The Manufacture or Production of Dye Stuffs.
Year: 1893

page_text: Date of Application, 16th June, 1893
Complete Specification Left, 16th Mar., 1894-Accepted, 21st Apr., 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 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:-
My foreign correspondents have described in the Specification of application for
Letters Patent No. 8898, dated 3rd May 1893, the production of blue basic azine
dye stuffs, or sulpho acids thereof, by reacting with disubstituted naphthylene
diamines (particularly meta naphthylene diamines), or sulpho acids thereof, on the
nitroso derivatives of secondary or tertiary aromatic amines.
In addition thereto, my foreign correspondents have now discovered that the
nitroso compounds mentioned in the aforesaid Specification can be replaced by all
those substances which act in the same, or in a similar manner, viz., by the so-called
chloro imides (employing, for instance, quinone dichloro imide), or analogous
products, or azo compounds obtainable by coupling diazo derivatives with primary,
secondary, or tertiary amines, or substituted amines, particularly sulpho acids
thereof, the same or analogous coloring matters being thus produced.
For instance, the same coloring matter resulting, as described in the second
example, of above named Specification, from nitroso dimethylaniline hydrochloride
and ditolylnaphthylene diamine, can be produced by employing dimethylamido azo
benzene, or analogous azo compounds derived from dimethylaniline, in place of
the nitroso dimethylaniline hydrochloride used in the said example.
It is of special technical value that these new methods are in part capable of a
much greater extension than that described in the above Specification No. 8898 of
1893, inasmuch as the azo derivatives of many amines (particularly of the naph-
thalene series) can be obtained with greater ease than the nitroso compounds, and
as nitroso compounds of primary amines are not obtainable in sufficient quantities
for commercial purposes.
Amongst the azo dye stuffs of the naphthalene series, for instance, those resulting
from alphanaphthylamine, alkylated alphanaphthylamine, phenyl, tolyl, xylyl, or
naphthylalphanaphthylamine sulpho acids (a1 B, or a₁ ẞ, or a₁ a) can be profitably
employed.
The production of the dye stuffs by means of the processes hereinbefore defined,
in general, is analogous to that described in the Specification above referred to,
No. 8898 of 1893, and consists in heating the said, azo products, or chloro imides,
with the substituted naphthylene diamines, or sulpho acids thereof, most practically
in the presence of suitable solvents or diluents, such as alcohol, acetic acid, or
the like.
In order to illustrate the nature of this invention and the manner in which it
can be carried into practical effect, the following example is given, which, however,
is merely to be regarded as typical, as the invention is not restricted thereto. The
parts are by weight.

page_text: EXAMPLE.
COLORING MATTER FROM BENZENE AZO-PHENYL l NAPHTHYLAMINE α
SULPHO ACID AND DIPHENYL a 3, NAPHTHYLENE DIAMINE a MONO-
SULPHO ACID.
7-8 parts of diphenyl α₁ ß, naphthylene diamine a mono sulpho acid, and 9 parts
of benzene azo phenyl a naphthylamine a, sulpho acid, mixed with 50 parts of
strong acetic acid, and with a small quantity of sodium acetate, are heated at from
80 to 100 degrees centigrade. The reaction is completed within a short time.
The reaction mixture is then poured into water, and the coloring matter thus
produced is salted out. After filtering off, it may be purified by redissolving and
precipitation.
Analogous coloring matters, which likewise dye on wool blue shades fast against
'the action of alkalies, are obtained, if, in the above example, the diphenylnaphthy-
lene diamine sulpho acid is replaced by diphenyl, ditolyl, dixylyl, or dinaphthyl
a ẞ, naphthylene diamine, diphenyl, ditolyl, dixylyl, or dinaphthylla ẞ, naphthylene
diamine B, monosulpho acid, diphenyl, ditolyl, dixylyl, or dinaphthyl a ẞ, naph-
thylene diamine B monosulpho acid, diphenyl, ditolyl, dixylyl, or dinaphthyl
a B naphthylene diamine Bs a disulpho acid, diphenyl, ditolyl, dixylyl, or
dinaphthyl a naphthylene diamine mono or disulpho acids (the last named mono
or disulpho acids being produced by sulphonating the corresponding diamines), or
ditolyl, dixylyl, dinaphthyl a, ẞ, naphthylene diamine a sulpho acid.
