Aug., 1899
Complete Specification Left, 25th July, 1899-Accepted, 26th Aug., 1899
Improvements in the Manufacture and Production of Colouring
Matters Containing Sulphur.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, King's Drive, Heaton Moor,
near Stockport, ALEXANDER MEYENBERG, Ph.D., of 13, Nelson Street, Manchester,
and THE CLAYTON ANILINE COMPANY, LIMITED, Chemical Manufacturers, of Clay-
ton, Manchester, all in the County of Laucaster, do hereby declare the nature of
this invention to be as follows:-
In our application for Letters Patent dated June 17th 1898 and numbered 13561
we have described the preparation, of a black colouring-matter or colouring-
matters obtained by the reaction of thiosulphuric acid upon paranitrosophenol in
strongly acid solution. We have now found that the thiosulphuric acid may be
replaced in this reaction by sulphuretted hydrogen and further that if the latter
reagent be employed the paranitrosophenol can be replaced by the following
compounds:
a) Paranitrosoaniline or its akyl derivatives.
b) Quinonimides, quinonchlorimides or analogous quinonoid compounds.
c) Paraamidophenol, paraphenylenediamine or their alkylated derivatives in
the presence of an oxidising agent.
d) Such nitroso, nitro or azo compounds which on reduction with sulphuretted
hydrogen give rise to paramidophenol, paraphenylene diamine or their alkylated
derivatives.
The present invention therefore relates to the preparation of colouring matters
containing sulphur by the reaction of sulphuretted hydrogen upon the above
named substances or mixtures of them in strongly acid solution. The changes
taking place are very similar to those brought about when thiosulphuric acid is
employed and the products are characterised by very similar properties. Their
shade varies from dark brown and dark blue to black. They dye unmordanted
cotton from a sodium sulphide bath and resist severe soaping acids and alkalies.
Like the compounds, of the before mentioned application for Letters Patent they
are possibly dithiazines and probably owe their origin to the intermediate forma-
tion of disulphhydroparaamidophenol (or its analogues) which then reacts with
a further quantity of the initial material.
Such disulphhydro bodies are also formed by reduction of the dithiosulphonic
acids whose preparation is described in our application for Letters Patent dated
October 17th 1898 and numbered 21832. Consequently the aforesaid colouring-
matters can also be produced from disulphhydro bodies thus prepared, by further
treatment with the before mentioned compounds.
The general method of carrying out this invention is illustrated by the follow-
ing examples but we do not limit ourselves to these examples or to the details
given in these examples as these may be varied within large limits.
3
EXAMPLE I.
100
2
11
L
上上

page_text: aqueous caustic soda (30 per cent. NaOH) is run into a cold mixture of 240 g. of
concentrated sulphuric acid and 500 c.c. of water. The mixture is saturated with
sulphuretted hydrogen and whilst a stream of the gas is continually passing the
liquid is warmed to 60°-70° Centigrade. Finally when the solution, which is
at first red, has become colourless it is raised to the boiling point and boiled for
some time. The insoluble black precipitate is filtered off, washed with hot water
and dried. The product dyes unmordanted cotton brownish-black from a sulphide
bath
EXAMPLE II.
109 g. of paraamidophenol are dissolved in 2000 c.c. or water and 200 g. of
concentrated sulphuric acid. 300 c.c. of a solution of sodium hypochlorite (con-
taining 14 per cent, available chlorine) are added to the cold solution and a stream
of sulphuretted hydrogen is led through the solution whilst gradually raising the
temperature to 60°-70° Centigrade. When the solution is decolourised the
passage of the gas is stopped and the mixture is boiled. The black precipitate
is filtered off washed and dried. It dyes unmordanted cotton from a sodium
sulphide bath an indigo blue-black.
Doted thi. 9541
Ա. 1.
1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture and Production of Colouring
Matters Containing Sulphur.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, King's Drive, Heaton Moor,
near Stockport, ALEXANDER MEYENBERG, Ph.D., of 18, Nelson Street, Manchester,
and THE CLAYTON ANILINE COMPANY, LIMITED, Chemical Manufacturers, of Clay-
ton, Manchester, all in the County of Lancaster, 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:
In our application for Letters Patent dated October 17th 1898 and numbered
21832 we have described the preparation of black colouring matters obtained by
the reaction of thio-sulphuric acid upon various components. We have now
found that the thio-sulphuric acid can be replaced in this reaction by sul-
phuretted hydrogen and further that if the latter reagent be employed the follow-
ing compounds can be caused to react therewith:-
a) Paranitrosoaniline or its akyl derivatives.
