The Manufacture or Production of Colouring Matters.
Year: 1895

page_text: Date of Application, 16th July, 1895
Complete Specification Left, 16th Apr., 1896-Accepted, 16th May, 1895.
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
In the Specification of Letters Patent No. 7337 of April 16th 1892, a process
for the production of new disazo colouring matters was described, consisting in
combining the diazo derivatives of amido azo compounds with phenyl or tolyl
naphthylamine sulphonic acids or the like.
My foreign correspondents have now found that valuable dye-stuffs are likewise
obtained by coupling the diazo derivatives of amido azo compounds with other
alkylated naphthylamine sulphonic acids, viz., such as methyl alpha or beta-
naphthylamine sulphonic acid, ethyl alpha or beta naphthylamine sulphonic acid,
benzyl alpha or beta naphthylamine sulphonic acid, or other alkylated naphthyl-
amine sulphonic acids, or alkylated naphthylamine disulphonic acids, and the like.
The shades produced with the dye-stuffs thus obtained generally vary from blue to
black, and they are remarkable for their fastness. The alkylnaphthylamine
sulphonic acids herein before mentioned are prepared in the known manner by
acting on naphthylamine sulphonic acid, or salts thereof, with alkylating agents,
in or without the presence of alkali. For instance, ethyl alpha, naphthylamine.
alpha, sulphonic acid may be produced in the following manner :-
A watery solution of one molecular proportion of the sodium salt of alpha,
naphthylamine alpha, sulphonic acid is mixed with one molecular proportion of
ethylbromide, and the mixture is heated during stirring in a vessel capable of
withstanding pressure, to about 90 or 100 degrees Centigrade, until the pressure
disappears. At this stage the heating is stopped. On cooling, the ethylated
naphthylamine sulphonic acid separates from the liquid in crystalline form, and it
is then isolated in the well-known manner.
For the preparation of the herein before defined disazo dye-stuffs, my foreign
correspondents proceed as follows. The parts are by weight.
DYE-STUFF FROM EQUAL MOLECULAR PROPORTIONS OF META SULPHANILIC
ACID, ALPHA NAPHTHYLAMINE, AND ETHYL ALPHA, NAPHTHYLAMINE
ALPHA SULPHONIC ACID.
A diazo solution prepared from 17.3 parts (one molecular proportion) of meta
sulphanilic acid by means of 7 parts of sodium nitrite, in the presence of muriatic
acid, is poured into a solution of 18 parts (one molecular proportion) of alpha-
naphthylamine hydrochloride in 800 parts of water, and the formation of the amido
azo compound is hastened by the addition of a suitable quantity of sodium acetate,
and by gently heating the mass. The intermediate product thus finished is
allowed to cool, and then 30 parts of muriatic acid (20° Bé.) and 7 parts of sodium
nitrate are added. The resulting mixture is allowed to stand during about
| Pain Q371

page_text: 12 hours, and then the so-formed diazo azo compound is filtered off, and stirred
into a solution of 25 parts (one molecular proportion) of ethyl alpha, naphthyl-
amine alpha, sulphonic acid dissolved in 100 parts of water by means of 5.3 parts
of sodium carbonate. The formation of the dye-stuff is accomplished by the
addition of 7 parts of sodium acetate, and by gently heating the mass.
isolated in the well-known manner. It dyes unmordanted cotton in fast bluish-
black shades: It has the formula:
It is
NHC,H
Analogous dye-stuffs are obtained either by replacing the metasulphanilic acid
used in the preceding example by other amido sulphonic acids, or by amines,
amido phenols, amidophenol ethers, nitramines, amido azo compounds of the
benzene or naphthalene series, or by replacing the alpha naphthylamine in the
preceding example, by alpha-naphthylamine sulphonic acids, or amidonaphthol-
sulphonic acids, amido naphtholethersulphonic acids, amidonaphthoxyacetic
sulphonic acids, or by other amido compounds which are capable of being further
diazotised when coupled with a diazo compound, or by employing, instead of ethyl
alpha, naphthylamine alpha4 sulphonic acid, any other ethyl naphthylamine
sulphonic acid, or ethyl naphthylamine disulphonic acid, or methylnaphthylamine
sulphonic or disulphonic acids, or benzylnaphthylamine sulphonic or disulphonic
acids, or, in general, any alkylated naphthylamine sulphonic acid or disulphonic
acid containing fatty alkyl radicles, including the benzyl radicle.
Dated this 16th day of July 1895.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Colouring Matters.
I, HENRY EDWARD NEWTON, of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention 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. 7337, of April 16th 1892, a process
for the production of new disazo colouring matters was described, which consisted
in combining the diazo derivatives of amido azo compounds with phenyl or tolyl-
naphthylamine sulphonic acids or the like.
My foreign correspondents have now found that valuable dyestuffs are also
obtained by coupling the diazo-derivatives of amido azo compounds with other
alkylated napthylamine sulphonic acids, such as methyl alpha or beta naphthyl-
amine sulphonic acid, ethyl alpha or beta naphthylamine sulphonic acid, benzyl
alpha or beta napthylamine sulphonic acid, or other alkylated naphthylamine
sulphonic acids, or alkylated naphthylamine disulphonic acids, and the like. The
shades produced by the dye-stuffs thus obtained generally vary from blue to black,
and are remarkable for their fastness. The alkyl-naphthylamine sulphonic acids
hereinbefore mentioned are prepared in the known manner by acting on naphthyl-
amine sulphonic acid, or salts thereof, with alkylating agents, if necessary in the
presence of alkali. For instance, ethyl alpha napthylamine alpha sulphonic acid
may be produced in the following manner :-
A solution in water of a molecular proportion of the sodium salt of alpha,
naphthylamine alpha, sulphonic acid is introduced, together with a molecular

