The Manufacture or Production of Basic Azine Dye-stuffs, and of New Derivatives thereof.
Year: 1895

page_text: Date of Application, 9th Mar., 1895
Complete Specification Left, 9th Dec., 1895-Accepted, 11th Jan., 1896
PROVISIONAL SPECIFICATION,
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & CO., of Elberfeld, Germany.]
The Manufacture or Production of Basic Azine Dye-stuffs, and of
New Derivatives thereof.
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 Letters Patent
No. 16815, dated 20th September 1892, a process for producing basic colouring
matters, which process consists in condensing monoalkylmetatoluylene diamines
-(NH, CH: NHR = 1:2:5)-such as monomethylmetatoluylene diamine,
monoethylmetatoluylene diamine, with amido azo compounds. The resulting dye-
stuffs, containing alkyl groups in combination with the one nitrogen atom of the
azine nucleus, are of technical value, as they yield shades distinguished by reason
of their purity and their fastness against the action of alkalies.
My foreign correspondents have now found that the same colouring matters, and
the analogues thereof, for instance, those derived from mono benzyl-meta-toluylene
diamine, can also be obtained by means of the other methods known and in use for
producing similar azine dye-stuffs.
According to the researches of my foreign correspondents, the following methods
can be employed with the same result.
A. In place of the aforesaid paramido azo compounds, the corresponding para
nitroso derivatives of primary, secondary, or tertiary aromatic amines, can be
condensed with the mono alkyl-meta-toluylene diamines (such as monomethyl-,
monoethyl-, monobenzyl-meta toluylene diamine or the like); or
B. The paradiamines obtainable by reducing the aforesaid amido azo compounds,
or paranitroso derivatives, can be subjected to a joint oxidation, together with the
mono alkyl-meta-toluylene diamines hereiubefore defined; or
C. The azo products resulting from the combination of the mono alkyl meta
toluylene-diamines above referred to, with the diazo derivatives of aromatic
amido compounds, may be condensed with primary, secondary, or tertiary aromatic
amines; or
D. The alkyltriamido toluenes obtainable, for instance, by reducing the last
named azo products, may be subjected to a joint oxidation, together with primary,
secondary, or tertiary amines of the benzene or naphthalene series.
The colouring-matters obtained by means of the processes hereinbefore defined,
distinctly differ, by their purity and their fastness against the action of alkalies,
from the dye-stuffs allied to neutral-red, and produced from the action of nitroso
derivatives on meta toluylene diamine itself. They are similar to the so-called
safranine colouring-matters.
In the production of the dye stuffs herein before defined, the following nitroso
derivatives may, for instance, be used, viz., nitroso dimethylaniline, nitroso diethyl-
aniline, nitrosomono methylaniline, nitrosomonomethyl-ortho toluidine, nitroso-
monoethyl ortho-toluidine, nitroso diphenylamine, nitroso methyldiphenylamine, or
the like.
The following examples are given, in order to illustrate the production of the

page_text: DYE STUFF OBTAINED FROM NITROSO DIMETHYLANILINE HYDROCHLORIDE
AND MONO-BENZYL-META-TOLUYLENE DIAMINE (OR ORTHO-AMIDO-MONO-
BENZYL-PARA-TOLUIDINE).
27 parts of nitroso dimethyl aniline hydrochloride and 21 parts of ortho-amido
monobenzyl-para-toluidine are dissolved in 100 parts of glacial acetic acid. The
resulting solution is heated, during some hours, by means of a water bath. The
red coloured liquid is then poured into a large quantity of hot water, and rendered
slightly alkaline by means of ammonia. The liquid is then filtered, and the
resulting filtrate is acidulated by means of hydrochloric acid. The finished dye-
stuff is precipitated by adding zinc chloride and common salt. It is then filtered
off, pressed, and dried.
The dye-stuff thus obtained produces reddish-violet shades on cotton prepared
with tannic acid or the like, and is identical with that resulting from dimethyl-
amido azo benzene and ortho-amido mono-benzyl-para-toluidine. It possesses the
following formula :-
COLOURING-MATTER OBTAINED
TOLUIDINE
FROM
HYDROCHLORIDE
NITROSO MONOMETHYL-ORTHO-
AND MONOETHYLMETA TOLUYLENE
DIAMINE (OR ORTHO AMIDO MONOETHYL PARA-TOLUIDINE).
A mixture prepared from 27 parts of nitroso mono methyl ortho toluidine hydro
chloride, 15 parts of monoethyl-meta-toluylene diamine (ortho-amido-mono-ethyl-
para-toluidine), and from 100 to 200 parts of alcohol, is heated, by means of a
water bath, until a clear red coloured solution results. The liquid thus formed is
poured into water, and is rendered slightly alkaline by means of ammonia. The
liquid is then filtered, and the resulting filtrate is acidulated by means of hydro-
chloric acid. The dye-stuff is precipitated by adding zinc chloride and common
salt. It is filtered off, pressed, and dried.
It produces yellowish-red shades on cotton prepared with tannic acid or the
like, and is identical with the colouring matter obtained from ortho amido-mono-
ethylparatoluidine, and the azo products of mono-methyl-ortho-toluidine.
It possesses probably the following formula :-

