The Manufacture of New Colouring Matters.
Year: 1892

page_text: Date of Application, 20th June, 1892
Complete Specification Left, 20th Mar., 1393-Accepted, 6th May, 1893
PROVISIONAL SPECIFICATION.
The Manufacture of New Colouring Matters.
I, BENJAMIN WILLCOX, of 47 Lincolns Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of Germany) to be as follows:-
In the Specification of my application for Letters Patent No. 5112 dated
15th March 1892 valuable colouring matters suitable for dyeing cotton, are
described, which colouring matters result from the so called thio condensation
products of para-toluidine, meta-xylidine and pseudo-cumidine, or the sulpho acids
of these thio compounds. In order to produce these dye-stuffs the diazo derivatives
of the said thio compounds are combined with Clève's a-naphthylamine beta mono-
sulpho acids (ẞ, y or 8) and the resulting amidoazo products after having been
rediazotised are combined with the known dye-stuff components such as amines,
phenols, amido-phenols, amido-phenol-ethers, the sulpho- or carboxylic-acids thereof,
especially with naphthols, amido-naphthols, amido-naphthol-ethers, dihydroxy-
naphthalenes and the sulpho- or carboxylic-acids thereof.
My foreign correspondents have now found that instead of Clève's alpha-
naphthylamine-beta-mono-sulpho acids the following products can also be employed
as second components viz. -alpha-naphthylamine-ortho-mono-sulpho acid, amido-
naphthols, amido-naphthol-ethers, amido-naphthol-sulpho acids, amido-naphthol-
ethers-sulpho acids, amido-naphthoxyl-acetic acids and amido-naphthoxyl-acetic-
sulpho acids.
In oudon to illustrate the process the following examples are given.
HIRD
DYESTUFF OBTAINED BY
XYLIDINE-SULPHO ACID
COMBINING
WITH
DIAZOTISED
DEHYDRO-THIO-META-
ALPHA-AMIDO-BETA-NAPHTHOL-ETHER,
REDIAZOTISING THE AMIDO-AZO PRODUCT SO FORMED AND COMBINING THE
RESULTING DIAZO-DERIVATIVE WITH 1.8-DIHYDROXY-NAPHTHALENE-
ALPHA-MONO-SULPHO ACID.
The diazo compound obtained in the usual manner from 37 parts, by weight, of
dehydro-thio-meta-xylidine-sulphonate of sodium by means of 7 parts, by weight of
sodium nitrite is (after having been filtered off) introduced into a muriatic acid
solution of 18-7 parts, by weight, of alpha-amido-beta-naphthol-ether and the
mixture is allowed to stand, with occasional agitation, until the formation of the
amido-azo compound is complete. After rendering alkaline the latter is filtered off
and mixed with water. It possesses the following composition
:-
A concentrated aqueous solution of 7 parts, by weight, of sodium nitrite is then
added thereto, and the further diazoation is effected by slowly acidifying with
muriatic acid. After about 24 hours the complete diazo compound is filtered off

page_text: and introduced into a watery solution of 26-2 parts, by weight, of 1.8-dihydroxy-
naphthalene-alpha-mono-sulphonate of sodium. In order to finish the formation of
the dye-stuff the mixture is heated for a short time at from about 60 to 70 degrees
centigrade and, after rendering alkaline, the complete dye-stuff is isolated in the
known manner, by salting out, filtering off, pressing and drying.
The colouring matter thus obtained corresponds with the following formula :-
DYE-STUFF
.
DIAZOTISED DEHYDRO-
RESULTING BY THE COMBINATION OF
THIO-META-XYLIDINE WITH ALPHA-AMIDO-BETA-NAPHTHOLETHER-DELTA-
MONO-SULPHO-ACID (DERIVED FROM BETA-NAPHTHOL-BETA-MONO-SULPHO
ACID F.), BY AGAIN DIAZOTISING THE AMIDO-AZO PRODUCT SO FORMED
AND ALLOWING THE DIAZO DERIVATIVE TO REACT UPON 1.8-DIHYDROXY-
NAPHTHALENE-ALPHA-MONO-SULPHO ACID.
