The Manufacture or Production of Azo Colouring-matters.
Year: 1894

page_text: Date of Application, 1st Mar., 1894
Complete Specification Left, 29th Nov., 1894-Accepted, 29th Dec., 1894
[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:-
H
=
In the Specification of the English Letters Patent No. 13,475, dated 23rd July
1892, the process for producing a mixed disazo dye-stuff is described, which
process consists in combining the tetrazo derivative of mono nitro benzidine
(NH, NO, 1:3) with one molecular proportion of salicylic acid and one
molecular proportion of a,-naphthol-a-mono-sulphonic acid. This dye-stuff yields,
on wool, a very beautiful and fast red (so-called "ponceau"). As mentioned in
the Specification of the said Letters Patent, an analogous colouring-matter results,
if ortho cresotinic acid is used in place of salicylic acid.
:
=
My foreign correspondents have now found, that still better dye-stuffs, producing
red shades with a bluer tinge, result, if the nitro benzidine used in the process of
the aforesaid Specification, is replaced by a corresponding quantity of meta nitro
tolidine (NH, NO, = 1:3), or meta dinitro tolidine (NH, NO, 1:3), or
analogous mono or dinitro compounds derived from diamines, or substituted
diamines, that is to say, if one molecular proportion of the tetrazo derivatives of
these mono or dinitro diamines, is first combined with one molecular proportion of
salicylic acid, or cresotinic acid, or analogous hydroxy carboxylic acids of the
benzene or naphthalene series, and if the intermediate products so formed are
subsequently coupled with one molecular proportion of a-naphthol-a, mono sulphonic
acid (Nevile-Winther), or another naphthol mono sulphonic acid, or naphthol
disulphonic acid, or a dihydroxy naphthalene sulphonic acid.
The new colouring-matters thus obtained produce, on wool mordanted and
unmordanted, very clear bluish-red shades, distinguished for their great fastness to
the action of acids, light, washing, and fulling.
In order to illustrate the method of producing these dye-stuffs, the following
example is given. The parts are by weight.
COLOURING-MATTER OBTAINED FROM ONE MOLECULAR PROPORTION OF
TETRAZOTISED META NITROTOLIDINE, ONE MOLECULAR PROPORTION OF
SALICYLIC ACID, AND ONE MOLECULAR PROPORTION OF α-NAPHTHOL-a,
MONOSULPHONIC ACID.
==
25-7 parts of meta nitrotolidine (NH,: NO, = 1:3), which results on treating a
solution of one molecule of tolidine sulphate in concentrated sulphuric acid with
one molecule of potassium nitrate, or the corresponding quantity of nitro sulphuric
acid, are, in the usual way, converted into the tetrazo compound, and the latter is
allowed to flow into an icy-cold solution prepared from 14 parts of salicylic acid
and 60 parts of sodium carbonate.
:

page_text: When the formation of the intermediate product is completed, a well-cooled
solution in water of 26 parts of the sodium salt of a naphthol a, mono sulphonic
acid (Nevile-Winther) is added. After standing during 12 hours, the liquid
mixture is heated to 30 degrees Centigrade, in order to complete the formation
of the dye, and after standing again during several hours, the mixture is
boiled up.
After cooling, the complete dye-stuff is. isolated by salting out, filtering off,
pressing, and drying.
It produces on wool, in an acidulated bath, a beautiful bluish-red, which is
distinguished for its great fastness to the action of acids, washing, and fulling.
Its composition is represented by the following formula :-
= N-CH
CH, (CH), NO,
N = N-CH
он
COONa
OH
SO,Na
A dye-stuff producing on wool, in an acidulated bath, a red shade, with a
somewhat less blue tinge, results, if the meta-nitro tolidine used in the above
example is replaced by the corresponding quantity of meta-dinitro tolidine, which
is obtained on nitrating tolidine sulphate dissolved in concentrated sulphuric acid,
by means of such a quantity of nitro-sulphuric acid as corresponds to 2 molecules
of nitric acid. The colouring-matter so formed, in other respects possesses the
same properties as the dye-stuff obtainable as described in the above example.
Analogous colouring-matters are obtained, if the nitro tolidine, or dinitro
tolidine, is replaced by equivalent quantities of analogous mononitro or dinitro
derivatives of diamines, or substituted diamines, or if the homologous cresotinic
acids, or analogous hydroxy carboxylic acids of the benzene or naphthalene series,
are used in place of salicylic acid, or if the a-naphthol-a, mono sulphonic acid is
replaced by the corresponding quantities of other naphthol mono sulphonic acids,
or naphthol disulphonic acids, or dihydroxy-naphthalene sulphonic acids.
It will be understood that my foreign correspondents do not claim the colouring-
matter resulting from nitrobenzidine (mono-ortho-nitro-para-diamido diphenyl)
and salicylic acid (or ortho cresotinic acid) and a-naphthol-a,-monosulphonic acid.
Dated this 1st day of March 1894.
NEWTON & SON,
Agents for the Applicant.
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 the English Letters Patent No. 13475, dated 23rd July
1892, a process for producing a mixed disazo dye-stuff is described, which
consists in combining the tetrazo derivative of mononitro benzidine, or mon-ortho-
nitro-para-amidodiphenyl (NH, NO₂ = 1:3), with one molecular proportion of

