The Manufacture and Production of New Colouring-matters and of a Product for Use therein.
Year: 1899

page_text: Date of Application, 19th Oct., 1899
Complete Specification Left, 6th July, 1900-Accepted, 11th Aug., 1900
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Colouring-matters and of a
Product for Use therein.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine, in the German Empire), to be as follows:-
This invention relates to the manufacture of new green-black, to black, colour-
ing-matters by the treatment of certain diphenylamine derivatives with sulphur
and sodium sulphide. The said di-phenylamine derivatives are obtained by the
condensation of di-nitro-chlor-benzene with ortho-amido-phenol, or ortho-amido-
phenol-suphoacid, under suitable conditions. When using the ortho-amido-
phenol an ortho-hydroxy-di-nitro-di-phenylamine results, (see Schöpff, Berichte
22, page 900, and Nietzki, Berichte 24, page 3588), and this, on treatment with
sulphur and sulphide of sodium at a high temperature, yields a colouring-matter
which dyes cotton black. The condensation of the ortho-amido-phenol-para-sul-
phoacid with dinitro-chlorbenzene leads to the production of a new ortho-hydroxy-
di-nitro-di-phenylamine-sulphoacid and this, after the treatment with sulphur
and sulphide of sodium, yields a colouring-matter that dyes unmordanted cotton
green-black. The condensations with di-nitro-chlor-benzene are effected in the
presence of bodies that are capable of binding hydrochloric acid.
The following examples will serve to further illustrate the nature of the
invention, and the manner in which the new colouring-matters can be obtained
The parts are by weight.
PRODUCTION OF GREEN-BLACK
EXAMPLE 1.
COLOURING-MATTER FROM HYDROXY-DI-NITRO-DI-
PHENYLAMINE-SULPHOACID.
Prepare the required di-phenylamine derivative by heating, in a vessel fur-
nished with an inverted condenser, an aqueous solution of the sodium salt of
ortho-amido-phenol-para-sulphoacid with the equimolecular proportion of di-
nitro-chlor-benzene and with a sufficient quantity of sodium acetate, or soda, to
bind the hydrochloric acid that is set free. Continue the heating until the di-
nitro-chlor-benzene has practically disappeared. Allow to cool, the desired di-
phenylamine derivative separates out in part in the form of its sodium salt
as a yellow red crystalline precipitate. Add common salt to complete the separa-
tion and collect.
Mix together forty-two parts of dry hydroxy-di-nitro-di-phenylamine-sulpho-
acid salt thus obtained with one hundred and fifty parts of crystallised sodium
sulphide, forty parts of sulphur, and ten parts of water. Heat the mixture,
slowly, to about 160° Centigrade. When the evolution of gas has ceased, and
the reaction mass has become dry, raise the temperature to about 170° and
continue heating for some time at this temperature. Allow the mass to cool

page_text: and reduce it to powder. The product so obtained can be used directly in dyeing
It is readily soluble in water and can be precipitated from its aqueous solution
by means of acid, or of ammonium chloride, the precipitate being black and
flocculent.
The colouring matter so obtained possesses a strong affinity for unmordanted
vegetable fibre which it dyes green-black with an excellent fastness against
the action of light, acids, soap, and alkalies. The treatment of the dyed goods
with chromates, copper salts and the like, does not materially alter, or add to
the fastness of, the shades produced.
EXAMPLE 2.
PRODUCTION OF BLACK COLOURING-MATTER FROM ORTHO-HYDROXY-DI-NITRO-DI-
PHENYLAMINE,
Mix together twenty parts of the aforesaid di-phenylamine derivative, forty
parts of flowers of sulphur, and one hundred parts of crystallised sodium sulphide,
and add five parts of water. Stir the mixture well, and heat it in an iron
pot to a temperature of about from 140° to 160° Centigrade. When the effer-
vescence ceases, and the reaction product has become dry, the production of the
colouring-matter can be regarded as complete. Allow the mass to cool, and
reduce it to powder. It can be used directly for dyeing. The product so
obtained dissolves in water (the solution being blue-violet) from which it is
precipitated as a black flocculent precipitate by common salt, or ammonium
chloride. The colouring-matter so obtained dyes unmordanted vegetable fibre
black, which is characterised by an excellent fastness against acid and alkalies.
On treatment of the dyed goods with chromates, copper salts, and the like, the
shade is changed to brown-black.
Dated this 19th day of Ociober 1899
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Colouring-matters and of a
Product for Use therein.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine, in the German Empire) and in what manner the same
is to be performed, to be particularly described and ascertained in and by the
following statement:-
-
The invention relates to the manufacture of new green-black colouring matter
by the treatment of a certain diphenyl-amine derivative with sulphur and
sodium sulphide. The said diphenyl-amine derivative is obtained by the con-
densation of di-nitro-chlor-benzene with ortho-amido-phenol sulpho acid under
suitable conditions and leads to the production of a new ortho-hydroxy-di-nitro-
diphenyl-amine sulphoacid, which, after treatment with sulphur and sulphide of.
sodium, yields a colouring matter that dyes unmordanted cotton green-black.
The condensation with di-nitro-chlor-benzene is effected preferably in the presence
of bodies that are capable of binding hydrochloric acid.
The following example will serve to further illustrate the nature of the in-

