The Manufacture of Colouring Matters.
Year: 1895

page_text: Date of Application, 19th Mar., 1895
Complete Specification Left, 19th Dec., 1895-Accepted, 7th Mar., 1896
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture of 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 those azo products of the naphthalene
series which contain the azo group in the "meta" position relatively to a sulphonic
group, can readily be converted by heating with aniline, toluidine, or other primary
aromatic amines, in the presence of salts thereof, or other agents capable of
facilitating the action, into azine derivatives, which are valuable dyestuffs, either
by themselves, or after sulphonation.
The first stage of this reaction consists in that the sulphonic group, being in the
"meta" position relatively to the azo group, is separated in the form of sulphurous
acid, and very probably is displaced by the phenyl-amido group, tolylamido group,
or the like. It is to be noted that this first stage is analogous to the process
described in the Specification of the Letters Patent No. 8898, dated 3rd May 1893,
which process consists in heating metanaphthylaminesulphonic acids with primary
aromatic amines, and proceeds in such a manner that the sulphonic group, being in
the "meta" position relatively to the amido group, is displaced by the phenylamido
group (if, for instance, aniline and aniline hydrochloride are used), sulphurous acid
being likewise split off. During the second stage of the aforesaid new process, the
substituted naphthylenediamine derivatives (probably first formed from the azo
sulphonic acids and primary aromatic amines used) are further acted on by the
primary aromatic amines, substituted eurhodines being thus obtained as further
products. If, for instance, aniline and aniline hydrochloride are allowed to act, at
150 degrees Centigrade, on the azo compound obtained by coupling diazobenzene-
chloride with alpha-naphthylamine-alpha, beta,-disulphonic acid, the whole process
in chief proceeds in the manner illustrated by the following equation :-
On effecting the action at more elevated temperatures, the hydrogen of the azine
nucleus is finally displaced by phenyl, a rosinduline monosulphonic acid being thus
formed, which contains one sulphonic group in place of hydrogen of the naphthalene
nucleus.
meta
According to the researches of my foreign correspondents, all azo sulphonic acids
of the naphthalene series which contain a sulphonic group in the " position
relatively to the azo group, and which can therefore be termed meta-azosulphonic
acids of the naphthalene series, can be used in the process herein before defined, and
the researches of my foreign correspondents have shewn that the following meta
D

page_text: azosulphonic acids of the naphthalene series give good results, riz :-those obtained
by coupling any diazo compounds with alpha-naphthionic acid, alpha, naphthol-
alpha-monosulphonic acid, alpha,-naphthylamine-beta-sulphonic acid, alpha-
naphthol-beta-sulphonic acid, or with such polysulphonic acids, derived from the
last mentioned sulphonic acids which do not contain any substituent in the "ortho"
para" position relatively to the amido or hydroxy group.
or
The resulting substituted eurhodines obtained by acting with primary aromatic
amines on the meta-azo-sulphonic acids of the naphthalene series herein before
defined, can be converted by a subsequent sulphonation into products soluble with
comparative ease.
In order to illustrate the process for producing these substituted azines or
eurhodines, the following examples are given. The parts are by weight.—

page_text: from alpha,-naphthylamine alpha, beta,-disulphonic acid, or alpha,-naphthylamine-
alpha, sulphonic acid, or if azo products obtained from alpha, naphthylamine
alpha, beta, disulphonic acid, or alpha,-naphthylamine alpha,-alpha,-disulphon
acid, or alpha-naphthylamine beta, monosulphonic acid, or alpha,-naphthylamide
beta, alpha, disulphonic acid, or from the corresponding naphthol sulphonic acid,
are used in place of the azo products used in the preceding examples. In general
all azo products can be used which are derived from such naphthylamine sulphonie
acids, or naphtholsulphonic acids, as contain no substituents in the "ortho or
para" position relatively to the amido or hydroxy group. The homologues and
analogues of aniline can be substituted for the aniline used in the foregoing two
examples; in place of the salts of the primary amines, other agents capable of
facilitating the action may be employed.
$6
"
The resulting dyestuffs are suitable for dyeing wool in acid baths, and can
be used as valuable materials to start from, for the production of other azine
dye-stuffs.
In the production of the dyestuffs herein before defined, my foreign correspondents
do not limit themselves to the directions given in the preceding two examples, as
the mode of working can be varied, and the action of the meta azo sulphonic acids
hereinbefore defined, on the primary aromatic amines, can also be effected at some-
what higher or lower temperatures. This action can also be facilitated by adding
suitable agents (such as benzoic acid or the like) capable of facilitating the action.
The method of sulphonating can also be varied, & all methods known and in use for
sulphonating purposes can be employed. Such or similar modifications do not alter
the nature of this invention, which in general relates to the production of dyestuffs
by acting with primary aromatic amines on meta azo products of the naphthalene
series, and derived from such naphthylamine or naphtholsulphonic acids as are,
not substituted in the "ortho " or "para" position relatively to the amido or
hydroxy group, and to the subsequent sulphonation of the so-formed products if
desired.
Dated this 19th day of March 1895.
NEWTON & SON,
Agents for the Applicant.
The Manulacture or corouring шамоло
I HENRY EDWARD NEWTON of the Office of Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention aud 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 on heating the alpha amido, or
alpha hydroxy, azo sulphonic derivatives of the naphthalene series containing the
azo group in the "meta" position relatively to a sulphonic group, with aniline,
toluidine, or other primary aromatic amines, in the presence of salts thereof, or
other agents capable of facilitating the action, azine derivatives are readily formed
which are themselves valuable dye-stuffs, or become such on sulphonation.
The first stage of the interaction involves the separation, in the form of
sulphurous acid, of the sulphonic group in the "meta" position relatively to the
azo group. Probably it is displaced by the phenylamido, tolylamido, or similar
group. In fact, the change during this first stage resembles that involved in the
process described in the Specification of the Letters Patent No. 8898, dated
3rd May 1893, which consists in heating naphthylamine metasulphonic acids with
primary aromatic amines, whereby the sulphonic group in the "meta position
"

