The Manufacture or Production of Colouring Matters.
Year: 1894

page_text: Date of Application, 16th June, 1894
Complete Specification Left, 18th Mar., 1895-Accepted, 20th Apr., 1895
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFAbriken, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production 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:-
The dialkylated meta naphthylene diamines (dialkyl a ẞ, naphthylene diamines),
and sulphonic acids thereof, can be coupled with diazo compounds, azo dye-stuffs
being thus formed which contain the azo group in the "para" position relatively
to the alkyl amido group in the position "alpha."
These azo colouring-matters derived, for instance, from dialkyl-a, ß, naphthylene
diamine, possess the general formula:
My foreign correspondents mean by the above letters R and R' any radicles of
the fatty or aromatic series (such as methyl, ethyl or the like, phenyl, tolyl, or the
like), whilst they understand by the above letter R" any aromatic radicle (such as
phenyl, tolyl, naphthyl, or the like), or any substituted aromatic radicle.
Analogous products containing one or more sulphonic groups in the naphthalene
nucleus result, if sulphonic acids of dialkyl-a, ẞ, naphthylene diamines are used
for producing such azo dye stuffs.
My foreign correspondents have now found, that the azo dye-stuffs hereinbefore
defined, and the analogous colouring matters derived from dialkyl-meta-phenylene
diamines, or dialkyl-meta-phenylene diamine sulphonic acids, are converted into
valuable azine dye-stuffs by heating with mineral acids. The formation of these
Dew azine colouring matters takes place in such a manner that the azo
group N N is broken up, and the radicle = N-R" is displaced in the
form of an amine, viz., NH,R", whilst the other nitrogen atom of the original
azo group is combined with the alkyl radicle R', which is in the adjacent alkylamido
group NHR!
-
The process can be illustrated by the following equation, if, for instance, azo
LD 037

page_text: dye-stuffs derived from diphenyl-a₁ ẞ, naphthylene diamine a monosulphonic acid
be used.
and of analogues of naphtho phenazine by heating with acids azo dye-stuffs
derived from phenyl-beta naphthylamine, tolyl-beta-naphthylamine, beta naphthyl
beta naphthylamine, or the like (see Witt, Berichte der Deutschen Chemischin 1
Gesellschaft, volume 20, page 573 and 579; Zincke, Berichte der Deutschen
Chemischen Gesellschaft, volume 23, page 1333).
According to the researches of my foreign correspondents, dilute and concen-
trated mineral acids can be used for producing azine dye-stuffs, as hereinbefore
defined, from azo colouring matters which are prepared by means of substituted 2

page_text: (dialkylated) meta-naphthylene diamines, meta phenylene diamines, or sulphonic
acids thereof. When using strong concentrated sulphuric acid, a sulphonating
process takes place at the same time.
Those of the products obtained by means of the process hereinbefore defined
which are insoluble, or difficultly soluble, can readily be converted into more
valuable sulphonic acids by a subsequent treatment with sulphonating agents. The
sulphonic acids thus formed dissolve with readiness.
The following example is given, in order to illustrate the process for producing
the new azine dye-stuffs, the parts being by weight.
COLOURING MATTER OBTAINED FROM BENZENE AZO DITOLYL a, ẞ, NAPH-
THYLENE DIAMINE a MONO SULPHONIC ACID.
5-23 parts of the dye-stuff obtained by coupling ditolyl a₁ ẞ, naphthylene
diamine-a, nonosulphonic acid with diazo benzene chloride, are dissolved in
20 parts of sulphuric acid (66 degrees Baumé), and the resulting liquid is heated
at from 80 to 90 degrees Centigrade, until the mass has assumed a pure green
colour. The liquid, when cooled, is poured on ice, and the sulphonic precipitated
is filtered off, and subsequently converted by means of sodium carbonate into the
sodium salt, which is the finished dye-stuff. It yields bluish-red shades on wool.
The process is carried out in a manner analogous to that described in the
preceding first example, if other azo dye-stuffs derived from ditolyl-a, ẞ, naph-
thylene diamine, or if, generally, azo colouring matters obtained by coupling any
diazo compounds with substituted (dialkylated) meta naphthylene diamines, meta
phenylene diamines, or sulphonic acids thereof, are used.
The azine dye-stuffs thus obtained in general produce shades varying from blue
to red.
My foreign correspondents have also found, that the azine dye-stuffs, herein before
defined, particularly those which are sulphonic acids, can be transformed into
colouring matters which withstand in a higher degree the action of alkalies, if they
are treated in a suitable manner with alkylating agents. My foreign corre-
spondents assume that the hydrogen atom, being combined with the so-called
azine nitrogen, is deplaced by any alkyl group during this alkylating process.
When using colouring matters derived from dialkyl a ß, naphthylene diamine
sulphonic acids in this process, dye-stuffs are obtained which materially differ from
the analogous dye-stuffs hitherto known, and being likewise sulphonic acids, as these
latter colouring matters contain sulphonic groups only in the benzene nucleus,
whilst the new dye-stuffs obtained by means of the last defined alkylating process,
also contain sulphonic groups in the naphthalene nucleus, these sulphonic groups
being in a definite position when using dialkyl a, 3, naphthylene diamine sulphonic
acids of a known composition.
This alkylating process is illustrated by the following example. The parts are
DYE-STUFF PRODUCED BY ALKYLATING THE COLOURING MATTER OBTAINABLE
AS DESCRIBED IN THE PRECEDING FIRST EXAMPLE.
4.5 parts of the azine dye-stuff, being the sodium salt of the sulphonic acid
obtained as described in the above first example, are mixed with 0-2 parts of
pottassa and 1-2 parts of ethylbromide and 12 parts of alcohol. The resulting
mixture is heated during about 3 hours at 120 degrees Centigrade. After cooling,
the mass is poured into water, and the dye-stuff thus formed is salted out, filtered
off, pressed, and dried. This colouring matter produces on wool, in acidulated
baths, clear bluish-red shades, which withstand alkalies, acids, and light.

