The Manufacture or Production of Colouring-matters.
Year: 1895

page_text: 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:-
My foreign correspondents discovered some time ago that the monalkylmeta-
toluylenediamines which result from the interaction of metatoluylenediamine
(paramidoorthotoluidine) and primary aromatic amines, could be used for producing:
azine dyestuffs. As typical representatives of the said monoalkylmetatoluylene-
diamines, phenylmetatoluylenediamine and paratolylmetatoluylenediamine may be
mentioned, which are obtained from metatoluylenediamine, and either aniline or
paratoluidine, and which have the following formulæ respectively :

page_text: COLOURING-MATTER OBTAINED FROM ALPHANAPHTHYLAMINE AND THE AZO
COMPOUND RESULTING FROM THE COMBINATION OF PHENYLMETA-
TOLUYLENEDIAMINE WITH DIAZOTISED PARASULPHANILIC ACID.
After
5-7 parts of the azo compound resulting from the combination of phenylmeta-
toluylene diamine (phenylparamido ortho toluidine) with diazotised parasulphanilic
acid, are finely powdered, and mixed with 1.4 parts of alphanaphthylamine.
adding 20 parts of phenol, the resulting mixture is stirred, and kept at from 90 to
110 degrees Centigrade, until the original brown colour of the heated mass has
cbanged into a pure red, and the unaltered azo compound is no longer distinguish-
able in test portions taken out. An excess of hot dilute soda-lye is added to the
resulting mass, and after cooling, the separated dyestuff is filtered off and pressed.
To purify the dyestuff, the mass filtered off is dissolved in hot water containing
muriatic acid, and the filtered hot solution is mixed with muriatic acid. On
cooling, the dye-stuff crystallises out. It is isolated in the usual manner, viz., by
filtering off, pressing & drying.
The colouring-matter thus obtained readily dissolves in water, and produces
bright bluish-red shades on cotton prepared with tannic acid or the like. It is
identical with the dye-stuff resulting by the interaction of benzeneazo´ alpha-
nanhthviamino and thonylnaramidaart hatoluiding
DIE STUFF FROM THENILIKI
TIDOTOLUENE
AND
2-2 parts of phenyltriamidotoluene (melting at 134 degrees Centigrade, and
produced, for instance, by reducing the azo compound from phenylinetatoluylene-
diamine, or phenylparamido-orthotoluidine, and diazotised parasulphanilic acid) are
mixed with 18 parts of alphanaphthylamine-hydrochloride and 20 parts of phenol.
The resulting mixture is stirred, and then heated by means of a water bath
(profitably using open vessels, that the air may be thoroughly in contact with the
heated mass), until the colour of the mixture has turned to a pure red, and the
intensity of the colour no longer increases. The thus formed dye-stuff is isolated
in the manner described in the first example. It is also identical with that
obtained by the process illustrated in the said example.
COLOURING-MATTER OBTAINED FROM ALPHANAPHTHYLAMINE AND PHENYL-
TRIAMIDOTOLUENE.
A solution prepared by dissolving 3 parts of sodium dichromate in 5 parts of
water is gradually added to a solution obtained on dissolving 2.2 parts of the
bereinbefore mentioned phenyltriamidotoluene melting at 134 degrees Centigrade,
and 14 parts of alpha aphthylamine, in 20 parts of dilute acetic acid (containing
50 per cent. of pure acetic acid), care being taken that the latter solution is kept
cool, and well agitated, during the addition of the sodium dichromate solution.
The resulting liquid is then heated by means of a water bath, until the intensity of
the colour no longer increases. After adding an excess of muriatic acid, the crude
dyestuff is salted out and filtered off. In order to purify the dyestuff, the product
thus obtained is dissolved in a small quantity of hot water, and the filtered solution