26-8 parts, by weight, of dehydro-thio-meta-xylidine are diazotised by means of
7 parts, by weight, of sodium nitrite and the resulting diazo compound is introduced
into a solution in water of 30 parts, by weight, of alpha-amido-beta-naphthol-ethyl-
ether-beta-mono-sulphonate of sodium and about 60 parts, by weight, of sodium
acetate. The amido-naphthol-ether-sulpho acid employed is obtained from the
so called beta-naphtbol-mono-sulpho acid F. by subsequently ethylising, nitrating,
and reducing.
After some days the resulting mixture is heated, for a short time, at from 60 to
70 degrees centigrade and the amido-azo product is isolated by rendering alkaline
adding common salt and filtering off. It has the formula :-
SO,Na
It is mixed with water and a concentrated watery solution of 7 parts, by weight,
of sodium nitrite and, on cooling with ice, hydrochloric acid is slowly added until
the liquid shews a lasting acid reaction. The diazo derivative of the aforesaid
amido-azo product formed in this manner, is, after some time, filtered off and
introduced into a watery solution of 26.2 parts, by weight, of 1.8 dihydroxy-
naphthalene-alpha-mono-sulphonate of sodium and about 50 parts, by weight, of
sodium acetate. In order to complete the production of the dye-stuff the mixture
is then heated for a short time at from 60 to 70 degrees centigrade. After
rendering alkaline the difficultly soluble colouring matter is isolated in the known
manner by filtering off, pressing and drying. It has the formula :-
:-

page_text: employing either instead of dehydro-thio-meta-xylidine or dehydro-thio-meta-
xylidine-mono-sulpho acid the analogous thio compounds such as dehydro-thio-
para-toluidine, primulin base, dehydro-thio-para-toluidine-sulpho acid, dehydro-
thio-pseudo-cumidine, dehydro-thio-pseudo-cumidine-sulpho acid and primuline by
which name are termed the sulpho acids of the mixture obtained by a treatment
of para-toluidine with sulphur and containing dehydro-thio-para-toluidine and
primuline base or by employing instead of amido-naphthol-ethyl-ether and amido-
naphthol-ethyl-ether-sulpho acid an isomeric compound thereof or amido-naphthol,
amido-naphthol-sulpho acid, amido-naphthoxylacetic acid or amido-naphthoxyl-
acetic sulpho acid; the combination of the latter two sulpho acids for producing
intermediate amido azo compounds being effected more advantageously in
moderately acid (muriatic or acetic acid) solution. As third components can be
employed all products known hitherto as dye-stuff components which are generally
termed amines, phenols, amidophenols, amido-phenol-ethers, sulpho-, carboxylic- or
sulpho-carboxylic acids thereof.
The number of the dye-stuffs obtainable in this manner and the variety of shades
produced by these products on unmordanted cotton, is of course great.
Those colouring-matters are of especial value which contain, as third components,
naphthol, amido-naphthol, amido-naphthol-ether, dihydroxy-naphthalene, or a
sulpho- or carboxylic-acid thereof. In the employment of 1-8-dihydroxy-
naphthalene-sulpho acids as third components colouring-matters result which
produce, on unmordanted cotton, shades from greyish-green to pure green and deep
greenish-black.
Clève's alpha-naphthylamine-beta-mono-sulpho acids employed as second com-
ponents as described in the Specification of my application for Letters Patent
No. 5112 dated 15th March 1892 can also be replaced as my foreign correspondents
have found by alpha-naphthylamine and the amido-azo products obtained from the
diazo derivatives of the aforesaid thio compounds by the combination with alpha-
naphthylamine yield, after rediazotising, and combining for example with naphthols,
amido-naphthols, amido-naphthol-ethers, amido-naphthoxyl-acetic acids, dihydroxy-
naphthalenes or sulpho acids thereof valuable colouring-matters which in general
are similar to the analogous products containing Clève's alpha-naphthylamine-beta-
monosulpho acids as second components.
In the Specification of my application for Letters Patent No. 5112 dated
15 March 1892 secondary disazo colouring matters suitable for dyeing wool are
described. These dyestuffs are obtained by combining the diazo derivatives
of amines, amido-phenols, amido-phenol-ethers, substitution products thereof
(especially sulpho- and carboxylic-acids thereof) with Clève's alpha-naphthyl-
amine-beta-mono-sulpho acids, rediazotising the amido-azo products thus formed
and coupling the resulting diazo compounds with the known dyestuff components:
amines, phenols, amido-phenolethers, sulpho- or carboxylic acids thereof, especially
with naphthols, amido-naphthols, dihydroxy-naphthalenes and sulpho acids thereof.