page_text: Other colouring matters result in an analogous manner, if other nitroso
compounds are used in place of the nitroso dimethylaniline and the nitroso
monomethyl ortho toluidine used in the foregoing examples, or if other mono
alkyl meta toluylene diamines are substituted for the mono benzyl meta toluylene
diamine and mono-ethyl-meta-toluylene-diamine used in these examples.
As above mentioned, the dye-stuffs herein before defined can also be obtained by
subjecting the mono alkyl meta toluylene diamines (ortho amido mono alkyl-para-
toluidines) to a joint oxidation, together with the para-diamines obtainable by
reducing the aforesaid para azo or para nitroso products.
This joint oxidation is effected by the methods known and in use for analogous
purposes.
Thus, for instance, the colouring matter obtained as described in the first
example, can also be produced by oxidizing together para amido dimethylaniline
and ortho-amido-mono-benzyl para-toluidine (mono-benzyl-meta-toluylene-diamine),
and the dye-stuff produced as described in the Second Example also results on
subjecting para-amido-mono-methyl-ortho-toluidine to a joint oxidation together
with ortho-amido mono ethyl-para toluidine (mono ethyl-meta-toluylene diamine).
In order to effect the oxidation, potassium dichromate, sodium dichromate, ferric
chloride, or similar oxidising agents may be used.
According to the researches of my foreign correspondents, the same colouring
matters can also be produced, if primary, secondary, or tertiary amines of the
benzene or naphthalene series are heated with the azo products resulting from the
combination of diazo derivatives of aromatic amines with the mono-alkyl-meta-
toluylene-diamines hereinbefore referred to, or if primary, secondary, or tertiary
amines of the benzene or naphthalene series are subjected to a joint oxidation
together with the alkyltri-amido-toluenes which are obtained either by reducing
the last named azo products, or in any other way.
The process for producing the dye-stuffs by means of the two last mentioned
methods is effected in the manner known and in use for producing analogous or
similar colouring matters.
The researches of my foreign correspondents have shewn, that the basic azine dye-
stuffs herein before defined, and derived from mono-alkyl-meta-toluylene diamines
can be readily diazotised, diazo compounds being thus obtained which, by a
subsequent combination with phenols or amines, or the like, yield valuable basic
azo colouring matters.
The last-named basic azine dye-stuffs differ from the real safranine dyes, in that
they contain the methyl, ethyl, benzyl group, or the like, in combination with the
one nitrogen atom of the azine nucleus, whereas the latter, viz., the safranine dyes,
contain the phenyl or tolyl group in combination with the one nitrogen atom of the
azine nucleus.
The basic azo dye-stuffs resulting, as hereinbefore referred to, from the com-
bination of phenols, amines, or the like, with the diazo derivatives of the basic
azine dye-stuffs herein before defined, possess a strong basic nature, and are superior,
by their greater solubility in water, to the colouring matters obtained by coupling
phenols or the like with the diazotised safranine dyes.
According to the researches of my foreign correspondents, those of the new
basic azo dyes possess the greatest value which are obtained by means of beta
naphthol.
The process for producing the new basic azo colouring matters is illustrated by
the following example. The parts are by weight.