In place of the azo product employed in the above example, other azo dye
stuffs resulting from diazo compounds and phenylnaphthylamine sulpho acid, or,
speaking more broadly, all azo products and substitution derivatives thereof, or
chloro imides and analogous substances of the benzene or naphthalene series, can
be used.
According to the researches of my foreign correspondents, the same or similar
dye stuffs result if, in place of the chloro imides or nitroso derivatives above referred
to, the corresponding products obtainable therefrom by reduction, are used, viz., by
employing, for instance, paraphenylene diamine, paratoluylene diamine, paraamido-
dialkyl aniline, or analogous diamines, or sulpho acids thereof. In this case, the
process must be effected by treating the said diamines or the like, and the substi
tuted naphthylene diamines (particularly meta naphthylene diamines), or sulpho
acids thereof, in the presence of suitable solvents or diluents, with suitable oxidising
agents, such as, for example, ferric chloride, potassium dichromate, or manganese
dioxide and acetic acid.
My foreign correspondents have further found, that the dye stuffs resulting in the
manner hereinbefore defined, and containing no sulpho group, or only one, can, by
a treatment with sulphonating agents, be converted into acid coloring matters,
which are soluble with ease, or with greater readiness than heretofore.
Dated this 16th day of June 1893.
7
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
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 :-
My foreign correspondents have described in the Specification of application for
Letters Patent No. 8898, dated 3rd May 1893, the method of producing basic

page_text: azine dye-stuffs, or sulphonic acids thereof, from "symmetrical" or "mixed"
dialkyl-ai B, naphthylene diamines, or dialkyl a₁ ẞ, naphthylene diamine sulphonic
acids, and nitroso derivatives of secondary or tertiary aromatic amines or amido
Bulphonic acids.
My foreign correspondents have now further discovered, that instead of the
nitroso compounds mentioned in the aforesaid Specification, any of the substances
can be used which act in the same or in a similar manner, viz., quinone dichlorimide,
or analogous products, or azo compounds such as are obtainable by coupling diazo
derivatives with primary, secondary, or tertiary amines, or substituted amines,
particularly sulphonic acids thereof, the same or analogous coloring matters being
thus produced.
For instance, a coloring matter which is identical with that formed as described
in the Example B of the above named Specification, No. 8898 of 1893, from
nitrosodimethylaniline hydrochloride and diparatolyl alpha, beta, naphthylene
diamine, can be produced by using dimethylamidoazobenzene, or analogous azo-
compounds derived from dimethylaniline, in place of the nitroso dimethylaniline
hydrochloride prescribed in the said example.
It is of special technical importance that these new methods are, in many cases,
of more general application than that described in the above Specification
No. 8898 of 1893, owing to the fact that the azo derivatives of many amines
(particularly those of the naphthalene series) can be obtained more easily than
the nitroso compounds, and as nitroso compounds of primary amines are not
obtainable in sufficient quantities for commercial purposes.
Amongst the azo dye-stuffs of the naphthalene series, for instance, which may
be advantageously used, are those prepared from alphanaphthylamine alkylated
alphanaphthylamine, or from phenyl or tolyl alpha naphthylamine sulphonic acids
(ai ß, or a ẞ, or ai a₁).
