The Manufacture or Production of Dye-stuffs.
Year: 1895

page_text: Date of Application, 18th June, 1895
Complete Specification Left, 18th Mar., 1896-Accepted, 18th Apr., 1896
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Dye-stuffs.
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:
-
By a joint oxidation of one molecular proportion of paramido-monoethylaniline,
together with two molecular proportions of aniline, or of one molecular proportion
of paraphenylene diamine, together with one molecular proportion of ethylaniline
and one molecular proportion of aniline, two isomeric safranines have already
been obtained (see Berichte der Deutschen Chemischen Gesellschaft, XIX,
pages 151 & 152). The monoethylphenosafranines thus obtained are, however,
dyestuffs of little value, as they only yield on fibre uncertain shades.
My foreign correspondents have now found, that most valuable dye stuffs,
remarkable for the clearness of their color, can be obtained by subjecting to a
joint oxidation one molecular proportion of paramidomonoalkylaniline (such as
paramidomonomethylaniline or paramidomonoethylaniline and the like), together
with two molecular proportions of orthotoluidine, or with a mixture of one
molecular proportion of orthotoluidine and one molecular proportion of another
primary amine (such as aniline naphthylamine or the like).
My foreign correspondents have also produced these coloring matters (which
chemically are 66
mono alkyltoluphenosafranines") by oxidising one molecular
proportion of para toluylene-diamine together with one molecular proportion of
alkylaniline (such as methyl or ethylaniline or the like) and with one molecular
proportion of any aromatic primary base (such as aniline, orthotoluidine and
the like).
The above-named safranines can also be obtained by means of the other so-called
"safranine processes," for instance, by acting on one molecular proportion of
nitroso-monoalkylaniline (such as nitrosomethyl aniline or nitrosethylaniline and
the like) with two molecular proportions of orthotoluidine, or with a mixture of
one molecular proportion of orthotoluidine and one molecular proportion of another
primary base, or by the action of one molecular proportion of quinone dichlorodiimide
upon one molecular proportion of alkylaniline and one molecular proportion of
orthotoluidine, or by the action of one molecular proportion of toluquinone
dichlorodiimide upon one molecular proportion of monoalkylaniline and one
molecular proportion of any primary amine.
My foreign correspondents give the following examples, in order to illustrate
the process of practically producing the dye-stuffs. The parts are by weight.
EXAMPLE 1.
PRODUCTION OF A SAFRANINE. DYE-STUFF FROM ONE MOLECULAR
PRO-
PORTION OF PARAMIDOMONOMETHYLANILINE HYDROCHLORIDE AND TWO
MOLECULAR PROPORTIONS OF ORTHOTOLUIDINE HYDROCHLORIDE.
A solution in water of 20 parts of paramidomonomethylaniline hydrochloride
(1 molecular proportion) is mixed with a solution of 14.5 parts of orthotoluidine

page_text: hydrochloride (1 molecular proportion). A 5 per cent. solution of potassium
dichromate, prepared from 20 parts of potassium dichromate, is slowly added, and
the resulting mixture is rendered acid by the addition of a small quantity of
acetic acid. After the formation of the indamine is complete, a solution of
14.5 parts of orthotoluidine hydrochloride (1 molecular proportion) and a 5 per
cent. solution of potassium dichromate, prepared from 20 parts of potassium
dichromate, is then added, and the resulting liquid is heated until the original
blue color has turned into a pure red. At this stage the heating is stopped, and
the coloring matter thus obtained is isolated in the usual manner.
It produces on cotton prepared with tannic acid bluish-red shades, which are
more blue, and which possess far more brilliancy, than those obtained with the
known dye-stuff "tolusafranine." The dye stuff has probably the formula :-
Dye-stuffs similar to that obtained in this example are produced, if either the
paramidomonomethylaniline used therein is replaced by paramidomonoethylaniline 1
or the like, or if a mixture of one molecular proportion of orthotoluidine and one
molecular proportion of another primary base (such as aniline, naphthylamine, and
the like) are used in place of two molecular proportions of orthotoluidine.
ONE
PRODUCTION OF A SAFRANINE DYE-STUFF FROM ONE MOLECULAR
PROPORTION OF PARATOLUYLENEDIAMINE HYDROCHLORIDE,
MOLECULAR PROPORTION OF MONOETHYLANILINEHYDROCHLORIDE, AND
ONE MOLECULAR PROPORTION OF ANILINE HYDROCHLORIDE.
A solution in water of 19.4 parts of paratoluylenediaminehydrochloride
(1 molecular proportion) is mixed with a solution of 16 parts of ethylaniline
hydrochloride. A 5 per cent. solution of potassium dichromate, prepared from
20 parts of potassium dichromate, is then added, and the mixture is rendered acid
by the addition of a small quantity of acetic acid. When the formation of the
indamine is complete, a solution in water of 13 parts of aniline hydrochloride, and
afterwards a per cent. solution of potassium dichromate, prepared from 20 parts
of potassium dichromate, are introduced during slow heating by a water bath.
The safranine thus completed is isolated in the usual manner. It dyes cotton
prepared with tannic acid in bright yellowish-red shades, only slightly more yellow
than those obtained with the dye stuff produced in the foregoing Example I. It
has probably the formula