6) Quinonimides, quinonchlorimides or analogous quinonoid compounds.
c) Paraamidophenol, paraphenylenediamine or their alkylated derivatives in
the presence of an oxidising agent.
d) Such nitroso compounds as on reduction with sulphuretted hydrogen, give
rise to paramidophenol, paraphenylenediamine or their alkylated derivatives.
The present invention therefore relates to the preparation of colouring matters
containing sulphur by the reaction of sulphuretted hydrogen upon the above
named substances or mixtures of them in strongly acid solution. The changes
taking place are very similar to those brought about when thiosulphuric acid is
employed and the products are characterised by very similar properties. Their
shade varies from dark brown and dark blue to black. They dye unmordanted
cotton from a sodium sulphide bath and resist severe soaping acids and alkalies.
Like the compounds of the before mentioned application for Letters Patent they

page_text: are possibly dithiazines and probably owe their origin to the intermediate forma-
tion of disulphhydroparaamidophenol (or its analogues) which then reacts with
a further quantity of the initial material.
Such disulphhydro bodies are also formed by reduction of the dithiosulphonic
acids whose preparation is described in the before mentioned application. Con-
sequently the aforesaid colouring matters can also be produced from disulph-
hydro bodies thus prepared, by further treatment with the before mentioned
compounds.
The general method of carrying out this invention is illustrated by the follow-
ing examples but we do not limit ourselves to these examples or to the details
given in these examples as these may be varied within large limits.
EXAMPLE I.
A solution of 50 g. of paranitrosophenol in 400 c.c. of cold water and 55 g. of
aqueous caustic soda (30 per cent. NaOH) is run into a cold mixture of 240 g. of
concentrated sulphuric acid and 560 c.c. of water. The misture is saturated with
sulphuretted hydrogen and whilst a stream of the gas is continually passing the
liquid is warmed to 60°-70° Centigrade. Finally when the solution, which is
at first red, has become colourless it is raised to the boiling point and boiled for
some time. The insoluble black precipitate is filtered off, washed with hot water
and dried. The product dyes unmordanted cotton brownish-black from a sulphide
baths
EXAMPLE II.
of
109 g. of paraamidophenol are dissolved in 2000 c.c. or water and 200 g.
concentrated sulphuric acid. 300 c.c. of a solution of sodium hypochlorite (con-
taining 14 per cent. available chlorine) are added to the cold solution and a stream
of sulphuretted hydrogen is led through the solution whilst gradually raising the
temperature to 60°-70° Centigrade. When the solution is decolourised the
passage of the gas is stopped and the mixture is boiled. The black precipitate
is filtered off washed and dried. It dyes unmordanted cotton from a sodium
sulphide bath an indigo blue-black.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed we declare that what we
claim is:-
1. The manufacture and production of black colouring matters containing
sulphur by the reaction of sulphuretted hydrogen in the presence of an oxidising
agent upon paraamidophenol, paraphenylene diamine, or their alkylated deriva-
tixes, in an acid solution the mixture being finally heated to boiling.
2. The manufacture and production of black colouring matters containing
sulphur by the reaction of sulphuretted hydrogen upon paranitrosophenol para-
nitrosoaniline or such other nitroso-compounds, quinoneimides quinonechlori
mideszar quinonedichlorimides, as, on reduction, give rise to para amidophenol,
parapheneng diamine, or their alkyl derivatives; the reaction being performed
an acid solution which is finally heated to boiling.
3. In the manufacture of colouring matters containing sulphur which dye
unmordanted cotton from a sodium sulphide bath, the employment of sulphuretted
hydrogen as the sulphur introducing agent, the operation being carried out in
an acid aqueous solution, substantially as herein before described.
4. The manufacture of colouring matters containing sulphur as hereinbefore
described in the examples.
Dal the 25th day of Tule 1800
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.