page_text: The last example is typical for alkylating the other azine dye-stuffs hereinbefore
defined.
The researches of my foreign correspondents have further shewn, that the
alkylated dye-stuffs obtainable as described in the foregoing second example, can
also be produced, if the azo colouring matters herein before mentioned, and derived
from substituted (dialkylated) meta-naphthylene diamines, meta phenylene
diamines, or sulphonic acids thereof, are first alkylated in a suitable manner (for
instance, according to the process illustrated by the foregoing second example),
and if the alkylated products thus obtained are subsequently treated with acids, in
order to form the azine dye-stuffs. This treatment with acids can be carried out
in the manner described in the foregoing first example.
My foreign correspondents have described in the foregoing two examples, some
distinct methods of practically producing the dye-stuffs hereinbefore defined.
Naturally, they do not limit themselves to the directions above given, as these can
be varied, and all those methods can be used which are known and in use for
analogous purposes. Such modifications do not alter the nature of this invention,
which generally relates to the production of valuable dye-stuffs from azo colouring
matters obtained by coupling diazo compounds with substituted (dialkylated)
meta naphthylene diamines, meta phenylene diamines, or sulphonic acids thereof,
and which process can be carried out as hereinbefore defined.
Dated this 16th day of June 1894.
NEWTON & SON,
Agents for the Applicant,
The Manufacture or Production 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 and in what manner the same is to be performed,
to be particularly described and ascertained in and by the following statement :-
The "symmetrical" and "mixed" dialkylated meta naphthylene diamines
(dialkyl alpha, beta, naphthylene diamines), which can, for instance, be obtained
by means of the processes described in the Specifications of Letters Patent
No. 8898, 16780, and 19623", and certain sulphonic derivatives of these
"symmetrical" and "mixed" dialkyl alpha, beta, naphthylene-diamines, can be
coupled with diazo compounds, azo products being thus formed which contain the
azo group in the "para" position relatively to the alkylamido group in the position
alpha." The azo coloring matters derived, for instance, from dialkylalpha,
beta, naphthylene diamine are represented by the fellowing general formula :-