page_text: and mono-ethyl-meta-toluylene diamine are dissolved in about 400 parts of water.
After adding about 3 parts of muriatic acid, a solution in water of 1-4 parts of
sodium nitrite is introduced during cooling. The original red colour of the
solution gradually turns into a pure greenish-blue. The so-formed diazo solution
is then allowed to flow slowly into a solution prepared from 3.3 parts of the sodium
salt of beta naphthol, and rendered alkaline by means of an excess of sodium
carbonate. The separated azo dye-stuff is filtered off, pressed, and crystallised
from alcohol. The resulting colouring matter dissolves even in cold water, and
very readily in hot water. It produces blue shades on cotton prepared with
tannic acid or the like, and probably possesses the following formula :-
The other colouring matters are obiained in an analogous manner, if, on the one
hand, analogous dye-stuffs derived from monoalkyl-meta-toluylenediamines are
substituted for that used in the preceding Third Example, or if, on the other hand,
the beta naphthol used therein is replaced by the corresponding quantities of
alpha naphthol or other phenols, or by amines of the benzene or naphthalene
series.
The resulting dye-stuffs are distinguished by reason of their great solubility in
water, and by their property of producing pure and very fast shades.
In the production of the dye-stuffs herein before defined, my foreign corre-
spondents do not limit themselves to the directions given in the preceding examples,
as these can be varied, and in general all methods known and in use for obtaining
analogous colouring matters can be employed.
Dated this 9th day of March 1895.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Basic Azine Dye-stuffs, and of
New Derivatives thereof.
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 Letters Patent
No. 16815, dated 20th September 1892, a process for producing basic colouring
matters, which process consists in condensing with amidoazo compounds, mon-
.alkylmetatoluylenediamines (NH, CH, NHR 1:25), such as monomethyl-
inetatoluylene diamine and monethylmetatoluylene diamine. The dye-stuffs
:
=

page_text: containing alkyl groups in combination with the one nitrogen atom of the azine
nucleus, which are thus formed, are of technical value, as they yield shades
distinguished for their purity and fastness in presence of alkalies.
My foreign correspondents have now found, that the same colouring matters,
and the analogues thereof, for instance, those derived from monobenzyl-meta-
toluylene diamine, can also be obtained by means of the other known methods in
use for producing similar azine dye-stuffs.
According to the researches of my foreign correspondents, the following methods
can be adopted with the same result.
A. In place of the aforesaid paramido azo compounds, the corresponding para
nitroso derivatives of primary, secondary, or tertiary aromatic amines, can be
condensed with the monalkyl-meta-toluylenediamines (such as monomethyl,
monethyl-, monobenzyl-meta-toluylene-diamine, or the like); or
B. The paradiamines, obtainable by reducing the aforesaid amidoazo compounds,.
or paranitrozo derivatives, can be subjected to oxidation conjointly with the
monalkyl-meta-toluylenediamines hereinbefore defined; or
C. The azo products formed by combining the monalkyl-meta-toluylenediamines.
above referred to, with the diazo derivatives of aromatic amido compounds, may be
condensed with primary, secondary, or tertiary aromatic amines; or
D. The alkyltriamido toluenes obtainable, for instance, by reducing the last-
named azo products, may be subjected to oxidation conjointly with primary,.
secondary, or tertiary amines of the benzene or naphthalene series.
The basic azine colouring-matters obtained by the processes herein before defined,.
distinctly differ in purity of shade and fastness, in presence of alkalies, from the
dye-stuffs allied to neutral-red, and produced by the action of nitroso derivatives
on metatoluylene diamine itself. They are similar to the so-called safranine
colouring matters, from which they differ by containing the methyl, ethyl, benzyl
group, or the like, in combination with the one nitrogen atom of the azine nucleus,
whereas the safranine dye-stuffs contain the phenyl or tolyl group, or the like, in
combination with the one nitrogen of the azine nucleus.
In the production of the dye-stuffs herein before defined, the following nitroso
derivatives may, for instance, be used, viz., nitroso dimethylaniline, nitroso
diethylaniline, nitroso monomethylaniline, nitroso monomethyl-ortho-toluidine,
nitrosomonethyl-ortho-toluidine, nitrosodiphenylamine, nitrosomethyldiphenylamine,
or the like,
The following examples are given, in order to illustrate the production of the
basic azine dyestuffs from nitroso compounds and monalkyl-meta toluylene-
diamines. The parts are by weight.
DYE-STUFF OBTAINED FROM NITROSODIMETHYLANILINE HYDROCHLORIDE AND
DIAMINE (OR ORTHO AMIDO MONO
MONOBENZYL META
TOLUYLENE
BENZYL-PARA-TOLUIDINE).
26 parts of nitroso dimethylaniline hydrochloride, and 21 parts of ortho-amido-
monobenzyl-para toluidine, are dissolved in 100 parts of glacial acetic acid. The
solution is heated during several hours by means of a water-bath. The red
coloured liquid is then poured into a large quantity of hot water, and rendered
slightly alkaline with ammonia. The liquid is then filtered, and the filtrate is
acidulated with hydrochloric acid. The finished dye-stuff is precipitated by adding
zinc chloride and common salt. It is then filtered off, pressed, and dried.
The dye-stuff thus obtained produces bluish-red shades on cotton prepared with
tannic acid or the like, and is identical with that formed from dimethylamido azo-