page_text: Analogous colouring matters are obtained on replacing the ethylaniline used in
the preceding example by equivalent quantities of methylaniline or the like, or in
employing other primary amines in place of aniline.
Of course the hereinbefore described safranines can also be obtained by means
of other so-called safranine processes," for instance, either by the action of one
molecular proportion of quinonedichlorodiimide upon a mixture of one molecular
proportion of orthotoluidine, and one molecular proportion of an alkylaniline, or
by acting on one molecular proportion of toluquinonedichlorodiimide with a
mixture of one molecular proportion of monoalkylaniline and one molecular
proportion of any primary base, or by the action of nitrosomonoalkylaniline,
nitrosomonomethylaniline, or the the like, upon two molecular proportions of
orthotoluidine, or upon a mixture of one molecular proportion of orthotoluidine
with one molecular proportion of another primary base.
My foreign correspondents give the following example in order to illustrate the
process of producing the herein before defined dye-stuffs from nitrosomonoalkyl-
anilines. The parts are by weight.
OF
PRODUCTION OF A SAFRANINE FROM ONE MOLECULAR PROPORTION
NITROSOMONOETHYLANILINE HYDROCHLORIDE AND TWO MOLECULAR
PROPORTIONS OF ORTHOTOLUIDINE.
17-2 parts of nitrosomonomethylaniline hydrochloride (one molecular proportion)
and 22 parts of orthotoluidine (two molecular proportions) are dissolved in alcohol.
The resulting solution is heated by means of a water bath until the original yellow
colour has turned into a pure red. Then the solution is rendered acid by means
of a small quantity of acetic acid, and during heating a 5 per cent. solution of
potassium dichromate, prepared from 20 parts of potassium dichromate, is slowly
added. After distilling off the alcohol, the safranine thus completed is isolated
in the usual manner. It is identical with that obtained in the foregoing first
example.
as these
In the production of the dye-stuffs hereinbefore defined my foreign correspondents
do not limit themselves to the directions given in the preceding examples,
can be varied, and, in general, all methods known & in use for obtaining safranine
colouring matters can be employed.
Dated th: 107
1005
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Dye-stuffs.
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 :—
Two isomeric safranines have been obtained by conjointly oxidising a molecular
proportion of paramidomonethylaniline together with two molecular proportions of
aniline, or of a molecular proportion of paraphenylenediamine, together with a
molecular proportion of ethyl aniline, and a molecular proportion of aniline (see
Berichte der Deutschen Chemischen Gesellschaft, XIX, pages 151 & 152)
The
monethylphenosafranines thus formed, however, are of little value as dye-stuffs, as
they produce but indefinite shades on fibres.
My foreign correspondents have now found, that valuable dye-stuffs, remarkable

page_text: for the clearness of the colours they afford, can be obtained by conjointly oxidising
a molecular proportion of a paramidomonalkylaniline (such as paramidomono-
methylaniline or paramidomonethylaniline and the like), and two molecular pro-
portions of orthotoluidine, or a mixture of a molecular proportion of orthotoluidine
with a molecular proportion of another primary amine (such as aniline, xylidine,
or the like).
My foreign correspondents have also produced these "monoalkyltolupheno-
safranines," by oxidising a mixture of a molecular proportion of paratoluylene-
diamine with a molecular proportion of an alkylaniline (such as methyl or
ethylaniline or the like), and a molecular proportion of any aromatic primary base
(such as aniline, ortho-toluidine, and the like).
The said safranines can also be produced by means of the other processes used
in preparing safranines, for instance, by acting on a molecular proportion of
nitrosomonalkylaniline (such as nitrosomethylaniline, or nitrosoethylaniline, and
the like) with two molecular proportions of orthotoluidine, or with a mixture of a
molecular proportion of orthotoluidine, and a molecular proportion of another
primary base, or by the action of a molecular proportion of quinonedichlorodiimide
on a molecular proportion of an alkylaniline and a molecular proportion of ortho-
toluidine, or by the action of a molecular proportion of toluquinonedichlorodiimide
on a molecular proportion of a monalkylaniline and a molecular proportion of any
primary amine.
The bereinbefore defined dye-stuffs are identical with those obtained from an
alphylmetatoluylenediamine and a paranitrosomonalkylaniline by the processes
described in the British Letters Patent 961094.
My foreign correspondents give the following examples as illustrations of the
processes to be used in producing the dye-stuffs. The parts are by weight.
PRODUCTION OF A SAFRANINE DYE-STUFF FROM A MOLECULAR PROPORTION
OF PARAMIDOMONOMETHYLANILINE HYDROCHLORIDE AND TWO MOLE-
CULAR PROPORTIONS OF ORTHOTOLUIDINE HYDROCHLORIDE.
A solution in water of 20 parts of paramidomonomethyl aniline hydrochloride
(1 molecular proportion) is mixed with a solution of 14-5 parts of orthotoluidine
hydrochloride (1 molecular proportion). A 5 per cent. solution of potassium
dichromate, prepared from 20 parts of potassium dichromate, is then slowly added,
the mixture being rendered acid from time to time by the addition of a small
quantity of acetic acid. When the formation of the indamine is at an end, a solution
of 14.5 parts of orthotoluidine hydrochloride (1 molecular proportion) is added,
and then a 5 per cent. solution of potassium dichromate, prepared from 20 parts of
potassium dichromate, is gradually introduced, and the liquid is heated until the
original blue colour has turned into a pure red. At this stage the heating is
stopped, and the colouring matter thus obtained is isolated in the usual manner.
It produces on cotton prepared with tannic acid, bluish-red shades which are
of a deeper blue, and far more brilliant, than those obtained on using the known
dyestuff tolusafranine."
66
The dyestuff is probably represented by the formula