page_text: vention and the manner in which the new colouring matter can be obtained but
the invention is not confined to the example. The parts are by weight.
EXAMPLE
PRODUCTION OF GREEN-BLACK COLOURING MATTER FROM HYDROXY-DI-NITRO-
DIPHENYL-AMINE SULPHO-ACID.
Prepare the required diphenyl-amine derivative by heating, in a vessel
furnished with an inverted condenser, an aqueous solution of the sodium salt of
ortho-amido-phenol-para sulphoacid with the equi-molecular proportion of di-
nitro-chlor-benzene and with a sufficient quantity of sodium acetate or soda to
bind the hydrochloric acid that is set free. Continue the heating until the
dinitro-chlor-benzene has practically disappeared. Allow to cool; the desired di-
phenylamine derivative separates out in part in the form of its sodium salt as
a yellow-red crystalline precipitate. Add common salt to complete the separa-
tion and collect.
Mix together forty two parts of dry hydroxy-di-nitro-diphenylamine sulpho-
acid salt thus obtained with one hundred and fifty parts of crystallised sodium.
sulphide, forty parts of sulphur, and ten parts of water. Heat the mixture,
slowly, to about one hundred and sixty degrees Centigrade. When the evolu-
tion of gas has ceased, and the reaction mass has become dry, raise the tem-
perature to about one hundred and seventy degrees Centigrade and continue heating
for some time at this temperature. Allow the mass to cool and reduce it to
powder. The product so obtained can be used directly in dyeing. It is readily
soluble in water and can be precipitated from its aqueous solution by means
of acid, or of ammonium chloride, the precipitate being black and flocculent.
The colouring matter so obtained possesses a strong affinity for unmordanted
vegetable fibre which it dyes green-black with an excellent fastness against the
action of light, acids, soap, and alkalies. The treatment of the dyed goods with
chromates, copper salts and the like does not materially alter, or add to the
fastness of, the shades produced.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what
I claim is:-
:-
1. The manufacture of a product for use in the production of colouring matter
by condensing di-nitro-chlor-benzene with ortho-amido-phenol sulphoacid sub-
stantially as hereinbefore described.
2. The manufacture of a product for use in the production of colouring matter,
substantially as described in the foregoing Example.
3. As a new product of manufacture the body which can be obtained by con-
densing di-nitro-chlor-benzene with ortho-amido-phenol sulphoacid substantially
as herein before described.
4. The manufacture of new colouring matter by treating the aforesaid con-
densation product of di-nitro-chlor-benzene and ortho-amido-phenol sulphoacid
with sulphur and an alkaline sulphide substantially as hereinbefore described.
5. The manufacture of new colouring matter substantially as described in
the foregoing Example.
6. As a new product of manufacture the colouring matter such as can be
obtained by treating the aforesaid condensation product of dinitro-chlor-benzene
and ortho-amido-phenol sulphoacid with sulphur and an alkaline sulphide, sub-
stantially as herein before described.
Toted this fith day of I.... 1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.