page_text: relatively to the amido group, is displaced by the phenylamido group (supposing
that aniline and aniline hydrochloride are used). In the second stage of the
aforesaid new process, the substituted naphthylene diamine derivative, which
probably is first formed by the interaction of the said azo sulphonic acid and the
primary aromatic amine, is further acted on by the primary aromatic amine, a
substituted eurhodine being formed as final product. If, for instance, aniline and
aniline hydrochloride are allowed to act, at 150 degrees Centigrade, on the azo
compound obtained by coupling diazobenzene chloride with alpha, naphthylamine
alpha, beta, disulphonic acid, the action chiefly takes place in the manner
illustrated by the following equation
:-
On effecting the action at more elevated temperatures, the hydrogen of the
azine nucleus is eventually displaced by phenyl, a rosinduline monosulphonic acid
being formed containing a sulphonic group in the naphthalene nucleus.
This new process is distinctly different from that described in the Specification
of the English Letters Patent No. 21205, dated 30 December 1890, as the
sulphonic groups in the azo compounds of the naphthalene series used in the last
mentioned process, either remain intact, or, if displaced, are not exchanged for
phenylamido or similar groups.
"
According to the researches of my foreign correspondents, all the alpha amido,
or alpha hydroxy azo products of the naphthalene series, containing a sulphonic
group in the "meta
position relatively to the azo group, and which can therefore
be termed metazo sulphonic acids of the naphthalene series, can be used in the
process herein before defined, the researches of my foreign correspondents having
shown that the following metazo sulphonic derivatives of the naphthalene series
give good results, viz., those obtained by coupling any diazo compounds with
alpha naphthionic acid, alpha, naphthol alpha, monosulphonic acid, alpha, naphthy-
lamine beta, sulphonic acid alpha, naphthol beta, sulphonic acid, or with the
corresponding polysulphonic acids, in which a substituent is absent from either
the "ortho
or the "
para position relatively to the alpha amido or alpha
hydroxy group.
"
The substituted eurhodines obtained by the interaction of primary aromatic
amines, and the metazo sulphonic acids of the naphthalene series hereinbefore
defined, can be converted by subsequent sulphonation into comparatively soluble
products.
The following examples are given in illustration of the method of producing
these substituted azines or eurhodines. The parts are by weight.
COLORING MATTER OBTAINED FROM BENZENE AZO ALPHA₁ NAPHTHYLAMINE
ALPHA, BETA, DISULPHONIC ACID AND ANILINE.
part of benzene azo alpha, naphthylamine alpha, beta, disulphonic acid
(produced by coupling alpha₁ naphthylamine alpha, beta, disulphonic acid, or
alkaline salts thereof, with diazo benzene chloride) is mixed with 4 parts of aniline
and 1 part of aniline bydrochloride. The mixture is heated, during about 5 hours,
at from 140 to 150 degrees Centigrade, being well stirred the while. When
sulphur dioxide is no longer disengaged, the temperature is raised to 160 degrees
Centigrade, and the mass is kept at this temperature until a test portion dissolved