Analogous dyestuffs, containing alpha-naphthylamine or alpha-amido-naphthol-
ether instead of Clève's alpha-naphthylamine-beta-mono-sulpho acids have also
been obtained by my foreign correspondents as described in the Specifications of
Letters Patents No. 13665 dated 29th August 1889, No. 3397 dated 4th March 1890
and No. 5984 dated 7th April 1891. My foreign correspondents have further found
that the products employed in the last named three Specifications and in the
Specification of my application for Letters Patent No. 51122 as second components
can be replaced either by alpha-naphthylamine ortho-mono-sulpho acid dis-azo
dye-stuffs being produced which are similar to those of the latter Specification or
by amido-naphthols, amido-naphthol-ethers (not being such as are employed in the
processes of the aforesaid three Specifications, amido-naphthol-sulpho acids, amido-
naphthol-ether-sulpho acids, amido-naphthoxyl-acetic acids or amido-naphthoxyl-
acetic-sulpho acids colouring-matters being formed which likewise are of technical
value. The products to start from are generally amines, amido-phenols, amido-

page_text: phenol-ethers of the benzene and naphthalene series, sulpho- and carboxylic-acids
of these three groups, including the amido-naphthoxy-acetic acids and amido-
naphthoxy-acetic-sulpho acids. These products are diazotised and combined with
the said compounds viz.:-alpha-naphthylamine-ortho-mono-sulpho acid, amido-
naphthol, amido-naphthol-ethers, amido-naphthol-sulpho acids, amido-naphthol-
ether-sulpho acids, amido-naphthoxyl-acetic acids, amido-naphthoxyl-acetic-sulpho
acids and the intermediate amido-azo products formed after having been diazotised
are coupled with the usual dye-stuff components namely amines, phenols, amido-
phenols, amido-phenol-ethers, of the benzine and naphthalene series, or the sulpho-,
carboxylic- or sulpho-carboxylic-acids thereof, including amido-naphthol-sulpho
acids, amido-naphthol-ether-sulpho acids, amido-naphthoxyl-acetic acids, amido-
naphthoxyl-acetic sulpho acids, dihydroxy-naphthalenes, and dihydroxy-naphtha-
lene-sulpho acids.
In order to illustrate the production of these new dye-stuffs the following
examples are given, the parts being by weight : —
-
OBTAINED BY COUPLING
DIAZOTISED
ALPHA-NAPHTHYLAMINE
-DYE-STUFF
WITH ALPHA-AMIDO-BETA-NAPHTHOL-ETHYL-ETHER-DELTA-MONO-SULPHO
ACID, REDIAZOTISING THE AMIDO AZO COMPOUND FORMED AND COMBINING
THE RESULTING DIAZO PRODUCT WITH 1.8 DIHYDROXY-NAPHTHALENE-
ALPHA-DISULPHO ACID.
The watery solution of alpha-diazo-naphthalene obtained from 14.3
parts of
alpha-naphthylamine, in the well known manner, by means of 7 parts of sodium
nitrite is allowed to flow into a solution in water of 29 parts of alpha-amido-beta-
naphthol-ethyl-ether-delta-mono-sulphonate of sodium and about 30 parts of sodium
acetate. After some days the mixture is heated for a short time at from 60 to 70
degrees centigrade; when the combination is complete soda-lye or sodium carbonate
is added and the amido azo-product formed is filtered off and is of the following
composition :
This amido azo compound is then mixed with water and a solution in water of
7 parts of sodium nitrite and muriatic acid is slowly added until the mixture shews
a lasting acid reaction. After some time the complete diazo-product filtered off is
introduced into the solution in water of 36.4 parts of 1.8 dihydroxy-naphthalene-
alpha-di-sulphonate of sodium and 72 parts of sodium acetate and the formation of 3
the dye-stuff is completed by heating for a short time at about 60 degrees centigrade.
After rendering alkaline the dye-stuff is isolated in the usual manner by salting
out, filtering off, pressing and drying. It possesses the following composition:

page_text: FOURTH EXAMPLE.
