The Manufacture and Production of New Azo Colouring Matters.
Year: 1894

page_text: Date of Application, 27th Mar., 1894
Complete Specification Left. 11th Dec., 1894-Accepted, 12th Jan., 1895
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Azo 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:-
This invention consists in the manufacture and production of new azo colouring
matters from alkylated meta-amido benzene-sulpho acids, which colouring matters
have most valuable characteristics, in that they possess in a high degree the
In this respect
property of giving very even shades when dyed on animal fibre.
the new colouring matters hereinafter described are equal to the very best hitherto
known; the shades thereof are very fast against the action of light and alkalies
and remain unchanged after treatment with acetic acid.
The alkylated meta-amido-benzene sulpho-acids have prior to this invention not
been commercially used in the production of any technical azo dyes. If it be
attempted to combine the said compounds with the ordinary diazo compounds such
as diazo-benzene, diazo-xylene, diazo-naphthalene and para-diazo-acetanilide, in the
usual way practically no formation of dye stuff takes place. Now my foreign
correspondents have discovered that if, instead of the aforesaid and similar diazo
compounds, such compounds be employed as contain a substituting nitro group or
substituting nitro groups or the like then the formation of colouring matter can
most readily be effected colouring matters resulting which possess the excellent
qualities hereinbefore set forth and which range in shade (according to the
components chosen for use) from yellow or orange through red to violet.
The alkylated meta-amido-benzene-sulpho acids which are specially adapted for
use according to this invention are dimethyl meta-sulphanilic acid, diethyl-meta-
sulphanilic acid and methyl and ethyl-benzyl-meta-sulphanilic acid but the invention
is not restricted to the use of these acids.
The diazo compounds which are specially adapted for use according to this
invention are those derived from nitro anilines and toluidines and other bases
containing strongly acid substituting groups in particular para-nitro-aniline and
dinitro aniline (NH,NO,NO₂ = 1. 2. 4).
The following example will serve to illustrate the nature of the invention but
the invention is not confined thereto as valuable colouring matters can be obtained
from other components as hereinbefore mentioned. The parts are by weight.
Diazotize about one hundred and thirty eight parts of para-nitro-aniline in the
usual way with about seventy parts of sodium nitrite and run the diazo compound
into a solution of about two hundred and fifty parts of dimethyl-meta-amido
benzene sulpho acid (sodium salt) five hundred parts of crystallized sodium acetate
and five thousand parts of water. Stir well for about three hours. The colouring
matter separates out as red crystalline needles having a metallic lustre. Filter
press and dry. It dyes wool from the acid bath giving very full shades of red.
A similar colouring matter differing slightly in shade, results if, instead of the
dimethyl-meta-sulphanilic acid, the diethyl-compound be used.
In a similar manner colouring matters can be obtained from the other components
herein before referred to. Amongst these I mention in particular the colouring

page_text: matters from dinitro aniline (1:2:4) and diethyl metanilic acid which yield very
valuable violet shades.
Dated this 27th day of March 1894
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, Agents."
The Manufacture and Production of New Azo 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 :-
This invention consists in the manufacture and production of new azo-colouring
matters from alkylated meta-amido-benzene-sulpho acids and nitro azo bodies which
colouring matters have very valuable characteristics some of them possessing in the
highest degree the property of giving very even shades when dyed on animal fibre,
being in this respect equal to the very best hitherto known. The shades produced
are further very fast against the action of light and alkalies and remain unchanged
after treatment with acetic acid.
The alkylated meta-amido-benzene-sulpho-acids have, prior to this invention, not
been commercially used in the production of any technical azo-dyes. If it be
attempted to combine the said compounds with the ordinary diazo-compounds, such
as diazo-benzene, diazo-xylene, diazo-naphthalene and para-diazo-acetanilide, in the
usual way, practically no formation of dye-stuff takes place. My foreign corre-
spondents have discovered that if, instead of the aforesaid and similar diazo
compounds, such compounds be employed as contain a substituting nitro-group or
substituting nitro-groups, then the formation of colouring matter can most readily
be effected, and valuable colouring-matters result which range in shade, according
to the components chosen for use, from yellow, or orange, through red, to violet.
The alkylated meta-amido-benzene-sulpho-acids which are specially adapted for
use according to this invention are di-methyl-meta-sulphanilie-acid, di-ethyl-meta-
sulphanilic acid and methyl- and ethyl-benzyl-meta-sulphanilic acid.
The diazo compounds which are specially adapted for use according to this
invention are those derived from nitro-anilines and toluidines, and in particular
para-nitro-aniline and dinitro-aniline (NH, NO, NO, = 1. 2. 4).
:
:
The following examples will serve to illustrate the nature of the invention and
the manner in which it can be carried into practical effect but it is not confined
thereto as valuable colouring matters can be obtained from the other components
hereinbefore mentioned. The parts are by weight.
EXAMPLE 1.
Diazotize about one hundred and thirty eight parts of para-nitro-aniline, in the
usual way, with about seventy parts of sodium nitrite and run the diazo-compound
into a solution of about two hundred and fifty parts of dimethyl-meta-amido-
benzene sulpho acid (sodium salt), five hundred parts of crystallized sodium acetate
and five thousand parts of water. Stir well for about three hours. The colouring
matter separates out as red crystalline needles having a metallic lustre. Filter,
press, and dry. It dyes wool from the acid bath giving very full shades of red.
A similar colouring matter differing slightly in shade results if instead of the
dimethyl-meta-sulphanilic acid the diethyl compound be used.

page_text: In a similar manner colouring matters can be obtained from the other components
hereinbefore referred to, amongst these I mention in particular the dye-stuff from
dinitro aniline (1:2:4) and diethyl metanilic acid which yields very valuable violet
shades, and is characterized by possessing in the highest degree the equalising
power or property of yielding even shades herein before mentioned.
EXAMPLE 2.
Add to a solution of about twenty eight parts of diethyl-meta-amido-benzene
sulpho acid containing an excess of sodium acetate, the diazo solution obtained
from about eighteen and a half parts of dinitro-aniline. The new colouring matter
separates out as a crystalline precipitate with a greenish lustre. Filter, press,
and dry.
The diazo-solution used in the foregoing example can best be obtained by adding
the dinitro-aniline to a solution of the calculated quantity of nitrosyl sulphuric acid
in concentrated sulphuric acid at the ordinary temperature, stirring for half an hour
and then pouring the liquid onto ice.
Having now particularly described and ascertained the nature of this 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 azo-colouring matters by the combination of the
alkylated meta-amido-benzene-sulpho acids hereinbefore defined with the diazo
compounds from nitro anilines and nitro toluidines.
2. The manufacture of new azo colouring matters in the manners described in the
foregoing Examples 1 and 2.
3. As new articles of manufacture the azo colouring matters such as can be
obtained substantially as hereinbefore described and claimed.
Dated this 10th day of December 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.