page_text: My foreign correspondents mean by the above letter R, any radicles of the
fatty or aromatic series (such as methyl, ethyl, phenyl, tolyl, or the like), and by.
the above letter R¹, any radicle of the aromatic series (such as phenyl, tolyl, or
the like), whilst they understand by the above letter R", any aromatic radicle
(such as phenyl, tolyl, naphthyl, or the like), or any substituted aromatic radicle.
Analogous azo products containing one or more sulphonic groups in the naph-
thalene nucleus are formed if sulphonic acids of dialkyl alpha, beta, naphthylene
diamines, which are not substituted in the para position relatively to the alkylamido
group in the "alpha" position are used for producing such azo dye-stuffs.
-
-
==
My foreign correspondents have now found that the azo products hereinbefore
defined are converted into valuable azine dye-stuffs when heated with mineral
acids. The formation of these azine coloring matters takes place in the following
manner: The azo group NN is broken up, and the radicle NR is
separated in the form of an amine, viz., NH,R", whilst the other nitrogen atom
of the original azo group combines with the alkyl radicle R¹, which is in the
adjacent alkylamido group NHR', alpha alkyl eurhodines, or homologues thereof,
or sulphonic derivatives of alkyl curhodines, being thus produced.
-
For instance, the azo products derived from diphenylalpha beta, naphthalene
diamine alpha, monosulphonic acid are converted into sulphonic derivatives of
alphaphenyleurhodine, which process can be represented by the following
equation
-
It is, however, to be noted, that under the conditions hereinafter defined, that is
to say, on using sulphuric acid in effecting the formation of the azine, a sulphonation
25 can take place at the same time."
The process illustrated by the above given equation is similar to that which
gives rise to the production of the naphthaphenazine of the formula :—
It is known that naphthaphenazine, and analogues thereof, are formed by heating
30 with acids azo products derived from phenylbetanaphthylamine, tolyl beta naphthyl-
amine, betanaphthyl betanaphthylamine, or the like (see Witt, Berichte der
Deutschen Chemischen Gesellschaft, volume 20, pages 573 and 579; Zincke,
Berichte der Deutschen Chemischen Gesellschaft, volume 23, page 1333).

page_text: According to the researches of my foreign correspondents, dilute and concentrated
mineral acids can be used for producing the azine dye-stuffs herein before defined
from azo products which are prepared by means of "symmetrical" or "mixed"
dialkylalpha, beta, naphthylene diamines, or certain sulphonic acids thereof. The
use of moderately concentrated sulphuric acid has been found to be most
advantageous, as the said azo products are dissolved by such an acid, and in
this case the formation of the azine proceeds very conveniently. If concentrated
sulphuric acid (at 66 degrees Baumé) be used, sulphonation takes place at the same
time, disulphonic acids being, as a rule, produced.
Those of the products obtained by means of the process herein before defineil,
which are insoluble or soluble with difficulty, are profitably converted into more
soluble and more valuable sulphonic acids, by a subsequent treatment with
sulphonating agents.
The following example is given in order to illustrate the process for producing
the said azine dye stuffs, the parts being by weight.
COLORING MATTER OBTAINED FROM BENZENESULPHONIC ACID AZO DITOLYL-
ALPHA BETA, NAPHTHYLENEDIAMINE ALPHA MONOSULPHONIC ACID.
5 parts of the azo product obtained by coupling diparatolylalpha, beta,
naphthylene diamine alpha, monosulphonic acid with diazo benzene sulphonic acid,
are dissolved in 20 parts of sulphuric acid (66 degrees Baumé), and the solution
is heated at from 80 to 90 degrees Centigrade, until the mass has assumed a pure
green color. On pouring the cooled liquid into ice water, a sulphonic acid is
precipitated, which is a derivative of the paratolyl homoeurhodine having the
formula
The acid is filtered off, and subsequently converted, by means of sodium
carbonate, into the sodium salt, which crystallises in scales, and is the finished
dye-stuff. It yields bluish-red shades on unmordanted wool in an acid bath.
The process is carried out in a manner analogous to that described in the
preceding Example A, when using other azo products derived from diparatolyl-
alpha, beta, naphthylene diamine, or azo products obtained by coupling any diazo
compounds with the "symmetrical" or "mixed " dialkyl-alpha,-beta,-naphthylene-
dianines hereinbefore defined, or sulphonic acids thereof, which are not substituted
in the para position relatively to the alkylamido group in the alpha position.
The azine dye-stuffs thus obtained in general produce shades varying from bluish-
red to red. For instance, an azine dye-stuff yielding brownish red shades on wool
is obtained in an analogous manner from benzene azo diphenyl-alpha, beta,-
naphthylenediamine-alpha sulphonic acid. The azine dye-stuff from benzene-
sulphonic acid-azo-diparatolyl-alpha, beta,-naphthylenediamine-beta-sulphonic acid
also yields brownish-red shades on wool.