COLOURING MATTER OBTAINED BY THE COMBINATION OF DIAZOTISED BETA-
NAPHTHYLAMINE-ALPHA-MONO-SULPIIO ACID WITH ALPHA-AMIDO-BETA-
NAPHTHOL-ETHER-BETA-MONO-SULPHO ACID, BY REDIAZOTISING THE
FORMED AMIDO AZO PRODUCT AND COUPLING THE RESULTING DIAZO
PRODUCT WITH 1.8 DIHYDROXY
ACID.
NAPHTHALENE-ALPHA-MONO-SULPHO
24.3 parts of the sodium salt of beta-naphthylamine-alpha-mono-sulpho acid are
diazotised in the usual manner and the diazo compound is slowly added to a solution
in water of 29 parts of alpha-amido-beta-naphthol-ether-beta-mono-sulpho acid
(derived from beta-naphthol-beta-mono-sulpho acid 2-6) and about 48 parts of
sodium acetate. After some time the mixture is heated for a short time at about
60 degrees centigrade, neutralised by adding soda, and the amido-azo product
precipitated by the addition of common salt is filtered off.
Its composition corresponds to the following formula :
SO,Na
SO,Na
and dyes wool in an acid bath a greenish black.
SO,Na
In an analogous manner to that described in the preceding two examples the
other colouring matters are obtained and in the employment of amido-naphthol-
sulpho acids different products are obtained according as they are allowed to react
on the diazo derivatives in alkaline or acid solution, whilst alpha-naphthylamine,
alpha-naphthylamine-ortho-mono-sulpho acid, amido-naphthols, amido-naphthol-
ethers, amido-naphthoxyl-acetic acids or amido-naphthoxyl-acetic-sulpho acids are
combined with the different diazo compounds preferably in moderately acid solution.
The colouring-matters are of especially high value which contain as last
components naphthols, amido-naphthols, naphthol-sulpho acids, amido-naphthol-
sulpho acids, dihydroxy-naphthalenes, or dihydroxy-naphthalene-sulpho acids.
Dated this 20th day of June 1892.

page_text: COMPLETE SPECIFICATION.
The Manufacture of New Colouring Matters.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farbenfabriken vorm. Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement :-
In the Specification of Letters Patent No. 5112 dated 15th March 1892 valuable
colouring matters suitable for dyeing cotton, are described, the which colouring-
matters are formed from the so-called thio condensation products of para-toluidine,
metaxylidine and pseudo-cumidine, or the sulpho acids of these thio compounds
(excluding however the so called primuline). In order to produce these dyestuffs,
the diazo derivatives of the said thio compounds are combined with Clève's alpha-
naphthylamine beta-monosulpho acids (beta or delta), and the resulting amidoazo
products, after having been rediazotised, are combined with the known dye-stuff
components such as amines, phenols, amido-phenols, amido-phenolethers, the sulpho-
or carboxylic-acids thereof, especially with naphthols, amido-naphthols, amido-
naphtholethers, dihydroxynaphthalenes or the sulpho- or carboxylic-acids thereof.
My foreign correspondents have now found, that instead of Clève's alpha-
naphthylamine-beta-monosulpho acids other amido compounds, which when
combined with the diazo derivatives of the said thio compounds yield amido-azo
products which may be further diazotised, can also be employed: viz., alpha-
naphthylamine-ortho-monosulpho acid, amido-naphthols, amido-naphtholethers,
amido-naphthol-sulpho acids, amido-naphthol-ether-sulpho acids, amido-naphthoxy-
acetic acids and amido-naphthoxyacetic-sulpho acids. Necessarily the last-named
substances can only be used, if after combining them with the diazotised thio
products amidoazo compounds result which can be again diazotised and then
coupled with the known dye-stuff components.
In order to illustrate the process the following examples are given. The parts
DYE-STUFF OBTAINED BY
FIRST EXAMPLE.
COMBINING
XYLIDINE-SULPHO ACID WITH
DIAZOTISED DEHYDRO-THIOMETA-
ALPHA-AMIDO-BETA-NAPHTHOLETHER,
REDIAZOTISING THE AMIDO-AZO PRODUCT SO FORMED AND COMBINING
THE RESULTING DIAZO DERIVATIVE WITH 1.8 DIHYDROXY-NAPHTHALENE-
ALPHA-MONO-SULPHO ACID.