page_text: Dye-stuffs similar to that obtained by following this example are produced if,
instead of the paramidomonomethyl aniline prescribed therein, paramidomonethyl-
aniline, or the like, be used, or if a mixture of a molecular proportion of ortho-.
toluidine, and a molecular proportion of another primary base (such as aniline,.
xylidine, and the like), be substituted for two molecular proportions of ortho--
toluidine
MARMI M
PRODUCTION OF A SAFRANINE DYE-STUFF FROM A MOLECULAR PROPORTION
A MOLECULAR PRO-
OF
HYDROCHLORIDE,
PARATOLUYLENEDIAMINE
A MOLECULAR.
PORTION OF MONETHYLANILINEHYDROCHLORIDE, AND
PROPORTION OF ANILINE HYDROCHLORIDE.
A solution in water of 19.4 parts of paratoluylenediamine hydrochloride-
(1 molecular proportion) is mixed with a solution of 16 parts of ethylaniline hydro--
chloride. A 5 per cent. solution of potassium dichromate, prepared from 20 parts
of potassium dichromate, is then added, and the mixture is rendered acid by the
addition of a small quantity of acetic acid. When the indamine is formed, it is
mixed with a solution, in water, of 13 parts of aniline hydrochloride, and
afterwards a 5 per cent. solution of potassium dichromate prepared from 20 parts of
potassium dichromate is gradually introduced, the mixture being heated on the
water bath.
The safranine thus produced is isolated in the usual manner. It dyes cotton
prepared with tannic acid bright-red shades similar to those obtained by means of
the dye-stuff produced in the foregoing Example I. It probably has the
Analogous colouring matters are obtained on substituting for the ethylaniline-
used in the preceding example, the equivalent quantity of methylaniline or the
like, or on using other primary amines in place of aniline.
Of course the herein before described safranines can also be obtained by means
of other so-called "safranine processes," for instance, either by the action of a
molecular proportion of quinonedichlorodiimide on a mixture of a molecular pro-
portion of orthotoluidine, and a molecular proportion of an alkyl aniline, or by
acting on a molecular proportion of toluquinonedichlorodiimide with a mixture of
a molecular proportion of monalkylaniline and a molecular proportion of any-
primary base, or by the action of nitrosomonalkylaniline, such as nitrosomono--
methylaniline or the like, on two molecular proportions of orthotoluidine, or on a
mixture of a molecular proportion of orthotoluidine with a molecular proportion of
another primary base.
My foreign correspondents give the following example, in order to illustrate the
process of producing the herein before defined dyestuffs from nitrosomonethyl-.
alkylanilines. The parts are by weight.
EXAMPLE III.
PRODUCTION OF
A SAFRANINE
FROM
NITROSOMONOETHYLANILINE AND TWO
ORTHOTOLUIDINE.
A
PROPORTION
MOLECULAR
OF
MOLECULAR PROPORTIONS of

page_text: and 22 parts of orthotoluidine (two molecular proportions) are dissolved in alcohol,
and the solution is heated by means of a water-bath, until the original yellow
colour has turned into a pure red. The solution is rendered acid by means of a
small quantity of acetic acid, and a 5 per cent. solution of potassium dichromate,
prepared from 20 parts of potassium dichromate, is slowly added to the hot liquid.
When the action is at an end, the alcohol is distilled off, and the safranine is then
isolated in the usual manner. It is identical with that obtained in the foregoing
first example.
In producing the dye-stuffs bereiubefore defined, my foreign correspondents do
not limit themselves to the directions given in the preceding examples, as these
can be varied, and all known methods of obtaining safranine colouring-matters can
be used.
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 monalkylated safranines:-
a) by conjointly oxidising a molecular proportion of paramidomonalkylaniline
either together with two molecular proportions of orthotoluidine, or together
with a molecular proportion of orthotoluidine and a molecular proportion
of another primary base;
b) by acting on two molecular proportions of ortho toluidine, or on a
molecular proportion of orthotoluidine and a molecular proportion of any
_primary base, with a molecular proportion of paranitrosomonalkylaniline.
2. The production of monalkylated safranines: by conjointly oxidising a
molecular proportion of paratoluylenediamine, together with a molecular pro-
portion of a monalkylaniline and a molecular proportion of any primary base.
Dated this 18th day of March 1896.
NEWTON & SON,
Agents for the Applicant..