The Manufacture or Production of Dye-stuffs, and Materials therefor.
Year: 1895

page_text: Date of Application, 17th May, 1895
Complete Specification Left, 15th Feb., 1896-Accepted, 21st Mar., 1896
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany:]
The Manufacture or Production of Dye-stuffs, and Materials
therefor.
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 since a new process for the
production of so-called " alphylparamidobenzylorthotoluidines," or "alphylbenzyl-
metatoluylendiamines," of the general formula
My foreign correspondents hereinafter describe radicles of hydrocarbons of the
benzene series, such as phenyl, tolyl, or the like, as "alphyls." This nomenclature
is based on a proposition of Bamberger (see Berichte der Deutschen Chemischen
Gesellschaft, vol. 27, page 2583).
My foreign correspondents have produced the said "alphylparamidobenzyl-
orthotoluidines, by treating alphylparamidoorthotoluidines with benzylating agents,
and they have obtained therefrom new azine dye-stuffs.
Further researches of my foreign correspondents have now shewn that by acting
on alphylparamidoorthotoluidines with methylating, ethylating, or the like
alkylating agents, in a suitable manner, alphylalkyl compounds are produced,
which have the general formula-
0 These new bases are likewise of great value, as they can be used for the
production of azine dyestuffs. In order to produce the alphylparamidoalkylortho-
toluidines (or alphylalkylmetatoluylendiamines), for instance, the free bases, viz.,
! Price 8d.1

page_text: alphylparamidoorthotoluidines (or alphylmetatoluylenediamines) are acted on with
alkylhaloids, such as methylchloride, ethylchloride, methylbromide, ethylbromide,
or the like alkylating agents, with or without solvents or diluents, or substances
capable of facilitating the action.
One method of producing these alphylalkyltoluylenediamines, or alphylpar-
amidoalkylorthotoluidines, is illustrated by the following example, the parts being
ht
PRODUCTION OF PHENYLETHYLMETATOLUYLENEDIAMINE.
A solution of 20 parts of phenylparamidoorthotoluidine, and 11 parts of ethyl-
bromide, in 40 parts of alcohol, is heated in a closed vessel capable of withstanding
pressure, at 150 to 170 degrees Centigrade, for about 10 hours. The resulting
mass is mixed with a small quantity of muriatic acid, and is then dissolved in
boiling alcohol. On cooling, the salt of the new base separates in crystalline form.
By the addition of sodium carbonate, the free base is separated as an oil, which
immediately becomes crystalline. It is purified by crystallization from ligroine.
The pure base melts at from 59 to 60 degrees Centigrade. It has the formula-
The homologues or analogues of phenylparamidoethylorthotoluidine are obtained
on replacing the ethylbromide used in the foregoing example, by other alkylhaloids,
or other alkylating agents, such as methyl bromide, methyl chloride, or the like,
or on using equivalent quantities of the homologous tolylparamidoorthotoluidine, or
he like, in place of phenylparamidoorthotoluidine used in the above first example.
The alphylalkylparamidoorthotoluidine thus obtained, possesses properties analogous
to those of the aforesaid phenylparamidoethyl orthotoluidine.
Instead of alcohol used in the example, another suitable solvent or diluent may
be employed. The process may also be carried out without the addition of
solvents or diluents, and the quantities of the substances employed in the foregoing
example may vary within certain limits. Likewise, other alkylating agents may
be used instead of the alkylhaloids, for instance, the alphyltoluylendiamines may
be acted on with alcohols in the presence of mineral acids. Such or the like
modifications do not alter the nature of this part of the invention, which relates,
in general, to the production of alphylalkylmetatoluylenediamines having the above
general formula, by treating alphylparamidoorthotoluidines with alkylating agents,
except benzylating agents.
My foreign correspondents have further found that the alphyl paramido alkyl
orthotoluidines, or alphylalkylmetatoluylenediamines, herein before defined, either
when condensed with nitroso compounds, or azo products, or quinone imides or the
like, or when subjected to a joint oxidation together with paradiamines, yield
valuable azine dye stuffs, and that the same or analogous colouring matters can be
produced, either by heating primary, secondary, or tertiary aromatic amines of the
benzine or naphthalene series, with azo products, such as are obtained by coupling
diazo derivatives of aromatic amines with the alphylalkylmetatoluylenediamines
herein before defined, or by subjecting to a joint oxidation, primary, secondary, or
tertiary amines of the benzene or naphthalene series, together with the alphyl-