The diazo compound obtained in the usual manner from 37 parts of dehydro-
thio-meta-xylidine-sulphonate of sodium by means of 7 parts of sodium nitrite
having been filtered off is introduced into a muriatic acid solution of 18.7 parts, of
alpha-amido-beta-naphthol-ether. The mixture is stirred and in order to promote
the formation of the amido-azo compound a suitable amount of sodium acetate is
.added.
When the interaction is complete, the solution is
amidoazo product is filtered off and mixed with water.
composition:
rendered alkaline, and the
It possesses the following

page_text: It is then mixed with a concentrated aqueous solution of 7 parts of sodium
nitrite and the further diazotisation is effected by slowly acidifying with muriatic
acid. After about 24 hours the finished diazo compound is filtered off and
introduced into a solution prepared by dissolving in water 26-2 parts of 1-8-di-
hydroxynaphthalene alpha-mono-sulphonate of sodium and about 50 parts of sodium.
acetate rendered moderately acid by means of acetic acid. In order to complete
the formation of the dye-stuff the mixture is heated for a short time at from
about 6 to 70 degrees centigrade and the mixture having been rendered alkaline,
the finished dye-stuff is isolated in the usual manner, by salting out, filtering off,.
pressing and drying.
The colouring matter thus obtained is represented by the following formula:
DYE-STUFF RESULTING FROM THE COMBINATION OF DIAZOTISED DEHYDRO-
THIO-META-XYLIDINE WITH ALPHA-AMIDO-BETA-NAPHTHOLETHER-DELTA-
MONOSULPIO
ACID
(DERIVED FROM BETA-NAPIITHOL-DELTA-MONO-.
SULPHO ACID 2.7), BY AGAIN DIAZOTISING THE AMIDO-AZO PRODUCT SO
DERIVATIVE TO ACT ON 1.8 DI--
FORMED AND ALLOWING THE DIAZO
HYDROXY-NAPHTHALENE-ALPHA-MONO-SULPHO ACID.
26-8 parts of dehydro-thio-meta-xylidine are diazotised by means of 7 parts, of
sodium nitrite and the resulting diazo compound is introduced into a solution in
water of 28-9 parts of alpha-amido-beta-naphthol-ethylether delta mono-sulphonate
The amidonaphthol-ether.
of sodium and about 60 parts of sodium acetate.
sulpho acid employed is obtained from the so-called beta-naphthol-mono-sulpho
acid F. by ethylating nitrating and reducing.
After several days the resulting mixture is heated during a short time at from
60 to 70 degrees centigrade and the amidoazo product is isolated by rendering
alkaline, adding common salt and filtering off. It has the formula:
It is mixed with water and a concentrated solution of 7 parts of sodium nitrite,.
and after cooling with ice muriatic acid is slowly added until the liquid shews a
permanent acid action.
The difficultly soluble diazo derivative of the aforesaid amidoazo product formed
in this manner is filtered off after some time and introduced into a solution, prepared
by dissolving in water 26°2 parts of 1: 8-dihydroxy-naphthalene-alphamonosulphonate
of sodium about 50 parts, of sodium acetate and sufficient acetic acid to render the
liquid moderately acid.
In order to complete the production of the dye-stuff the mixture is then heated
for a short time at from 60 to 70 degrees centigrade. After rendering the liquid

page_text: alkaline the difficultly soluble colouring matter is isolated in the known manner by
filtering off, pressing and drying. It has the formula:
AT
and produces on unmordanted cotton in an alkaline soap-bath a pure green.
An analogous manner of operating is to be adopted in preparing the other dye-
stuff's which may be formed either by employing instead of dehydro-thic-meta-
xylidine or dehydro-thio-meta-xylidine-sulpho acid the analogous thio compounds
such as dehydro-thio-para-toluidine, primuline base dehydro-thio-para-toluidine-
sulpho acid, dehydro-thio-pseudo-cumidine, dehydro-thio-pseudo-cumidine-sulpho
acid and primuline (designating by this name the sulpho acids of the mixture
obtained by treating para-toluidine with sulphur and containing dehydro-thio-para-
toluidine and primuline base) or by employing instead of amido-naphthylethyl-
ether and amido-naphthyl-ethyl-ether-sulpho acid an isomeride thereof or amido-
naphthol, amido-naphthol-sulpho acid, amido-naphth-oxy-acetic acid or amido-
naphthoxy-acetic-sulpho acid. As third components all products can be employed
in use and known hitherto as dye-stuff components such as are termed generally
amines, phenols, amidophenols, amidophenol-ethers, sulpho-, carboxylic- or sulpho-
carboxylic acids thereof.
