The Manufacture or Production of Azo Colouring Matters.
Year: 1893

page_text: Date of Application, 17th May, 1893
Complete Specification Left, 17th Feb., 1894-Accepted, 17th Mar., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Azo 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:-
My foreign correspondents have found that a a-amidonaphthol a-monosulpho
acid, which can be obtained by slowly melting with alkalies the so-called alpha-
naphthylamine disulpho acid S, possesses the capability of reacting with two
molecules of diazo compounds (employing either the same diazo product or two
different ones), valuable primary disazo dye-stuffs being formed which yield from
blue to bluish-black shades.
The colouring matters obtainable in this manner are particularly distinguished
for their dyeing power and for their property of striking easily on fibre, and
producing thereon, shades which are very fast against the action of light.
The method of producing these new dye-stuffs, in general, consists either in
allowing two molecular proportions of the same diazo compound to act on one
molecular proportion of the above-mentioned ai, a-amidonaphthol-a,-monosulpho
acid (preferably in alkaline solution), or in combining the latter acid at first with
one molecular proportion of a diazo product, and in subsequently reacting with
one molecular proportion of another diazo derivative on the so-formed intermediate
product, effecting, in the latter case, the first coupling preferably in acid solution,
whilst the second combination is carried out advantageously in alkaline solution.
In order to illustrate the method of producing these dye-stuffs, the following
examples are given, the parts being by weight :-
COLOURING-MATTER FROM 2 MOLECULAR PROPORTIONS OF ALPHA DIAZO
NAPHTHALINE CHLORIDE AND ONE MOLECULAR PROPORTION OF
a₁ a-AMIDO NAPHTHOL-a₂-MONO SULPHO ACID.
The solution of alpha diazo naphthalene chloride obtained in usual manner
from 28.6 parts of alpha naphthylamine by means of 14 parts of sodium nitrite, is
allowed to flow (while being carefully cooled) into a watery solution prepared by
dissolving 24 parts of a, a-amido naphthol-a,-mono sulpho acid, and about 120 parts
of anhydrous sodium carbonate, in water.
The reaction mixture is cooled with ice, and repeatedly stirred, until the
formation of the dye-stuff is complete. After, say, about 24 hours, the mixture is
slowly heated to boiling, and the dye-stuff, which is soluble with difficulty, is
filtered off, after cooling.
It produces on wool, in acidulated baths, deep bluish-black shades.
DYE-STUFF FROM EQUAL MOLECULAR PROPORTIONS OF DIAZO BENZENE
CHLORIDE, DIAZO BENZENE SULPHO ACID AND a aAMIDO NAPH-
THOL-a-MONO SULPHO ACID.
A solution of diazo benzene chloride, obtained in usual way from 9-3 parts of
מז

page_text: aniline by means of 7 parts of sodium nitrite (on cooling) is stirred into a mixture
containing 24 parts of finely powdered a₁ a-amido naphthol-a,-monosulpho acid,
and a small quantity of free muriatic acid. As soon as the formation of the
intermediate product is complete, the mass is rendered alkaline by the addition of
sodium carbonate, and a solution of diazo benzene sulpho acid (corresponding to
7 parts of sodium nitrite) is then added. The reaction mixture is cooled by ice,
and the combination is facilitated by stirring.
The formation of the dye-stuff is complete after a very short time, and the
complete dye-stuff is then isolated in the manner described in the foregoing first
example.
This dye-stuff yields on wool, in acidulated baths, bluish-black shades.
Analogous dye-stuffs result in a similar manner, if the diazo products employed
in the preceding examples are replaced by the corresponding quantities of other
diazo-compounds. derived from amido compounds of the benzene or naphthalene
series.
In place of the diazo products derived from amines of the benzene or naph-
thalene series, those derived from substituted amines of these two series likewise
can be used, employing, for instance, the diazo derivatives of amido phenols,
amido phenolethers, amido carbonic acids, amido sulpho acids, or substitution
products thereof.
The shades obtainable by means of the dye-stuff's hereinbefore defined, are
generally distinguished for their intensity and fastness against the action of light.
Of course, my foreign correspondents do not limit themselves to the processes
described in the above examples, as these processes can be varied, and the production
in general can be effected by means of the known methods of producing analogous
or similar dye-stuffs.'
Dated this 17th day of May 1893.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Azo 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 :-
My foreign correspondents have found. that alpha, alpha, amidonaphthol alpha,
monosulphonic acid, which can be obtained by the action of alkalies on the
so-called alphanaphthylamine disulphonic acid S., is capable of interacting with two
molecules of diazo compounds (using either a single or two different diazo
compounds), valuable primary disazo dye stuffs being formed, which, for the most
part, yield from blue to bluish-black shades.
The coloring matters obtainable in this manner, have not only great dyeing
power, but also strike easily on fabrics, producing thereon shades which withstand
the action of light in a high degree.
The method of producing these new dye-stuffs in general consists either in
allowing two molecular proportions of a diazo compound to act on one molecular
proportion of the said alpha, alpha, amidonaphthol alpha, monosulphonic acid
(preferably in alkaline solution), or in combining this acid, first with one molecular
proportion of a diazo compound, and subsequently causing a molecular proportion
of another diazo compound to act on the so-formed intermediate product, in the
latter case effecting the first coupling preferably in acid solution, whilst the second
combination is advantageously carried out in alkaline solution.