page_text: In producing these azine dye-stuffs, my foreign correspondents do not limit
themselves to the directions given in the above example, as these can be varie l.
For instance, a more dilute or concentrated sulphuric acid may be used in place of
sulphuric acid (66 degrees Baumé)..
My foreign correspondents have also found that the azine dye stuffs hereinbefore
defined can be transformed into colouring matters which withstand, in a higher
degree, the action of alkalies, if they are treated in a suitable manner with
alkylating agents. My foreign correspondents assume that the hydrogen atom
combined with the so-called azine nitrogen, is displaced by the alkyl group during
this alkylating process.
On using colouring-matters derived from dialkyl-alpha beta, naphthylene-
diaminesulphonic acids in this process, dye stuffs are obtained which materially
differ from the analogous sulphonated dye stuffs hitherto known, as these latter
colouring matters contain sulphonic groups only in the benzene nucleus, whilst the
new dye-stuffs obtained by means of the last defined alkylating process also
contain sulphonic groups in the naphthalene nucleus, these sulphonic groups being
in a definable position, if dialkyl-alpha, beta,-naphthylenediamine sulphonic acids
of known composition are used.
This alkylating process is illustrated by the following example. The parts aro
DYE STUFF PRODUCED
MATTER
BY ALKYLATING
COLOURING
THE
OBTAINABLE AB DESCRIBED IN THE PRECEDING EXAMPLE A.
4.5 parts of the sodium salt of the sulphonated azine dye stuff obtained as
described in the above Example A, are mixed with 0-2 parts of potash and 17 parts
of ethyliodide, and 12 parts of alcohol, and the mixture is heated during about
3 hours at 120 Centigrade. After cooling, the mass is poured into water, and the
dye stuff thus formed is salted out, filtered off, pressed, and dried. This colouring
matter produces on wool, in acidulated baths, clear bluish red shades which
withstand alkalies, acids, and light.
The last Example B is typical of the method of alkylating the other azine dye
stuffs hereinbefore defined.
The process for alkylating alpha-methylhomoeurhodine, phenyleurhodine,
phenylhomoeurhodine & sulphophenyleurhodine, which process is described and
claimed in the Specifications of Letters Patent No. 10138A, 10138B, and 10138c
of 1892, is hereby disclaimed.
My foreign correspondents have described in the foregoing two examples, several
distinct methods of practically producing the dyestuffs hereinbefore defined.
Naturally, they do not limit themselves to the directions above given, as these
can be varied, and all methods can be used which are known and in use for
analogous purposes. Such modifications do not alter the nature of this invention
which generally relates to the production of valuable azine dyestuffs and alkylated
azine colouring matters from azo products obtained by coupling diazo compounds
with the "symmetrical" or "mixed" dialkylnaphthylene diamines hereinbefore
defined, or certain sulphonic acids thereof.
Having now particularly described and ascertained the nature of the said
invention 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 azine dyestuffs from the azo products obtainable by coupling
diazotised aromatic amines, or substituted amiues, either with the "symmetrical
or "mixed" dialkyl-alpha, beta,-naphthylenediamines described in the Specifications
of Letters Patent No. 88983, 16780%, and 19623, or with sulphonic acids of
these symmetrical" or "mixed" dialkyl-alpha,-beta, naphthylenediamines, which
are not substituted in the para position relatively to the alkyl amido group in

page_text: alpha-position, which process consists in heating with mineral acids, such as
sulphuric acid, the said azo products, until the formation of the azine has been
effected, sulphonating the so formed products, if desirable, and finally converting
the azine sulphonic acids thus formed into alkaline salts.
2. The conversion of the azine dye-stuffs obtainable as described in the preceding
first claim, into new colouring matters capable of withstanding the action of
alkalies in a higher degree than the original products, which process consists in
treating the said azine dyestuffs with alkylating agents. (The process for
alkylating alphamethylhomoeurhodine, phenyleurhodine, phenylhomoeurhodine
and sulphophenyleurhodine, which process is described and claimed in the
Specifications of Letters Patent No. 10138a, 10138в, and 10138c, of 1892, is hereby
disclaimed.)
3. As new products of manufacture, the new azine dye stuffs and alkylated
azine colouring matters produced by the processes hereinbefore defined, or by any
other process affording the same result.
Dated this 18th day of March 1895
NEWTON & SON,
Agents for the Applicant.