The Manufacture and Production of New Acid Colouring Matters.
Year: 1893

page_text: Date of Application, 30th Aug., 1893
Complete Specification Left, 30th Apr., 1894-Accepted, 2nd June, 1894
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Acid Colouring Matters.
I BENJAMIN WILLCOX of 47 Lincoln's 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 Badische Anilin and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:-
In the Specification of the application for Letters Patent No. 3487 of 1893
there is described the production of new acid dyes by the interaction, under
suitable conditions, of the nitroso compounds of dialkyl-meta-amido-phenol with
mono-, and di-sulpho-acids of alpha naphthylamine and derivatives thereof.
The present invention relates to the manufacture of similar acid dyes using
certain mono- and higher sulpho-acids of aniline toluidine and the like and of beta-
naphthylamine and of alkyl and benzyl derivatives of these bodies.
These sulpho acids are caused to interact under suitable conditions with the
nitroso compounds of di-alkyl-meta-amido-phenol.
As instances of the sulpho acids which can be used I mention the following but
I do not restrict myself to those named as many analogues and derivatives can be
used in a similar manner with similar results. Sulphanilic acid, meta-sulphanilic
acid, aniline-disulphoacid, ortho-toluidine meta-sulpho acid, the so called alpha-,
beta-, gamma- and delta beta naphthylamine mono-sulpho acids beta naphthylamine-
disulpho-acid G and beta naphthylamine-disulpho-acid (2.5.7) [See Thorpe's
Dictionary of Applied Chemistry.]
To further illustrate the nature of the invention I give the following example in
which the preparation of one of the new dyes from sulphanilic acid and nitroso-di-
ethyl-metamido-phenol is described. This is however but a single case of the
application of the invention and not only can it be applied to the said other
materials but the details of the method of carrying it into effect can in every case
be considerably varied without departing from the nature of the invention. The
parts are by weight. Mix together about sixty nine parts of the hydrochlorate
nitroso-diethyl-meta-amido-phenol about fifty parts of crystallized sodium
sulphanilate and about one hundred and six parts of acetic acid (containing
about 30 per cent. real acid C₂HO₂) and heat the mixture on the water-bath for
about ten or twelve hours. A sample of the melt should dissolve in water giving a
pure blue-violet solution. Dilute with about one thousand parts of hot water add
sufficient alkali to neutralize the main quantity of acid and precipitate the dye
with common salt. The dye is usually obtained possessing a resinous consistency.
Wash this with a dilute solution of common salt, press and dry.
of
Instead of acetic acid other diluents can be used such for instance as glacial
acetic acid, water glycerol and instead of the sodium salt of sulphanilic acid the
free acid can be used but then an equivalent quantity of sodium acetate should be
added.
The new dyes obtained according to this invention dye animal fibre from the
acid bath giving for the most part blue-violet shades. The said dyes possess a most
valuable degree of fastness against the action of alkalies, and of light, and
readily yield very even shades either when used alone or in admixture with
other dyes.
Dated the 30th day of August 1893.

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of New Acid Colouring Matters.
*I, BENJAMIN WILLCOX, of 47 Lincoln's Inn Fields in the County of London
Patent Agent do hereby declare the nature of this invention (which has been
communicated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen-on-Rhine 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. 3487 of 1893 granted to James Yate
Johnson on a communication from my foreign correspondents there is described the
production of new acid dyes by the interaction, under suitable conditions, of the
nitroso compounds of dialkylmeta-amido-phenol with mono- and di-sulpho acids of
alpha-naphthylamine and derivatives thereof.
The present invention relates to the manufacture of similar acid dyes using
certain mono- and higher sulpho acids of aniline, toluidine, beta-naphthylamine
and the like. These sulpho acids are caused to interact under suitable conditions
with the nitroso-compounds of di-alkyl-meta-amido-phenol in particular of diethyl
and dimethyl-meta-amido-phenol.
The following are the sulpho-acids which my foreign correspondents recommend
for use. Sulphanilic acid, meta-sulphanilic acid, aniline-di-sulpho acid, ortho-
toluidine-meta-sulpho acid, the so-called alpha-, beta-, gamma and delta,
beta-naphthylamine-mono-sulpho acids, beta-naphthylamine-di-sulpho acid G, and
beta-naphthylamine-disulpho acid (2.5.7). [See Thorpe's Dictionary of Applied
Chemistry.]
To further illustrate the nature of the invention and the manner in which it can
.be carried into practical effect I give the following example in which the preparation
of one of the new dyes from sulphanilic acid and nitroso-di-ethyl-meta-amido-phenol 1
is described. This is however but a single case of the application of the invention
and not only can it be applied to the other materials herein before mentioned but
the details of the method of carrying it into effect can in every case be
considerably varied without departing from the nature of the invention. The parts
are by weight.
Mix together about sixty nine parts of the hydrochlorate of nitroso-di-ethyl-
meta-amido phenol, about fifty parts of crystallized sodium sulphanilate and about
one hundred and six parts of acetic acid (containing about thirty per cent. real
acid C,HO2) and heat the mixture, on the water-bath, for about ten, or twelve,
hours. A sample of the melt should dissolve in water giving a pure blue-violet
solution. Dilute with about one thousand parts of hot water, add sufficient alkali
to neutralize the main quantity of acid, and precipitate the dye by means of
common salt. The dye is usually obtained possessing a resinous consistency.
Wash this with a dilute solution of common salt, press, and dry.
Instead of acetic acid other diluents can be used; such, for instance, as glacial
acetic acid, water, or glycerol, and, instead of the sodium salt of sulphanilic acid,
the free acid can be used but then an equivalent quantity of sodium acetate should
be added.
The new dyes obtained according to this invention dye animal fibre from the
acid bath giving blue-violet shades. The said dyes possess a most valuable 4
degree of fastness against the action of alkalies, and of light, and readily yield
very even shades, either when used alone, or in admixture with other dyes.

page_text: 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 manufacture of new acid colouring-matters by heating together a
nitroso-derivative of the dialkylated meta-amido-phenols herein before mentioned
with a sulpho-acid hereinbefore mentioned, substantially under the conditions
hereinbefore described.
2. The manufacture of new acid colouring-matters substantially in the manner
hereinbefore described in the example.
3. As new articles of manufacture the new acid colouring-matters such as can be
obtained substantially as hereinbefore described.
Dated this 30th day of April 1894.
JOHNSONS & WILLCOX.