page_text: COLORING
ALPHA DIAZO
2 MOLECULAR PROPORTIONS OF
MATTER FROM
NAPHTHALENE CHLORIDE, AND ONE MOLECULAR PROPORTION OF ALPHA
ALPHA AMIDONAPHTHOL ALPHA, MONOSULPHONIC ACID.
The carefully-cooled solution of alphadiazonaphthalene chloride, obtained in the
usual manner from 28-6 parts of alpha naphthylamine, by means of 14 parts of
sodium nitrite, is allowed to flow into a solution prepared by dissolving 24 parts
of alpha, alpha, amidonaphthol alpha, monosulphonic acid, and about 120 parts of
anhydrous sodium carbonate in water. The mixture is cooled with ice, and
repeatedly stirred, until the formation of the dye stuff is complete. After, say,
about 24 hours, the mixture is slowly heated to boiling. The dye-stuff, which is
difficultly soluble, is subsequently filtered off from the cooled liquid.
In acidulated baths. it produces deep bluish-black shades on wool.
DYE STUFF FROM EQUAL MOLECULAR PROPORTIONS OF DIAZO BENZENE
CHLORIDE, DIAZO BENZENE SULPHONIC ACID, AND ALPHA₁ ALPHA AMIDO
NAPHTHOL ALPHA, MONO SULPHONIC ACID.
A solution of diazo benzene chloride, obtained in the usual way from 9.3 parts
of aniline by means of 7 parts of sodium nitrite, is stirred into a mixture
containing 24 parts of finely powdered alphai alphaa amidonaphthol alpha, mono-
sulphonic acid, and a small quantity of muriatic acid. As soon as the formation of
the intermediate product is complete, the solution is rendered alkaline by the
addition of sodium carbonate, and a solution of diazo benzene sulphonic acid
(corresponding to 7 parts of sodium nitrite) is then added. The mixture is cooled.
by ice, and the combination is facilitated by stirring. The formation of the dye-
stuff is complete after a very short time, and when this is the case, the dye-stuff is
isolated in the manner described in the foregoing first example.
In acidulated baths, this dye stuff produces bluish-black shades on wool.
Analogous dye stuffs are formed in similar manner by substituting for the
diazo compounds used in the preceding examples the corresponding quantities of
other diazo compounds derived from amido compounds of the benzene or
naphthalene series. In place of the diazo compounds derived from amines of the
benzene or naphthalene series, those derived from substituted amines of these two
series can also be used, for instance, the diazo derivatives of amido phenols, amido
phenol ethers, amido carboxylic acids, amido sulphonic acids, or substitution
products thereof.
The shades obtainable by means of the dye-stuffs herein before defined, are
generally distinguished for their intensity and fastness on exposure to light.
My foreign correspondents do not limit themselves to the directions given in the
above examples, as these can be varied, and the production of such dye-stuffs in
general can be effected by means of the known methods of producing analogous or
similar 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, as communicated to me
from abroad, I declare that what I claim is :-
1. The production of new disazo dye-stuff's, which process consists in allowing
two molecular proportions of a diazo compound derived from an amine, amido-
phenol, amidophenolether, amidosulphonic acid, or amidocarboxylic acid of the

page_text: benzene or naphthalene series, to act on one molecular proportion of alpha, alpha,
amidonaphthol-alpha, monosulphonic acid, in an alkaline solution.
2. The process for producing new disazo coloring matters, which process consists
in first combining one molecular proportion of alpha, alpha, amidonaphthol alpha,
monosulphonic acid, in an acidulated solution, with one molecular proportion of a
diazo comprund derived from an amine, amidophenol, amidophenolether, amido-
sulphonic acid, or amidocarboxylic acid of the benzene or naphthalene series, and
subsequently coupling the intermediate azo compound so formed with one molecular
proportion either of the same or another diazo compound derived from an amine,
amidophenol, amidophenolether, amidosulphonic acid, or amidocarboxylic acid of
the benzene or naphthalene series, effecting the latter combination in alkaline
solution.
3. As new products of manufacture, the new disazo dye-stuffs produced by the
process herein before defined, or by any other means affording the same result.
Dated this 14th day of February 1894.
NEWTON & SON,
Agents for the Applicant.