page_text: proportion of ethyl bromide, into a vessel capable of withstanding pressure, and
the mixture is heated to about 90 or 100 degrees Centigrade, being well stirred the
while, until the pressure disappears. At this stage the heating is stopped. As
the liquid cools, the ethylated naphthylamine sulphonic acid separates in a crystal-
line form, and may be isolated in the well-known manner.
For the preparation of the hereinafter defined disazo dye-stuffs, my foreign:
correspondents proceed as follows. The parts are by weight.
DYE-STUFF FROM MOLECULAR PROPORTIONS OF META SULPHANILIC ACID,.
ALPHA NAPHTHYLAMINE, AND ETHYL ALPHA, NAPHTHYLAMINE ALPHA
SULPHONIC ACID.
A diazo solution prepared from 17.3 parts (one molecular proportion) of meta
sulphanilic acid by means of 7 parts of sodium nitrite, and sufficient muriatic acid,
is poured into a solution of 18 parts (one molecular proportion) of alpha naphthyl-
amine hydrochloride in 800 parts of water, and the formation of amido azo
compound is hastened by the addition of a suitable quantity of sodium acetate, and
by gently heating the liquid.
The mixture containing the intermediate product thus formed is allowed to cool,
and 30 parts of muriatic acid (20° Bé.), and 7 parts of sodium nitrite, are then
added. After about 12 hours, the diazo-azo-compound, into which the amido azo
compound is converted, is filtered off, and stirred into a solution of 25 parts (one
molecular proportion) of ethyl alpha, naphthylamine alpha, sulphonic acid,
dissolved in 100 parts of water by means of 5.3 parts of sodium carbonate. The
formation of the dye-stuff is accomplished by the addition of 7 parts of sodium
acetate, and by gently heating the mixture. It is isolated in the known manner.
It dyes unmordanted cotton fast bluish-black shades. It is represented by the
formula:-
CH⭑
-
N = N – CH.N = N - CH
SO,H
TY
Analogous dye-stuffs are obtained by substituting, for the meta sulphanilic acid
used in the preceding example, either other amido-sulphonic acids, or amines,
amidophenols, amidophenolethers, nitramines, amido azo compounds of the benzene
or naphthalene series, or, by using instead of the alpha naphthylamine prescribed
in the preceding example, alpha-naphthylamine sulphonic acid, or amidonaphthol
sulphonic acids, amidonaphtholether sulphonic acids, amidonaphthoxy acetic
sulphonic acids, or other amido compounds which are capable of being further
diazotised, when coupled with a diazo compound, or, by using, instead of ethyl
alpha naphthylamine alpha, sulphonic acid, any other ethyl-naphthylamine
sulphonic acid, or ethyl naphthylamine disulphonic acid, or methyl naphthylamine
sulphonic or disulphonic acid, or benzyl-naphthylamine sulphonic or disulphonic
acids, or, in general, any alkylated naphthylamine sulphonic acid or disulphonic
acid containing fatty alkyl radicles, including the benzyl radicle.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed (as communicated to me
from abroad), I declare that what I claim is :-
1. The production of colouring matters by combining the diazo-derivatives of
amines, amidophenols, amidophenolethers, nitramines, amido azo-compounds of the
benzene or naphthalene series, the sulpho or carboxylic derivatives thereof, with
alpha naphthylamine, alpha naphthylamine sulphonic acids, amidonaphthol, amido-
naphthol sulphonic acids, amidonaphtholethers, amidonaphtholether sulphonic

page_text: acids, amidonaphthoxy acetic acids, amidonaphththoxy acetic sulphonic acids, or
with other amido compounds capable of being further diazotised, when coupled
with a diazo compound, and subsequently coupling the diazo derivatives of the
amido azo-compounds so formed with alkylated naphthylamine sulphonic acids
containing fatty alkyl radicles, including the benzyl radicle.
2. The new dye-stuffs produced by the processes hereinbefore defined, or in any
-other manner affording the same result.
NEWTON & SON,
Agents for the Applicant.