Manufacture of Black Disazo-colouring Matters.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
Manufacture of Black Disazo-colouring Matters.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Chancery Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the German
Empire, Chemical Manufacturers,) to be as follows :-
In the manufacture of black secondary disazo-dyestuffs containing a-naphthyl-
amine in the middle position, simple amidosulphonic acids of the benzene or
naphthalene series have first been used such as for instance sulphanilic acid,
p-toluidinesulphonic acid, naphthylaminesulphonic acids (fast violet, blue-black B,
naphthol black etc., Schultz & Julius, Tabellarische Uebersicht, 3rd ed. p. 51
etc.).
Then amidocarbonic acids, such as amidosalicylic acid (diamond black, Schultz &
Julius, .c., p. 54) and nitro-amidosalicylic acid (French patent, No. 247770) have
been substituted for amidobenzenesulphonic acids.
Further, amidophenolsulphonic acids have been used as first components (German
patents Nos. 45994 and 70612). But the dyestuffs so produced being of no value,
the patents have been abandoned.
My foreign correspondents have now discovered, that very precious black disazo-
colouring matters are produced by the combination of the diazo-derivatives of a
sulphonic acid of paramidodiphenylamine or its homologues with a-naphthylamines,
rediazotisation of the products thus obtained and combination with another dyestuff
component.
The colouring matters produced in this way are distinguished by their extraordinary
intensity and their bluish-black shade. This property is the more remarkable, as
hitherto deep black dyestuffs have been prepared only by means of naphthyl-
amine derivatives as first components.
For carrying out the new process the method of proceeding may be as set forth in
the following examples.
EXAMPLE 1.
26-4 kilos. of paramidodiphenylaminesulphonic acid (Berichte der deutschen
chemischen Gesellschaft 24, 3798) are diazotized by means of 6-9 kilos. of sodium
nitrite and of hydrochloric acid. The diazo-compound is allowed to flow into a
solution of 143 kilos. of a-naphthylamine in the equivalent quantity of hydrochloric
acid. A quantity of sodium acetate sufficient for the neutralisation of the mineral
acid is added and the mixture stirred during 24 hours. The azo-compound is
precipitated in indigo blue flakes; it is isolated in the usual manner and purified by
means of its sodium salt, which dissolves in water with orange colour. From this
solution the compound is precipitated as a black powder of a coppery lustre which
dissolves in concentrated sulphuric acid with bluish red colour and separates by

page_text: By combining the diazo-derivative of the amidoazo-compound prepared by the
method described in Example 1 by means of 43.2 kilos. of paramidophenylparatoly-
laminesulphonic acid and of a-naphthylamine with 304 kilos. of B₁-naphthol-B
B-disulphonic acid R in a solution kept alkaline by means of sodium carbonate, a
dyestuff is obtained which dissolves readily in water and dyes wool in an acidified
bath a greenish black. Its solution in concentrated sulphuric acid has a bluish green
colour. After some time this colour turns to blue; by addition of water the colouring
matter is precipitated with blue colour.
Similar dyestuffs are produced if amidodiphenylaminedisulphonic acid (prepared by
the action of nitrochlorobenzenesulphonic acid upon metanilic acid and by reduction
of the product thus obtained) or its homologues are substituted for anidodiphenyl-
aminemonosulphonic acid. In the preparation of these dyestuffs B-naphthol may be
used as third component, instead of naphtholsulphonic acids.
EXAMPLE 3.
34.4 kilos. of paramidodiphenylaminedisulphonic acids are diazotized by means of
6.9 kilos. of sodium nitrite and of hydrochloric acid. The dark yellow diazo-solution
is allowed to flow into a solution of 14.3 kilos, of a-naphthylamine in hydrochloric
acid, while a solution of sodium acetate, sufficient for the neutralisation of the
mineral acid, is added. The combination I complete is a short time.
49.8 kilos. of the intermediate product thus obtained are dissolved in a solution of
sodium carbonate, 6.9 kilos. of sodium nitrite are added and the mixture allowed to
flow into hydrochloric acid. A reddish violet diazo-solution is formed in this way
and is added to a solution of 14.1 kilos. of ẞ-naphthol in an equivalent quantity of
soda lye and kept alkaline by means of sodium carbonate. The black colouring
matter is almost completely precipitated and forms a green powder of a metallic
lustre, which dies wool in an acidified bath a bluish black.
Dated thin and day of Ontation1003
ABEL & IMRAY,
Agents for the Applicant.

page_text: Manufacture of Black Disazo-colouring Matters.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Chancery Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the German
Empire, Chemical Manufacturers,) and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:—
In the manufacture of black secondary disazo-dyestuffs containing a-naphthylamine
in the middle position, simple amido sulphonic acids of the benzene or napthalene
series have first been used such as for instance sulphanilic acid, p-toluidinesulphonic
acid, naphthylamine, sulphonic acids (fast violet, blue. black B, naphthol black etc.,
Schultz & Julius, Tabellarische Uebersicht, 3rd ed. p. 51 etc.).
Then amidocarbonic acids, such as amidosalicylic acid (diamond black, Schultz &
Julius, L.c., p. 54) and nitro-amidosalicylic acid (French patent, No. 247770) have
been substituted for amidobenzenesulphonic acids.
Further, amidophenolsulphonic acids have been used as first components (German
patents Nos. 45994 and 70612). But the dyestuffs so produced being of no value,
the patents have been abandoned.
My foreign correspondents have now discovered, that very precious black disazo-
colouring matters are produced by the combination of the diazo-derivatives of a
sulphonic acid of paramidodiphenylamine or its homologues with a-naphthylamines,
rediazotisation of the products thus obtained and combination with another dyestuff
component.
The colouring matters produced in this way are distingushed by their extraordinary
intensity and their bluish-black shade. This property is the more remarkable, as
hitherto deep black dyestuffs have been prepared only by means of naphthylamine
derivatives as first components.
For carrying out the new process the method of proceeding may be as set forth in
the following examples.
EXAMPLE 1.
26.4 kilos. of paramidodiphenylaminesulphonic acid (Berichte der deutschen
chemischen Gesellschaft 24, 3798) are diazotised by means of 6.9 kilos. of sodium
nitrite and of hydrochloric acid. The diazo-compound is allowed to flow into a
solution of 14.3 kilos of a-naphthylamine in the equivalent quantity of hydrochloric
acid. A quantity of sodium acetate sufficient for the neutralisation of the mineral
acid is added and the mixture stirred during 24 hours. The azo-compound is
precipitated in indigo blue flakes; it is isolated in the usual manner and purified by
means of its sodium salt, which dissolves in water with orange colour. From this
solution the compound is precipitated as a black powder of a coppery lustre which
dissolves in concentrated sulphuric acid with bluish red colour and separates by
addition of water in pure blue flakes.
41.8 kilos. of this product, in the form of its sodium salt, are dissolved in water, a
solution of 6.9 kilos. of sodium nitrite is added and the mixture allowed to flow into
a sufficient quantity of dilute hydrochloric acid kept cold. The diazotisation is
effected immediately. The bluish-black diazo-compound, sparingly soluble in water,
is added to a solution of a-naphthol-a,-monosulphonic acid kept alkaline by means
of sodium carbonate. After 36 hours' stirring the combination is complete. The
dyestuff is isolated in the usual manner as a black powder of a coppery lustre, which
dissolves rather readily in water with dark blue colour and is precipitated by acids in
blue flakes. It dissolves in concentrated sulphuric acid with green colour, which by