The number of the dye-stuffs obtainable in this manner and the variety of shades
produced by these products on unmordanted cotton, is of course, great.
Those colouring-matters are of especial value which contain as third components
naphtholsulpho acids, amidonaphthol-sulpho acids or 1-8-dihydroxy-naphthalene-
sulpho acids. By employing the latter acids as third components colouring-matters
are formed which produce on unmordanted cotton shades varying from greyish-
green to pure green and deep greenish-black.
In place of Clève's alpha-naphthylamine-beta-mono-sulpho acids employed as
second components as described in the Specification of Letters Patent No. 5112
dated 15th March 1892 my foreign correspondents have found, that it is possible
to use alpha-naphthylamine and that the amido-azo products obtained from the
diazo-derivatives of the aforesaid thio compounds by combination with alpha-
naphthylamine when rediazotised and combined with naphtholsulpho acids, amido-
naphtholsulpho acids or 1-8-dihydroxy-naphthalenesulpho acids yield valuable
colouring-matters which in general are similar to the analogous products containing
Clève's alpha-naphthylaminebeta-monosulpho acids as second components.
My foreign correspondents do not claim the colouring-matters obtained by com-
bining diazotised primuline with alphanaphthylamine rediazotising the amidoazo-
compounds so produced and combining the diazoderivatives with a phenol, or amine
or sulphonic acid thereof, as these dye-stuffs are already described in the Speci-
fication of the Letters Patent No. 10448 dated July 5th 1890.
In the Specification of the Letters Patent No. 22641 dated 28th December 1891
disazo colouring-matters suitable for dyeing wool are described. These dye-stuffs
are obtained by combining the diazo derivatives of amines or substituted amines
with Clève's alpha-naphthylamine-beta-mono-sulpho acids (beta or delta), rediazo-
tising the amido-azo products thus formed and coupling the resulting diazo com-
pounds with known dye-stuff components: e.g. amines, phenols, amido-phenolethers,
sulpho- or carboxylic acids thereof, especially with naphthols, amido-naphthols,
dihydroxy-naphthalenes and sulpho acids thereof.
Analogous dye-stuffs, containing alpha-naphthylamine or alpha-amido-naphthol-
ether instead of Clève's alpha-naphthylamine-beta-mono-sulpho acids have also
been obtained by my foreign correspondents, as described in the Specifications of
Letters Patents No. 13665 dated 29th August 1889, No. 3397 dated 4th March 1890

page_text: and No. 5984 dated 7th April 1891. My foreign correspondents have turther
found that in place of the products employed in the last named three Specifications
and in the Specification of the Letters Patent No. 22641 dated 28th December 1891
as second components it is possible to use either alpha-naphthylamine-ortho-mono-
sulpho-acid, (dis-azo dye-stuffs being produced which are less valuable than thoses
of the latter Specification) or amido-naphthols, amido-naphtholethers (not being.
such as are employed in the processes of the aforesaid three Specifications) amido-
naphthol-sulpho acids, amido-naphthol-ether-sulpho acids, amido-naphthoxy-acetic
acids or amido-naphthoxy-acetic-sulpho acids, colouring-matters being formed
which in part are of high technical value. The products to start from are
generally amines, amido-phenols, amido-phenol-ethers of the benzene and
naphthalene series, sulpho- and carboxylic-acids of these three, groups, including
the amido-naphthoxy-acetic acids and amido-naphthoxy-acetic-sulpho acids. These
products are diazotised and combined with one of the following compounds
(excluding however those of the resulting combinations which are not amido azo
products and cannot be again diazotised alpha-naphthylamine-ortho-mono-sulpho
acid, amido-naphthol, amido-naphthol-ethers, amido-naphthol-sulpho acids, amido-
naphthol-ether-sulpho acids, amido-naphthoxy-acetic acids, amido-naphthoxy-acetic-
sulpho acids. The resulting intermediate amido-azo-products having been diazo-
tised, are coupled with the usual dye-stuff components particularly with 1.8-di-
hydroxynaphthalenesulpho acids.