page_text: is then mixed with muriatic acid. On cooling, the dyestuff crystallises out.
isolated by filtering off, pressing, and drying.
It is
The colouring matter thus obtained is identical with those resulting from the
processes described in Examples One and Two.
The process proceeds in a similar manuer, if, on the one hand, the azo compound
used in the preceding First Example, and produced from diazotised parasulphanilic
acid and phenylparamidoorthotoluidine, is replaced by equivalent quantities of
other azo products resulting from the combination of diazo compounds with the
monalkylmetatoluylene, diamines herein before defined, or if, on the other hand, a
corresponding quantity of another primary or secondary or tertiary aromatic amine
of the benzene or naphthalene series is employed in place of alphanaphthylamine
used in the above First Example. Other analogous paradiamines, resulting from
the reduction of the azo compounds from diazo derivatives and the monalkylmeta-
toluylenediamines above referred to, or produced in any other manner, can be used
in place of phenyltriamidotoluene used in the preceding Examples Two and Three,
and, on the other hand, the alphanaphthylamine used in these two examples can be
replaced by equivalent quantities of other primary, secondary, or tertiary amines
of the benzene or naphthalene series.
In the production of the azine dye-stuffs herein before defined, my foreign
correspondents do not limit themselves to the particulars given in the preceding
three examples, as the mode of working can be varied, and, in general, all
methods can be employed which are known and in use for analogous or similar
purposes.
For instance, the oxidation which, according to the Examples Two and Three,
is effected by means of the atmospheric oxygen, or sodium dichromate, can also be
carried out in other ways, for example, by means of potassiumdichromate, chloride
of lime, lead dioxide, manganese dioxide, or the like. Other solvents or diluents,
such as alcohol, glacial acetic acid, glycerinol, or the like, can be used in place of
the solvents or diluents (viz.: phenol or dilute acetic acid) used in the foregoing
three examples.
Such or similar modifications do not alter the nature of the present invention,
which in general relates to the production of azine dye-stuffs, either by acting
with primary, secondary, or tertiary amines of the benzene or naphthalene series
on the azo products resulting from the combination of diazo compounds with the
monalkylmetatoluylenediamines herein before defined, or by subjecting to a joint
oxidation, primary, secondary, or tertiary amines of the benzene or naphthalene
series, together with the paradiamines obtained either by reducing the last-named
azo products, or in another manner.
Dated thin 10th day of January 1895
NEWTON & SON,
Agents for the Applicant.
CUMI LEID DIBUITIVATIO
The Manufacture or Production of Colouring-matters.
1 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 stated in the Specification of Letters Patent
No. 9610, dated 16th. May 1894, that the monalkylmeta toluylenediamines formed
by the interaction of metatoluylenediamine (paramido-ortho-toluidine) and primary
aromatic amines, can be used to produce azine dye stuffs.

page_text: As typical representatives of the said monalkylmeta toluylene diamines may
be mentioned, the monophenyl-meta-toluylene diamine and mono-paratolyl-meta-
toluylene diamine obtained from meta toluylenediamine, and either aniline or para
toluidine, and represented by the following formulæ respectively:--
The process for producing the above mentioned azine dye-stuffs, in general,
consists in allowing nitroso derivatives of secondary or tertiary aromatic amines, or
amido sulphonic acids, or such products as act in an analogous manner (viz., para-
quinone-imides, paraquinone-chlorimides, or the like compounds of the benzene or
naphthalene series, or paramido azo compounds formed by combination of diazo
derivatives with primary, secondary, or tertiary aromatic amines, or substituted
amines, of the benzene or naphtalene series), to act on the said monalkylmeta
toluylene diamines, or in subjecting the monalkylmeta toluylene diamines herein-
before, defined together with para diamines, or with alkylated para dianines, or
para diamine sulphonic acids containing, in one of their amido groups, either a
single or two alkyl groups, to a joint oxidation in the presence of suitable solvents
or diluents.
My foreign correspondents have now found that the same or analogous colouring
matters can be obtained, if either primary, secondary, or tertiary amines of the
benzene or naphthalene series, are heated with the azo compounds formed by
combining diazo derivatives of aromatic amido compounds with the monalkyl-
metatoluylene diamines hereinbefore defined, or if primary, secondary, or tertiary
amines of the benzene or naphthalene series, are subjected to a joint oxidation,
together with the paradiamido compounds (such as phenyltriamidotoluene para
tolyltriamidotoluene, or the like), formed by the reduction of the last mentioned
azo derivatives, or produced in any other suitable manner.
The above mentioned azo compounds, obtainable by coupling diazo derivatives
of aromatic amido compounds with the said monalkylmetatoluylene-diamines, are
represented by the general formula :-
in which R signifies phenyl, para-tolyl, or some similar aromatic alkyl group, the
radicles of diazotised aromatic amido compounds being represented by R¹.

page_text: The paradiamido compounds obtainable, as hereinbefore mentioned, by reduction
of the aforesaid azo derivatives, are represented by the general formula
COLOURING-MATTER OBTAINED FROM ALPHANAPHTHYLAMINE AND THE AZO
... COMPOUND FORMED BY COMBINING PHENYLMETA TOLUYLENE DIAMINE
WITH DIAZOTISED PARA SULPHANILIC ACID.
5-7 parts of the azo compound formed by combining phenyl meta toluylene
diamine (phenyl paramido ortho toluidine) with diazotised para sulphanilic acid,
are finely powdered, and mixed with 14 parts of alpha naphthylamine. After
adding 20 parts of phenol, the mixture is stirred and kept at from 90 to 110 degrees
Centigrade, until the original brown colour of the heated inass has changed into a
pure red, and unaltered azo compound is no longer distinguishable. An excess of
hot dilute soda-lye is then added to the mass, and after cooling, the separated
dye-stuff is filtered off and pressed. To purify the dye-stuff, the press cake is
dissolved in hot water containing muriatic acid, and the filtered hot solution is
mixed with muriatic acid. The dye-stuff crystallizes on cooling. It is isolated in
the usual manner, viz., by filtering, pressing, and drying.