"
The method of producing the dye-stuffs by means of the processes herein before
defined, is, generally speaking, analogous to that described in the Specification
above referred to, No. 8898 of 1893, and consists in heating the quinone
dichlorimide, or the said azo products, with the "symmetrical
"mixed
dialkyl alpha, beta, naphthylene diamines, or dialkyl alpha, beta, naphthylene
diamine sulphonic acids, preferably in the presence of suitable solvents or diluents,
such as alcohol, acetic acid, or the like.
or
In order to illustrate the nature of this invention, and the manner in which it
can be carried into practical effect, the following examples are given, which,
however, are merely to be regarded as typical, as the invention is not restricted
thereto. The parts are by weight.

page_text: contain sulpho groups, or only one, can. be converted into more soluble dye stuffs
by suitable treatment with sulphonating agents. The coloring matters obtainable
by means of the process herein before illustrated, in general produce shades
varying from bluish-red, bluish-violet, to blue, when fixed on cotton prepared with
tannic acid or the like.
COLORING MATTER
FROM BENZENE AZO PHENYL ALPHA, NAPHTHYLAMINE
ALPHA SULPHONIC ACID AND DIPHENYL ALPHA BETA, NAPHTHYLENE
DIAMINE ALPHA, MONOSULPHONIC ACID.
A mixture of 7.8 parts of diphenyl alpha beta, naphthylenediamine alpha
monosulphonic acid, 9 parts of benzene azo phenyl alpha, naphthylamine alpha
sulphonic acid, together with 50 parts of strong acetic acid, and a small quantity
of sodium acetate, is heated at from 80 to 100 degrees centigrade. The action is
completed within a short time. The mixture is then poured into water, and the
coloring matter thus produced is salted out and filtered off. It may be purified
by dissolving it and re-precipitating.
Analogous coloring matters, which also produce shades on wool mostly varying
from blue to bluish-green, and which are comparatively very fast in presence both
of alkalies and acids, are obtained, if, in the above Example B, instead of the
diphenyl alpha, beta, naphthylene diamine alpha, monosulphonic acid, othe
corresponding quantities of other "symmetrical" or "mixed" dialkyl alpha, beta,
naphthylene diainine sulphonic acids, or dialkyl alpha beta, naphthylene diamines,
are used.
Moreover, other azo products can be used in place of the azo products prescribed
in the above Example B., viz. such as are formed by the combination of diazo
compounds with other phenylnaphthylamine sulphonic acids or the like, or, speaking
more broadly, with primary, secondary, or tertiary amines, or amido sulphonic acids
of the benzene or naphthalene series, or amidophenols or amidophenol ethers.
Of the products obtainable by means of the process illustrated in the above
Example B., those which either do not contain sulphonic groups, or only one, can be
converted into dyes which are more readily soluble than the original products by a
subsequent treatment with sulphonating agents.
According to the researches of my foreign correspondents, the same or similar
dye-stuffs are formed, if, in place of the nitroso derivatives of the secondary or
tertiary aromatic amines, or amido sulphonic acids above referred to, the corre-
sponding amido compounds containing the amido group in place of the nitroso
group, are used, viz., on using, for instance, paraamidomonoalkylaniline, paraamido-
dialkylaniline, or analogous diamines or sulphonic acids thereof, containing either
one or two alkyl radicles in one of the amido groups. In such cases, the process is
carried out by treating the said diamines, or the like, and the "symmetrical" or
"mixed" dialkyl alpha₁ beta, naphthylene diamines, or dialkyl alpha, beta,
naphthylenediamine sulphonic acids, in the presence of suitable solvents or diluents,
with suitable oxidising agents, such as, for example, ferric chloride, potassium
dichromate, or manganese dioxide, in the latter case profitably in the presence of
acetic acid.
This joint oxidation of "symmetrical" or mixed dialkyl alpha beta, naphthylene
diamines, or dialkyl alpha, beta, naphthylene diamine sulphonic acids, and para-
amido monoalkylaniline, paraamidodialkylaniline, or analogous alkylated diamines,
or sulphonic acids thereof, is illustrated by the following example. The parts are
by weight.