My foreign correspondents do not claim the colouring-matters which are described
in the Specification of the Letters Patent No. 7067 dated 27th April 1889 and
which are formed by combining aniline, toluidine, xylidine, alpha- or beta naphthyl-
amine or sulpho acids thereof with oxyethers of alpha naphthylamine or their
sulpho acids, rediazotising and coupling the thus formed diazo products with
phenols, or phenol sulpho acids, such as alpha- or beta naphthol or dioxynaphthalenes
and the mono-,
di- or trisulphonic acids therefrom. The 18-dihydroxynaphthalene
alpha mono- or alpha disulpho acids, which my foreign correspondents employ, were
not yet known, when the above Letters Patent No. 7067 of 1889 were applied for.
In order to illustrate the production of these new dye-stuffs the following examples
are given, the parts being by weight:
LHIRD LAABILE
DYE-STUFF OBTAINED BY COUPLING DIAZOTISED
ALPHA-NAPHTHYLAMINE
WITH ALPHA-AMIDO-BETA-NAPHTHOL-ETHYL-ETHER-DELTA-MONO-SULPHO
ACID, REDIAZOTISING THE RESULTING AMIDO AZO COMPOUND AND COM-
BINING THE DIAZO PRODUCT WITH 1.8-DIHYDROXY-NAPHTHALENE ALPHA-
DISULPHO ACID.
The solution in water of alpha-diazo-naphthalene, obtained from 14.3 parts of
alpha-naphthylamine in the well known manner by means of 7 parts of sodium
nitrite, is allowed to flow into a solution in water of 28.9 parts of alpha-amido-
beta-naphthol-ethyl-ether-delta-mono-sulphonate of sodium and about 30 parts of
sodium acetate. After several days the mixture is heated during a short time at
from 60 to 70 degrees centigrade; when the combination is complete, the mixture
is rendered moderately alkaline by means of soda-lye or sodium carbonate and the
resulting amidoazo product is filtered off. It is of the following composition:

page_text: has a permanent acid action. After some time the finished diazo product is filtered
off and introduced into a solution in water of 364 parts of 1-8-dihydroxy-
naphthalene-alpha-di-sulphonate of sodium and 72 parts of sodium acetate, together
with a small quantity of acetic acid, and the formation of the dye-stuff is completed
after about 24 hours by heating during a short time at about 60 degrees centigrade. 5
After rendering the mixture alkaline the dye-stuff is isolated in the usual manner
by salting out, filtering off, pressing and drying. It possesses the following
composition:
COLOURING-MATTER OBTAINED BY THE COMBINATION OF DIAZOTISED BETA-
NAPHTHYLAMINE-ALPHA-MONO-SULPHO ACID WITH ALPHA-AMIDO-BETA-
NAPHTHOL-ETHER-BETA-MONO-SULPHO ACID, REDIAZOTISING THE
SULTING AMIDO AZO PRODUCT
RE-
AND COUPLING THE DIAZO PRODUCT
WITH 1.8-DIHYDROXY-NAPHTHALENE-ALPHA-MONO-SULPHO ACID.
24:5 parts of the sodium salt of beta-naphthylamine-alpha-mono-sulpho acid are
diazotised in the usual manner, and the diazo compound is slowly added to a solu-
tion in water of 28-9 parts of alpha-amido-beta-naphthol-ether-beta-mono-sulpho
acid (derived from beta-naphthol-beta-mono-sulpho acid 2.6) and about 48 parts
of sodium acetate. After some time the mixture is heated during a short time at
about 60 degrees centigrade neutralised by adding soda and the amido-azo product
is precipitated by the addition of common salt and filtered off. Its composition
corresponds to the following formula :
In order to diazotise the above amido-azo product, it is mixed with water and a
concentrated solution of 7 parts of sodium nitrite and muriatic acid is slowly added
until the liquid is acid. The filtered diazo compound is then introduced into a
solution in water of 26.2 parts of 1.8-dihydroxy-naphthalene-alpha-mono-sulphonate
of sodium, about 72 parts of sodium acetate and a small quantity of acetic acid;
after 24 hours the mixture is slowly heated to about 70 degrees centigrade. After
rendering the mixture alkaline the finished dye-stuff is isolated in the usual
manner by salting out, filtering off, pressing and drying. It has the following
formula:

page_text: in the preceding last two examples. By the employment of amido-naphthol-sulpho
acids as second components different products are obtained, according as they are
allowed to act on the diazo derivatives in alkaline or acid solution. In producing
the disazo dye-stuffs, diamines containing alkyl radicles in one of the amido groups