page_text: salicylic acid and one molecular proportion of alpha, naphthol-alpha, monosulphonic
acid. This dye-stuff dyes wool a very beautiful and fast red (so-called "ponceau ")..
As mentioned in the Specification of the said Letters Patent, an analogous.
colouring matter is formed, if ortho cresotic acid is used in place of salicylic acid.
My foreign correspondents have now found, that still better dye-stuffs, producing
red shades with a bluer tinge, are formed, if, instead of the nitro benzidine used in.
the process of the aforesaid Specification, a corresponding quantity of mono nitro
tolidine (NH, NO, = 1:3) be used, that is to say, if one molecular proportion of
the tetrazo derivative of mononitro-tolidine is first combined with one molecular
proportion of salicylic acid, or ortho cresotic acid, and if the intermediate products.
so formed are subsequently coupled with one molecular proportion of alpha
naphthol alpha, monosulphonic acid (Nevile & Winther), or an alkaline salt.
thereof.
The new colouring-matters thus obtained produce on mordanted and unmordanted.
wool, very clear bluish-red shades, distinguished for their great fastness when
exposed to the action of acids, light, washing, and fulling.
In order to illustrate the method of producing these dye-stuffs, the following
example is given. The parts are by weight.
COLOURING-MATTER OBTAINED FROM ONE MOLECULAR PROPORTION OF
TETRAZOTISED MONO NITROTOLIDINE, ONE MOLECULAR PROPORTION OF
SALICYLIC ACID, AND ONE MOLECULAR PROPORTION OF ALPHAI NAPHTHOL.
ALPHA, MONOSULPHONIC ACID.
=
25-7 parts of mononitrotolidine (NH, NO,
1:3), such as is formed, for
instance, on treating a solution of one molecular proportion of tolidine sulphate in
concentrated sulphuric acid, with one molecular proportion of potassium nitrate, or
the corresponding quantity of nitro sulphuric acid, are converted in the usual way
into the tetrazo compound, and the latter is allowed to flow into an icy-cold solution
prepared from 14 parts of salicylic acid and 60 parts of sodium carbonate. When
the formation of the intermediate product is completed, a well-cooled solution in
water of 25 parts of the sodium salt of alpha, naphthol alpha, monosulphonic acid
(Nevile and Winther) is added. After standing during 12 hours, the liquid
mixture is heated to 30 degrees Centigrade, in order to complete the formation of
the dye, and after standing again during several hours, the mixture is boiled
up. The dye-stuff is salted out, filtered off, pressed, and dried, in the usual
manner.
It produces on wool, in an acidulated bath, a beautiful bluish-red, distinguished
by its great fastness on exposure to the action of acids, washing, and fulling.
Its composition is represented by the following formula :-

page_text: It will be understood that my foreign correspondents do not claim the colouring-
matter formed from nitro benzidine (mon-ortho-nitro-para-diamido-diphenyl) and
salicylic acid (or ortho cresotic acid) and alpha, naphthol alpha, monosulphonic
acid.
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 mixed disazo dye-stuffs by coupling one molecular
proportion of the tetrazo derivative of mononitrotolidine (NH, NO, = 1:3)
with one molecular proportion of salicylic acid or orthocresolcarboxylic acid
(CH, OH: COOH 1:2:3), or an alkaline salt thereof, and with one molecular
proportion of alpha, naphthol-alpha, mono sulphonic acid, or an alkaline salt
thereof.
=
2. As new products of manufacture, the new mixed disazo dye-stuffs produced
by the process hereinbefore defined, or by any other means affording the same
result.
Dated this 12th day of November 1801
NEWTON & SON,
Agents for the Applicant.