Manufacture of Novel Azo Colouring Matters Dyeing Directly on Cotton.
Year: 1892

page_text: Date of Application, 4th June, 1892.
Complete Specification Left, 27th Feb., 1893-Accepted, 8th Apr., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst a/Main; Germany, Chemical Manufacturers.]
Manufacture of Novel Azo Colouring Matters Dyeing Directly on
Cotton.
1, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane,
in the County of London, Chartered Patent Agent, do hereby declare the nature
of this invention to be as follows:-
Hübner in his paper upon anhydro bases (Ann. d. Chem. 208. 291) mentions
that benzanilide CH,NH - COCH, on being nitrated with red fuming nitric
acid forms two isomeric benz-nitranilides.
The benz-ortho-nitranilide on being reduced is transformed into benz-ortho-amido-
anilide which owing to the heat developed in the transformation, immediately
separates water.
"The so called para-nitrobenzanilide on being nitrated furnishes a trinitrobenz-
anilide...
etc. This compound, on being amidised, forms a very easily
decomposable base, probably an anhydro base."
From experiments made, by, my correspondents it appears very improbable that
Hübner's product was the anhydro base..
That is to say they found that when benzanilide is treated with a mixture of
strong nitric acid and monohydrate, there is obtained the trinitrobenzanilide of the
constitution.

page_text: This triamine crystallises from water in the form of rather long needles of the
melting point 185° C. In the usual solvents alcohol, ether, bisulphide of carbon,
chloroform &c. it is easily soluble, with somewhat more difficulty in hydrocarbons.
The triamine does not split off water except on being heated to higher degrees of
temperature, and there is obtained a base of great value for the production of azo
colouring matters, namely amido-benz-anhydro-triamido-benzene
This anhydro_base is soluble with difficulty in water, but easily in most of the
other solvents. Its melting point is above 250° C. Its hydrochloric and sulphuric
salts are very easily soluble in water.
With the requisite quantities of hydrochloric acid and nitrite of sodium a tetrazo
compound which combines with phenols, naphtholes and their carbonic and sulphonic
acids with amines and amido sulphonic acids to form colouring matters, which dye
cotton directly.
The novel colouring matters have the advantage over the "Congo" colouring
matters, that they are not so easily affected by acids as the latter.
They are of easy solubility, dye the fibre easily and with a good yield and they
particularly excel by great resistance to the action of soap.
The colouring matters prepared with amido-naphthol sulphonic acids can be
further diazotised on the fibre and on being further combined furnish valuable
shades.
The two amido groups in the anhydro base can be combined with the same or
with different components; when the amido compounds have been coupled, these
amido bases can be further diazotised and coupled etc., etc., thus producing a very
large number of varied combinations.
EXAMPLE:
a) 112 parts of amido-benz-anhydro-triamido-benzene, with the addition of
about 36 parts of hydrochloric acid of 30 per cent., are dissolved in such quantity
of water that there results a solution of about 10 per cent. strength and for the
diazotising this is admixed at a temperature of from 0 to 5° C. with 6.9 parts of
nitrite dissolved in about 35 parts of water.
The tetrazo compound forms smoothly and remains in solution.
:
The tetrazo compound thus obtained is caused to flow at 0° C. into a solution of
about 10 per cent. strength of 15 parts of salicylic acid and 35 parts of soda. The
combination begins immediately and is complete after about 12 hours.
The formed colouring matter separates already during the operation; it is
obtained in the usual manner and purified.
b) Into the tetrazo solution of 11.2 parts of amido-benz-anhydro-triamido benzene
obtained as described under (a) there is caused to flow at 0° C. a solution of
about 10 per cent. strength of 12 parts of naphthionate of soda and 45 parts of
acetate of sodium and the mixture is stirred for from 3 to 4 hours.
The intermediate product thus obtained is caused to flow at this temperature
into a solution of about 10 per cent, strength of 6 parts of resorcine and 35 parts of
soda and the mixture is stirred for about 12 hours longer. The colouring matter
separates during the operation; it is obtained in the usual manner and purified.
In the above described manner may be produced for example,
a. Simple coloring matters by combining amido-benz-anhydro-triamido-benzene
with phenol.