monoacetylised diamines or mononitroamines (such as mono- or dialkylaniline, mono-
acetyl-para-phenylene diamine, monoacetyltoluylene diamine acetyl-naphthylene
diamine, nitroaniline, nitrotoluidine, nitronaphthylamine, analogues or homologues
thereof, including the sulpho derivatives thereof) can also be used. If the diazo
compounds of these monoacetyled diamines or mononitroamines be combined with
the last named middle components (viz. alpha-naphthylamine-ortho-monosulpho
acid, amido-naphthol, amidonaphtholether, amidonaphthol-sulpho acid, amido-
naphtholether sulpho acid, amidonaphthoxy-acetic acid or amidonaphthoxy-
acetic sulpho acid) and if the diazo derivatives of the resulting amido
azo products be further coupled with 1:8-dihydroxynaphthalene-alpha-mono-
sulpho-acid or 1:8 dihydroxynaphthalene alpha-disulpho acid monoacetylised or
mononitrated dis-azo dye-stuffs are formed which can be converted into the corre-
sponding amido dis-azo colouring-matters by a subsequent treatment having
as its object either the removal of the acetyl group or reduction of the nitro
group.
My foreign correspondents have described in the above four examples methods
of practically producing some of the dye-stuffs herein before defined, but they do
not limit themselves to the directions given in the said examples. Necessarily
these colouring-matters and the analogues thereof can be obtained by means of all
the methods which are in use for the production of analogous dye-stuffs.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The process for producing new dye-stuffs by combining one molecular proportion
of diazotised dehydrothio-para-toluidine, dehydrothio-meta-xylidine, dehydrothio-
pseudo-cumidine, the so called primuline base or the sulpho acids of the aforesaid
thio compounds (excluding however the so called primuline) with one molecular
proportion of alphanaphthylamine-ortho-monosulpho acid, amidonaphthol, amido-
naphtholether, amidonaphthol-sulpho acid, amidonaphtholether sulpho acid, amido-
naphthoxyacetic acid or amidonaphthoxyacetic sulpho acid (excluding those of the
resulting combinations which are not further diazotisable amidoazo products) and
coupling the diazo derivatives of the so formed amidoazo compounds with equi-
molecular proportions of the known dye-stuff components such as amines, phenols,
amidophenols, amidophenolethers or sulpho- or carboxylic acids thereof, especially
naphtholsulpho acids, amido-naphthol sulpho acids or 1-8-dihydroxynaphthalene
sulpho acids.
2. The production of colouring-matters by combining one molecular proportion
of the diazo products of dehydrothio-para-toluidine, dehydrothio-meta-xylidine,
dehydrothio-pseudo-cumidine, the so called primuline base, or the sulpho acids of
the aforesaid thio compounds (excluding however the so called primuline) with one
molecular proportion of alpha-naphthylamine, rediazotising the amidoazo-products
so formed and coupling the resulting diazo-derivatives with equimolecular propor-
tions of naphthol-sulpho acids, amidonaphthol sulpho acids or 18-di-hydroxy-
naphthalene sulpho acids.
3. The process for producing new disazo colouring-matters by combining
the diazo derivatives of amines, amido-phenols, amidophenolethers of the
benzene or naphthalene series, sulpho- or carboxylic acids thereof with equi-
molecular proportions of alpha-naphthylamine-ortho-mono-sulpho acid, amido-
naphthol, amidonaphtholether, amido-naphthol-sulpho acid, amidonaphtholether
sulpho acid, amidonaphthoxyacetic acid or amidonaphthoxyacetic sulpho acid
(excluding however those of the resulting combinations which are not further
diazotisable amidoazo products,) rediazotising the amidoazo products so formed and

page_text: combining one molecular proportion of the resulting diazo derivatives with one
molecular proportion of 1.8-dihydroxynaphthalene alpha-mono- or alpha disulpho
acid. (The dye-stuffs containing amidonaphtholether as second component and
described in the Specifications of the Letters Patents No. 13665*, 3397* and
5984 are not claimed.)
4. As new articles of manufacture the new products which are obtained by
means of the processes described in the foregoing claims one, two, three or by any
other process producing the same result.
1000