page_text: benzene and orthamidomonobenzyl para-toluidine. It is probably represented by
the following formula :-
:―
The analogous dye-stuff from nitrosomonomethyl-ortho-toluidine hydrochloride
and monobenzyl-meta toluylene diamine, produces red shades on cotton prepared 5
with tannic acid or the like.
COLOURING-MATTER OBTAINED FROM NITROSO MONO METHYL-ORTHO TOLUIDINE
HYDROCHLORIDE AND MONETHYL META TOLUYLENE (OR ORTHAMIDO
MONETHYL-PARA-TOLUIDINE).
A mixture prepared from 28 parts of nitroso-mono-methyl-orthotoluidine hydro-
chloride, 15 parts of monethyl-meta-toluylene diamine (orthamido-monethyl-para-
toluidine), and from 100 to 200 parts of alcohol, is heated by means of a water
bath, until a clear red coloured solution results. The liquid thus formed is poured
into water, and is rendered slightly alkaline by means of ammonia. The liquid is
then filtered, and the filtrate is acidulated with hydrochloric acid. The dye-stuff
is precipitated by adding common salt. It is filtered off, pressed, and dried.
It produces yellowish-red shades on cotton prepared with tannic acid or the like,
and is identical with the colouring matter obtained from orthamido-monethyl para-
toluidine, and the azo products of monomethylortho-toluidine.
It is probaby represented by the following formula :-

page_text: toluidines) to oxidation conjointly with the paradiamines obtainable by reducing
the aforesaid parazo or para-nitroso products.
This conjoint oxidation is effected by the known methods in use for analogous
purposes.
Thus, for instance, the colouring-inatter obtained as described in the Example A,
can also be produced by oxidising a mixture of paramidodimethylaniline and
orthamidomonobenzyl-para-toluidine (monobenzyl-meta-toluylene diamine), and the
dye-stuff produced as described in the Example B is also formed on subjecting
paramido-mono-methyl-ortho-toluidine to oxidation conjointly with orthamidomon-
ethyl-para-toluidine (monethyl-meta-toluylene diamine). In order to effect the
oxidation, potassium dichromate, sodium dichromate, ferric chloride, or similar
oxidising agents, may be used.
According to the researches of my foreign correspondents, the same colouring
matters are also produced, if primary, secondary, or tertiary amines of the benzene or
naphthalene series are heated the azo products formed by combining diazo
derivatives of aromatic amines with the monalkyl-meta-toluylene diamines herein-
before referred to; or if primary, secondary, or tertiary amines of the benzene or
naphthalene series are subjected to oxidation conjointly with the alkyl triamido-
toluenes which are obtained either by reducing the last-named azo products, or in
any other way.
The process for producing the dye-stuffs by means of the two last mentioned
methods is effected in the known manner in use for producing analogous or similar
colouring matters.
The researches of my foreign correspondents have shown, that the basic azine
dye-stuffs herein before defined, and derived from monalkyl meta toluylenediamines
can be readily diazotised, diazo compounds being thus obtained which are capable
of combining with phenols or amines, or the like, to form basic azo colouring
matters.
Of the basic azo dye stuffs produced, as herein before stated, from the diazo
derivatives of the basic azine dye-stuffs hereinbefore defined, those obtained by
means of phenols, or phenolic bodies, such as naphthol, are superior, on account of
their greater solubility in water, to the colouring matters obtained by coupling
phenols or the like with the diazotised safranine dyes.
According to the researches of my foreign correspondents, the most valuable of
the new basic azo dyes are obtained by means of beta naphthol.
The process for producing the new basic azo colouring matters is illustrated by
the following example. The parts are by weight.
COLOURING-MATTER OBTAINED
DERIVATIVE
FROM
OF THE DYE-STUFF
NAPHTHOL AND
BETA
NITROSO
FROM
THE DIAZO
DIMETHYLANILINE
HYDROCHLORIDE, AND MONETHYL-META-TOLUYLENEDIAMINE.
6.3 parts of the colouring-matter from nitroso dimethylaniline bydrochloride,
and monethyl meta-toluylene diamine, are dissolved in about 400 parts of water.
After adding about 3 parts of muriatic acid, a solution in water of 14 parts of
sodium nitrite is introduced, the mixture being kept cool. The original red colour
of the solution gradually turns into a pure greenish-blue. The diazo solution is
then allowed to flow slowly into a solution of 3.3 parts of the sodium salt of beta
naphthol, supersaturated with sodium acetate. The azo dye-stuff is precipitated by
adding a small quantity of common salt, and is then filtered off, pressed, dried, and
purified by re-crystallization from water containing acetic acid. The colouring-
matter thus formed dissolves even in cold water, and very readily in hot water.