page_text: in alcohol, yields a solution which is not rendered colorless by the addition of
alkalies. At this stage, the mass is poured into hot dilute muriatic acid. The
precipitate is filtered off and washed with hot water, in order to remove the aniline.
The azine monosulphonic acid thus obtained is almost insoluble in hot water,
but is slightly soluble in alcohol, affording a bluish-red colored solution. The
sodium salt can be obtained by carefully neutralizing the acid with diluted soda-
lye; it is soluble in hot water, and can be salted out by adding soda-lye or common
salt. A readily soluble disulphonic acid is produced by treating the last-named
monosulphonic acid, or salts thereof, with concentrated sulphuric acid. For this
purpose, 1 part of the monosulphonic acid is stirred into 5 parts of sulphuric acid
(at 66 degrees Baumé), and the liquid is heated at 100 degrees Centigrade, until a
sample readily dissolves in hot water. At this stage, the sulphonated mass is
poured onto ice; the product is then filtered off, and the sodium salt, or other
alkaline salt, of the disulphonic acid thus formed, which is the finished dye-stuff, is
prepared in the usual manner. It yields red shades.
DYE-STUFF PRODUCED FROM ANILINE AND BENZENE AZO ALPHANAPHTHIONIC
ACID.
A mixture of 1 part of the metazo product, benzene azo alphanaphthionic acid,
4 parts of aniline, and 1 part of aniline hydrochloride; is heated first at 140 degrees,
and finally at 160 degrees Centigrade. When cool, the product is treated with
dilute hydrochloric acid, and the residue is extracted with toluene. The azine is
then obtained in the form of a dark crystalline powder. This azine is converted
by means of fuming sulphuric acid (containing 20 per cent. of sulphuric anhydride),
acting at the ordinary temperature, into a disulphonic acid, which is readily soluble
in hot water, similar in dyeing properties to the dyestuff commercially known as
"Azocarmine."
Other azines are formed in an analogous manner, on using, instead of the
metazo, compounds prescribed in the preceding examples, other inetazo products
derived from alpha, naphthylamine alpha, beta, disulphonic acid, or alpha
naphthylamine alpha, sulphonic acid, or metazo products obtained from
alpha, naphthylamine alpha, beta disulphonic acid, or alpha, naphthylamine
alpha, alpha, disulphonic acid, or alpha, naphthylamine beta, monosulphonic acid,
or alpha-naphthylamine beta, alpha, disulphonic acid, or the corresponding
naphtholsulphonic acids. Speaking generally, my foreign correspondents use all
alpha amido or alpha hydroxy azo products of the naphthalene series containing
the azo group in the meta position relatively to a sulphonic group, obtained by
coupling any diazo compound with alpha, amido or alpha hydroxy-naphthalene
alpha, or beta, sulphonic acid, or with the corresponding alpha, amido or alpha,
hydroxy naphthalene polysulphonic acids, in which a substituent is absent from
either the ortho or the para position relatively to the alpha amido or hydroxy
group. The homologues and analogues of aniline can be substituted for the
aniline used in the foregoing two examples, and, in place of the salts of the primary
amines, other agents capable of facilitating the action can be used.
Azines which are polysulphonic compounds are suitable for dyeing wool in
acid baths, and may be used as valuable materials in preparing other azine
dye-stuffs.
In producing the azines and dye-stuffs hereinbefore defined, my foreign corre
spondents do not limit themselves to the directions given in the preceding two
examples, as the mode of working can be varied, and the action of the metazo
sulphonic acids herein before defined on the primary aromatic amines, can also be
effected at somewhat higher or lower temperatures. The action can also be
facilitated by adding suitable agents (such as benzoic acid or the like) capable of
assisting the action. The method of sulphonating can also be varied, and all

page_text: known methods in use for sulphonating can be adopted. Such or similar modifica-
tions do not alter the nature of this invention, which, speaking generally, relates
to the production of azines and azine sulphonic acids, by the action of primary
aromatic amines on the metazo sulphonic derivatives of the naphthalene series
herein-before defined, and to the subsequent sulphonation of the products, if
desirable.
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 azines or azine sulphonic acids from primary aromatic
amines, and the herein before defined alpha amido or alpha hydroxy azo products of
the naphthalene series containing the azo group in the meta position relatively to a
sulphonic group.
2. The process for producing azines or azine sulphonic acids, which process
consists in heating primary aromatic amido compounds; and salts of the respective
amines or other agents capable of facilitating the action, with the alpha amido or
alpha hydroxy azo derivatives of the naphthalene series containing the azo group
in the meta position relatively to a sulphonic group, and which are obtained by
coupling any diazo compound with alpha, amido or alpha, hydroxynaphthalene
alpha, or beta, sulphonic acid, or with the corresponding alpha, amido or alpha,
hydroxy naphthalene poly sulphonic acids, in which a substituent is absent from
either the ortho or para position relatively to the alpha amido or alpha hydroxy
group.
3. In the process defined by the preceding claims one and two, the use of the
metazo sulphonic products obtainable by coupling any diazo compounds with the
following alphanaphthylamine or alphanaphthol sulphonic acids or salts thereof,
viz., alpha, naphthylamine alpha2 sulphonic acid, alpha, naphthylamine beta
sulphonic acid, alpha, naphthylamine alpha, beta, disulphonic acid, alpha-
naphthylamine alpha, beta, disulphonic acid, alpha naphthylamine alpha,
alpha disulphonic acid, alpha, naphthylamine beta, alpha, disulphonic acid, or
alpha, naphthol alpha, sulphonic acid, alpha, naphthol beta, sulphonic acid, alpha,
naphthol alpha, heta, disulphonic acid, alpha, naphthol alpha, beta, disulphonic
acid, alpha, naphthol alpha, alpha, disulphonic acid, alpha, naphthol beta, alpha,
disulphonic acid.
4. The conversion of the azines and of azine sulphonic acids containing but a
single sulphonic group, into azine polysulphonic acids, by subsequently sulpho-
nating them, and isolating the polysulphonic acids, as such, or in the form of
salts.
5. As new products of manufacture, the new azines and azine sulphonic acids
produced by the processes herein before defined, or in any other way affording the
same result.
Dated this 17th day of December 1895.
NEWTON & SON,
Agents for the Applicant.