page_text: naphthylene diamine hydrochloride, are dissolved in from 6 to 8 parts of hot
alcohol, and 0-6 parts of glacial acetic acid are added to the solution. The liquid
having been heated to about 60 degrees centigrade, a concentration solution, in
water, of 2.95 parts of potassium bichromate is slowly introduced. The formation
of the dye-stuff immediately begins, and is completed within a short time. In order
to precipitate it, concentrated muriatic acid is added in excess. The coloring
matter which separates in the form of crystals is filtered off, washed with alcohol,
and dried. When reduced to powder it has a crystalline, bronze-colored, lustrous
appearance. This dye-stuff produces very clear violet shades on cotton prepared
with tannic acid or the like.
The process is effected in a manner analogous to that described in the foregoing
Example C., if, on the one hand, the paramido dimethylaniline is replaced by the
corresponding quantities of paramido diethylaniline or other analogous paradiamines
(containing, in one of the amido groups, either two or a single alkyl group), or
sulphonic acids thereof, or if, in place of the diphenyl alpha beta, naphthylene
diamine used in the said Example C, other "symmetrical" or "mixed" dialkyl
alpha beta, naphthylene diamines, or dialkyl alpha, beta2 naphthylene diamine
sulphonic acids, are used.
The oxidation may also be carried out by means of ferric chloride, or manganese
dioxide, in the presence of acetic acid or other oxidising agents.
Should the products thus obtained either not contain sulphonic groups, or only
one, a suitable treatment with sulphonating agents suffices to convert them into
more soluble dye-stuffs.
My foreign correspondents have described in the above Examples A, B, and C,
distinct methods of producing several of the dye-stuffs hereinbefore defined, but,
of course, they do not limit themselves to the directions given therein, as these can
be varied.
For instance, other solvents or diluents can be used, and the processes can be
carried out at higher temperatures.
According to the researches of my foreign correspondents, a difference caused by
the use of certain solvents or diluents, or by higher temperatures, only becomes
apparent when condensing the above defined azo products with "symmetrical"
"mixed
dialkyl-alpha-beta-naphthylene diamines, or dialkyl-alpha-beta2-
or
"
naphthylene diamine sulphonic acids.
"
On using neutral or basic solvents or diluents, and also on effecting the change at
temperatures above 100 degrees centigrade, dye-stuffs are formed differing from
those obtained, as the case may be, either by acid solvents or diluents, or at less
elevated temperatures.
My foreign correspondents account for this peculiar fact, by assuming that, on
using acid solvents or diluents (such as glacial acetic acid), the amine which is
liberated from the azo compound during the condensation of the latter with the
said dialkyl-alpha,-beta,-naphthylene diamines, or sulphonic acids thereof, at once
combines with a part of the acid solvent or diluent used, a salt being thus formed:
which is incapable of acting on the resulting dye-stuff, and that on using alcohol
as solvent, the temperature (when the interaction takes place in open vessels)
cannot be raised above 100 degrees centigrade, whilst if neutral or basic solvents or
diluents are used, on the one hand, the amine which is liberated as above mentioned
is not converted into a salt, and therefore is capable of further acting on the dye-
stuff which is first formed, and that, on the other hand, on using, in place of
alcohol, other neutral or basic solvents boiling at higher temperatures, the higher
temperature to which the mixture can be heated, causes a further action of the
amine (liberated from the azo compound) on the colouring-matter which is first
formed. If, for instance, azo benzene and diparatolyl-alpha1-beta,-naphthylene
diamine are heated in glacial acetic acid solution, and the product is subsequently
sulphonated, a dye-stuff is obtained which yields shades tending more towards
yellow, in contrast with dilute alkalies, whilst the dye-stuff produced in˜an'

page_text: analogous manner, when phenol is used as solvent or diluent, yields shades which
withstand the action of alkalies, and possess a blue hue.
The production of the dye-stuffs such as, in general, yield blue or green shades
which withstand alkalies, is illustrated by the following example. The parts are by
weight.