page_text: It produces blue shades on cotton prepared with taunic acid or the like, and is
probably represented by the following formula :-
The other colouring-matters are obtained in an analogous manner, if, on the one
hand, analogous basic azine dye-stuffs derived from monalkyl-meta-toluylene
diamines are substituted for that used in the preceding Example C, or if, on the
other hand, instead of the beta naphthol used therein, the corresponding quantities
of other phenolic bodies are taken.
Instead of effecting the combination of the diazo derivatives of the basic azine
dye-stuffs herein before defined, in solutions containing sodium acetate, as described
in the foregoing Example C, the dye-stuffs can also be produced by effecting this
combination in solutions containing sodium carbonate, soda-lye, or the like. This
process is illustrated by the following example..
THE
DYE-STUFF FROM BETA NAPHTHOL AND THE DIAZO DERIVATIVE OF
COLOURING MATTER OBTAINED FROM NITROSO MONOMETHYLORTHO-
TOLUIDINE HYDROCHLORIDE, AND MONETHYLMETATOLUYLENE DIAMINE.
3.1 parts of the azine dye-stuff produced, as described in the preceding
Example B, from nitrosomonomethyl-orthotoluidine hydrochloride, and monethyl-
metatoluylene diamine, are dissolved in hot water. When cold, this solution is
slowly stirred into a solution of 0.7 parts of sodium nitrite, and from 3 to 4 parts of
muriatic acid, in a large quantity of ice-cold water, care being taken that the
temperature does not rise above 5 degrees Centigrade. As soon as the liquid has
assumed a clear blue colour, a solution of 1.5 parts of beta naphthol in the calculated
quantity of soda-lye, is added, and then diluted soda lye or sodium carbonate is
stirred into the liquid, until, on salting out and filtering a test portion, a neutral
filtrate is obtained. At this stage, the finished dye-stuff is salted out, filtered off,
pressed, and dried. If desired, it can be purified by crystallization. This dye
produces blue shades on cotton prepared with tannic acid or the like.

page_text: In the following table are indicated several other basic azo dye-stuffs of the series
hereinbefore defined, and the shades produced thereby, on cotton mordanted with
tannic acid or the like.-
Such dye-stuffs are distinguished for their great solubility in water, and by their
roperty of producing pure and very fast shades.
In the production of the dye-stuffs hereinbefore defined, my foreign correspondents
o not limit themselves to the directions given in the preceding examples, as these
an be varied, and, speaking generally, all known methods in use for obtaining
nalogous colouring matters can be adopted.
Having now particularly described and ascertained the nature of the said
vention and in what manner the same is to be performed (as communicated to me
om abroad), I declare that what I claim is :—
1. The production of basic azine dye-stuffs, which process consists
a) in condensing monalkyl metatoluylene diamines (such as monomethylmeta-
toluylene diamine, monethyl metatoluylene diamine, monobenzylmeta-
toluylene diamine), with nitroso derivatives of secondary or tertiary
aromatic amines, or substituted amines; or
b) in subjecting monalkylmetatoluylene diamines (such as monomethylmeta-
toluylenediamine, monethylmetatoluylene diamine, monobenzylmetato-
luylenediamine) to oxidation conjointly with paradiamido compounds obtained
by reducing the aforesaid nitroso-derivatives, or in any other manner; or
c) in condensing primary, secondary, or tertiary aromatic amido compounds,
with the azo products formed by the combination of the aforesaid monalkyl-
metatoluylene diamine with the diazo derivatives of aromatic amines, or
substituted amines; or

page_text: d) in subjecting primary, secondary, or tertiary aromatic amido compounds to
oxidation conjointly with the alkyltriamido toluenes derived from the
aforesaid monalkylmetatoluylene diamines, and obtainable, for instance, by
reducing the azo compounds defined under c.
2. The process for producing basic azo dye-stuffs, which process consists in 5
diazotising the basic azine dye-stuffs defined by the foregoing claim one, and in
subsequently combining, in moderately acidulated, or in alkaline solution, the so
formed diazo derivatives with phenolic bodies, such as beta naphthol.
3. As new products of manufacture,
a) the basic azine dye-stuffs derived from mono-
benzylmeta toluylene diamine, and
b) the basic azo dye-stuffs derived from mono-
methylmetatoluylene diamine, monethylmeta-
toluylene diamine, or monobenzylmetatoluylene
diamine
produced by the processes
hereinbefore defined, or
in any other manner
affording the same result.
Dated this 7th day of December 1895.
NEWTON & SON,
Agents for the Applicant.