page_text: The colouring matter thus obtained readily dissolves in water, and produces
bright bluish red shades on cotton prepared with tannic acid or the like. It is
identical with the dye-stuff formed by the interaction of benzene azo alpha
naphthylamine and phenyl paramido ortho toluidine, according to the process
described in the Specification of the aforesaid Letters Patent No. 9610 of 1894.
DYE-STUFF FROM PHENYLTRIAMIDO
NAPHTHYLAMINE.
TULUMA
2-2 parts of phenyltriamido toluene (melting at 134 degrees Centigrade, and
produced, for instance, by reducing the azo compound from phenylmeta toluylene-
diamine, or phenyl paramido ortho toluidine, and diazotised para sulphanilic acid),
are mixed with 1-8 parts of alpha naphthylamine hydrochloride, and 20 parts of
phenol. The mixture is stirred, and then heated by means of a water bath
(advantageously in open vessels, so that the air may have access to the heated
mass), until the colour of the mixture has turned to a pure red, and the intensity
of the colour no longer increases. The thus formed dye-stuff is isolated in the
manner described in the Example A. It is identical with that obtained by the
process illustrated in the said example.
.COLOURING-MATTER OBTAINED FROM ALPHA NAPHTHYLAMINE
PHENYL TRIAMIDO TOLUENE.
AND
A solution prepared by dissolving 3 parts of sodium dichromate in 5 parts of
water is gradually added to a solution of 2-2 parts of the herein before mentioned
phenyltriamido toluene, and 14 parts of alphanaphthylamine in 20 parts of dilute
acetic acid (containing 50 per cent. of pure acetic acid), care being taken that the
latter solution is kept cool and well agitated during the addition of the sodium
dichromate solution. The liquid is then heated by means of a water bath, until
the intensity of the colour no longer increases. After adding an excess of muriatic
acid, the crude dyestuff is salted out and filtered off. In order to purify the dye-
stuff, the product thus obtained is dissolved in a small quantity of hot water, and
the filtered solution is then mixed with muriatic acid. On cooling, the dye stuff
crystallizes out. It is isolated by filtering off, pressing, and drying.
The colouring matter thus obtained is identical with that formed by the processes
described in Examples A and B.
The process proceeds in a similar manner, if, on the one hand, instead of the
azo compound used in the preceding Example A, and produced from diazotised
parasulphanilic acid and phenylparamido or orthotoluidine, equivalent quantities
are taken of other azo products formed by the combination of diazo compounds
with the monalkylmetatoluylene diamines hereinbefore defined, or if, on the other
hand, a corresponding quantity of another primary or secondary, or tertiary, aromatic
amine of the benzene or naphthalene series, is used in place of alpha naphthylamiue
specified in the above Example A. Other analogous alkyltriamidotoluenes, formed
by the reduction of the azo compounds from diazo derivatives and the monalkyl-
metatoluylene diamines above referred to, or produced in any other manner, can be
used in place of phenyltriamidotoluene used in the preceding Examples B and C,
and, on the other hand, instead of the alphanaphthylamine specified in these two
examples, equivalent quantities of other primary, secondary, or tertiary amines of
the benzene or naphthalene series can be used.
In producing the azine dye-stuffs bereinbefore defined, my foreign corre-
spondents do not limit themselves to the particulars given in the preceding three

page_text: examples, as the mode of working can be varied, and all known methɔds can be
used which are in use for analogous or similar purposes.
For instance, the oxidation, which, in the case of the Examples B and C, is
effected by atmospheric oxygen, or sodium dichromate, can also be carried out in
other ways, for example, by means of potassium dichromate, chloride of lime, lead
dioxide, manganese dioxide, or the like. Other solvents or diluents, such as
alcohol, glacial acetic acid, glycerol, or the like, can be used in place of the
solvents or diluents (viz., phenol or dilute acetic acid) specified in the foregoing
three examples.
Such or similar modifications do not alter the nature of the present invention,
which in general relates to the production of azine dye-stuffs, either by acting
with primary, secondary, or tertiary amines of the benzene or naphthalene series,
on the azo compounds formed by combining diazo compounds with the monalkyl-
metatoluylenediamines hereinbefore defined, or by subjecting to a joint oxidation
primary, secondary, or tertiary amines of the benzene or naphthalene series,
together with the alkyltriamido toluenes obtained either by reducing the last
named azo compounds, or in another manner.
Having now particularly described and ascertained the nature of this 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 process for producing azine dye stuffs, which process consists in acting
with primary, secondary, or tertiary amines of the benzene or naphthalene series,
on the azo compounds formed by combining diazo compounds with monophenyl-
metatoluylene diamine (CH3: NH, NHCH, 1: 2: 4), monoparatolylmeta
toluylene diamine (CH, NH, NHC,H,
:
12:4), or analogous monalkyl-
metatoluylene diamines."
=
2. The production of azine dye-stuffs, by subjecting primary, secondary, or tertiary
aromatic amines of the benzene or naphthalene series, together with phenyltri-
amidotoluene (CH, NH, NHCH: NH,
:
12:45), paratolyitriamido-
toluene (CH, NH, NHC,H,NH, 1:24:5), or analogous compounds, to
a joint oxidation in the presence of suitable solvents or diluents.
Dated this 18th day of October 1895.
NEWTON & SON,
Agents for the Applicant.