COLOURING-MATTER OBTAINED FROM AZO BENZENE AND
DI-PARA-TOLYL-
ALPHA-BETA NAPHTHYLENE DIAMINE ALPHA-MONOSULPHONIC ACID, IN
THE PRESENCE OF PHENOL, AS SOLVENT OR DILUENT.
A mixture prepared from 10 parts of dipara-tolyl-alpha,-beta-naphthylene
diamine-alpha monosulphonic acid,-6.6 parts of azo benzene,-and 20 parts of
phenol, is heated, during 5 hours, at 130 degrees centigrade, in a vessel provided
with a stirrer, until the action is complete. When the mixture is cool, the phenol
is removed with the aid of alkalies.
The sodium salt of the rosinduline monosulphonic acid thus formed, being but
slightly soluble in water, remains in crystals. It is filtered off, pressed, dried, and
Bubsequently converted, by treatment with sulphonating agents, into the disulphonic
acid, which, in the form of sodium salt, constitutes the dye-stuff. The shades
produced therewith withstand the action of alkalies and acids.
The phenol used in the last example can be replaced by its homologues, or by
aniline or homologues thereof, naphthalene, diphenylamine, naphthylamine,
naphthol, or the like.
On using aniline, naphthalene, or the like, the solvent or diluent in excess is
removed (when the action is complete), by distillation with steam, or by treatment
with dilute acids.
The action proceeds in a manner analogous to that described in the said
Example D, if the corresponding quantities of azo toluene or azoxylene, or other
of the azo products herein before defined, are used, or if the dipara-tolyl-alpha₁-
beta-naphthylene diamine alpha, monosulphonic acid 18 replaced by the equivalent
quantities of other "symmetrical" or "mixed" dialkyl-alpha-beta-naphthylene
diamine sulphonic acids, or dialkyl-alpha1-beta-naphthylene diamines.
The shades afforded by the colouring-matters which are thus obtainable, are, in
general, more bluish or green, and are distinguished for the manner in which they
withstand the action of alkalies.
My foreign correspondents mean by the above expression --" symmetrical" or
"mixed dialkyl-alpha-beta-naphthylene diamines, or dialkyl-alpha1-beta,-
naphthylene diamine sulphonic acids, the products defined in the Specification of
application for Letters Patent No. 8898, dated 3rd May 1893.
Having now particularly described and ascertained the nature of this 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 basic azine dye-stuffs, or sulphonic acids thereof, more or
less difficultly soluble, by allowing the "symmetrical or "mixed" dialkyl-alpha-
beta-naphthylene diamines, or dialkyl-alpha,-beta-naphthylene diamine sulphonic
acids herein before referred to, to act in the presence of acid, neutral or basic
solvents, or diluents, at more or less elevated temperatures, on quinone dichlorimide,
or azo products resulting from the combination of diazo compounds with primary,
secondary, or tertiary amines, or amidosulphonic acids of the benzene or naphtha-
lene series, or amidophenols, or amidophenolethers.
66
sym-
2. The process for producing basic azine dye-stuffs, or sulphonic acids thereof,
more or less difficultly soluble, which process consists in subjecting the
metrical" or "mixed" dialkyl-alpha,-betas-naphthylene diamines, or dialkyl-alpha-
beta-naphthylene diamine sulphonic acids herein before referred to, together with

page_text: alkylated para diamines or para diamine sulphonic acids, containing, in one of
their amido groups, either a single or two alkyl radicles, to a joint oxidation in the
presence of suitable solvents or diluents.
3. The conversion of the basic azine dye-stuffs, or difficultly soluble sulphonic
acids thereof, obtainable as described in the foregoing first and second claim, into
more readily soluble acid dye-stuffs, by a subsequent treatment with sulphonating
agents.
4. As new products of manufacture, the new dye-stuffs produced by the
processes herein before defined, or by any other means affording the same result.
Dated this 16th day of March 1894.
NEWTON & SON,
Agents for the Applicant.