page_text: COMPLETE SPECIFICATION.
Manufacture of Novel Azo Colouring Matters Dyeing Directly on
. Cotton.
_1.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane, in
the County of. London, Chartered Patent Agent, do hereby declare the nature of this
invention and in what manuer the same is to be performed to be particularly
described and ascertained in and by the following statement:-
Hübner, in his paper upon anhydro bases (Ann. d. Chem. 208. 291), mentions
that benzanilide CH,NH-COCH, on being nitrated with red fuming nitric
acid, forms two isomeric benz-nitranilides.
The benz-ortho-nitranilide on being reduced is transformed into benz-ortho-
amido-anilide which, owing to the heat developed in the transformation, immediately
separates water.
Anhedohenz-diamide beazoA
NH
or C.H.{NHCC
1.NHg.
In another paper (Ber. d. deutsch. chem. Gesell. 10. 1708) the same investigator
BaƑs: "The so called para-nitrobenzanilide, on being nitrated, furnishes a trinitro-
benzanilide.
etc. This compound, on being amidised, forms a very easily
decomposable base, probably an anhydro base."
From experiments made by my correspondents it appears very improbable that
Hübner's product was the anhydro base.
That is to say, they found that, when benzanilide is treated with a mixture of

page_text: strong nitric acid and monohydrate, there is obtained the trinitro benzanilide of
the constitution :-
This triamine crystallises from water in the form of rather long needles of the
melting point 185° C. In the usual solvents alcohol, ether, bisulphide of carbon,
chloroform &c. it is easily soluble, with somewhat more difficulty in bydrocarbons.
The triamine does not split off water except on being heated to higher degrees
10 of temperature, and there is obtained a base of great value for the production of
azo colouring matters, namely amido-benz-anhydro-triamido-benzene
This anhydro base is soluble with difficulty in water, but easily in most of the
other solvents. Its melting point is above 250° C. Its hydrochloric and sulphuric
salts are very easily soluble in water.
With the requisite quantities of hydrochloric acid and nitrite of sodium it forms
a tetrazo compound which combines with phenols, naphtholes and their carbonic
and sulphonic acids, with amines and amido sulphonic acids to form colouring
matters, which dye cotton directly.
The novel colouring matters have the advantage over the "Congo" colouring
matters, that they are not so easily affected by acids as the latter.
They are of easy solubility, dye the fibre easily and with a good yield and they
particularly excel by great resistance to the action of soap.
The colouring matters prepared with amido naphthol sulphonic acids can be
farther diazotised on the fibre and, on being farther combined, furnish valuable
shades.
The two amido groups in the anhydro base can be combined with the same or
with different components; when the amido compounds have been coupled, these
amido bases can be farther diazotised and coupled etc., etc., thus producing a very
large number of varied combinations.

page_text: of water that there results a solution of about 10 per cent. strength, and, for the
diazotising, this is mixed at a temperature of from 0° to 5° C. with 6.9 parts of
nitrite dissolved in about 35 parts of water.
The tetrazo compound forms smoothly and remains in solution.
The
The tetrazo compound thus obtained is caused to flow at 0° C. into a solution of
about 10 per cent. strength of 15 parts of salicylic acid and 35 parts of soda. The
combination begins immediately, and is complete after about 12 hours.
formed colouring matter separates already during the operation; it is obtained in
the usual manner and purified.
6.) Into the tetrazo solution of 11.2 parts of amido-benz-anhydro-triamido-benzene,
obtained as described under (a), there is caused to flow at 0° C. a solution of about
10 per cent. strength of 12 parts of naphthionate of soda and 45 parts of acetate
of sodium, and the mixture is stirred for from 3 to 4 hours.
The intermediate product thus obtained is caused to flow at this temperature
into a solution of about 10 per cent. strength of 6 parts of resorcine and 35 parts of
soda, and the mixture is stirred for about 12 hours longer. The colouring matter
separates during the operation; it is obtained in the usual manner and purified.
In the above described manner may be produced for example,
a.) Simple colouring matters by combining amido-benz-anhydro-triamido-benzene
with phenol.

page_text: Patent 27378 by action of ammonia upon the ẞ naphtholdisulphonic
acid R of German Patent 3229.
th ẞ naphthylamine disulphonic acid R produced according to German
Patent 27378 by action of ammonia upon the B-naphtholdisulphonic
acid R of German Patent 3229.
19
amido naphtholsulphonic acid G of German Patent 53076.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The manufacture of colouring matters dyeing directly on cotton by combining
the amido-benz-anhydro-triamido-benzene obtained from benzanilide by nitration
and subsequent reduction and separation of water, with phenoles, naphtholes, their
carbonic and sulphonic acids and with amines and amido sulphonic acids, substan-
tially as described.
2. Colouring matters produced in the manner above referred to, examples of
which are hereinbefore mentioned.
Deted this 22nd day of Feb 1802
ABEL & IMRAY,
Agents for the Applicant.