page_text: alkyltriamidotoluenes obtained by reducing the last named azo products, or in any
other suitable manner.
The new dyestuffs thus obtained from the alphylmetatoluylenediamines herein-
before referred to, are, chemically, alkylated derivatives of the corresponding
colouring matters- produced by ny foreign correspondents from alphylparamido-
orthotoluidines or alphylmetatoluylenediamines. The former dyes, in general,
are similar to the last named colouring matters, particularly as to their fastness
against the action of light and alkalies, but they are far superior to the last defined
dye-stuffs in brilliancy & beauty of shades produced therewith, resembling in all
their properties the azine dye-stuffs which my foreign correspondents have already
obtained from the corresponding benzylated alphylmetatoluylenediamines.
The processes for producing the colouring matters herein before defined, on the
one hand from alphylalkylmetatoluylenediamines and nitroso compounds or azo
products or quinone imides or the like, & on the other hand by a joint oxidation
of the said alphylalkylmeta toluylenediamines with paradiamines, are illustrated by
the following examples 2, 3, 4, 5, 6, and 7. The parts are by weight.
COLOURING MATTER OBTAINED FROM PHENYLETHYLMETATOLUYLENE
DIAMINE AND NITROSODIMETHYLAMINE HYDROCHLORIDE.
28 parts of nitrosodimethylaniline hydrochloride are gradually stirred into a
solution prepared by dissolving 23 parts of phenylethylmetatoluylenediamine, or
phenylparamidoethylorthotoluidine, in 100 litres (in case the parts are kilos. by
weight) of alcohol. The resulting mixture is gently heated in a vessel provided
with a reflux condenser, until the nitrosodimethylaniline is no longer distinguishable.
On cooling, the dye-stuff thus formed crystallies out. It is purified by filtering off
and washing with alcohol. It produc's on cotton morlanted with tannic acid or
the like, shades which are bluer and clearer than those of the analogous colouring
matter from phenylparamidoorthotoluidine & nitrosodimethylaniline hydrochloride.
The dyestuff is identical with that which my foreign correspondents have
obtained by joint oxydation of paramidodimethylaniline with monoethylortho-
toluidine and aniline in eq timolecular proportions.
DYESTUFF
OBTAINED FROM
PHENYLETHYLMETATOLUYLENEDIAMINE
NITROSOMONOMETHYLORTHOTOLUIDINE HYDROCHLORIDE.
AND
23 parts of phenylethylmetatoluylenediamine or phenylparamidoethylortho-
toluidine, are dissolved in 100 litres (in case the parts are kilos. by weight) of alcohol.
Under continuous stirring, 29 parts of nitrosomonomethylorthotoluidinehydro-
chloride are gradually added, and the so-formed mixture is heated until the nitroso
compound is no longer distinguishable. On cooling, the dyestuff entirely
It
crystallises out. It is purified by filtering off and washing with alcohol.
produces on cotton prepared with tannic acid or the like, extremely beautiful and
brilliant red shades, which are scarcely inferior to those obtainable with the aid of
the dyestuff known in commerce as Rhodamine P.
My foreign correspondents obtained this dyestuff some time ago by joint oxydation
of paramidomonomethylorthotoluidine with monoethylorthotoluidine and aniline
in equimolecular proportions.

page_text: COLOURING
MATTER PRODUCED FROM
PHENYLETHYLMETATOLUYLENE-
DIAMINE AND QUINONEDICHLORDIIMIDE.
1-8 parts of quinondichlordiimide are gradually added to a slightly warm solution,
in alcohol, of 2-3 parts of phenylparamidoethylorthotoluidine. While stirring,
the mixture gently heated until the quinon edichlordiimide is no longer distinguish-
able. The alcohol is then distilled over, & the residue is treated with hot water.
The filtered solution is rendered alkaline by means of soda lye. The precipitated
mass is filtered off and treated with boiling water, until the whole dyestuff contained
therein has dissolved. The resulting filtrates are acidulated with muriatic acid,
and the finished dye-stuff is salted out, filtered off, pressed, and dried.
This colouring matter is identical with that obtained as described in the preceding
fourth example, from phenylethylmeta toluylenediamine and amidoazobenzene.
DYESTUFF OBTAINED FROM
SEVENTH EXAMPLE.
PHENYLETHYLMETATOLUYLENE DIAMINE AND
PARAMIDODIMETHYLANILINE.
2-3 parts of phenylparamidomonoethylorthotoluidine & 1-4 parts of paramido-
dimethylaniline are dissolved in about 20 parts of glacial acetic acid. A solution
prepared by dissolving 3 parts of sodium dichromate in the smallest possible
quantity of hot water, is allowed to flow gradually into the above liquid during
agitation. The mixture is heated, until the colour has turned into pure magenta-
red & the intensity of this colour no longer increases. The dyestuff is salted out,

page_text: filtered off, redissolved in water, and this solution is rendered alkaline by means of
soda-lye. After filtering, the filtrate is acidulated with muriatic acid, and the dye-
stuff is salted out, filtered off, pressed, and dried.
My foreign correspondents have also produced this dye-stuff by joint oxidation
of monethylorthotoluidine with paramidodimethylaniline and aniline in equi-
molecular proportions.
Other coloring matters result in an analogous manner, if other nitroso
compounds, or azo products, are used in place of those employed in the preceding
example, or if other alkylated paradiamines containing, in one of their amido
groups, either a single or two alkyl groups, are substituted for the paramido-
dimethylaniline used in the last-mentioned example, or if the quinone dichlordiimide
used in the sixth example is replaced by other para-quinone imides, or chlorimides,.
or if the phenylethyl metatoluylene diamine, and the phenylmethylmetatoluylene
diamine, are replaced by other alphylparamidoalkylorthotoluidines herein before
defined, such as paratolylparamidoethylorthotoluidine, paratolylparamidomethyl-
orthotoluidine, or the like. The oxidation effected in the seventh example by
means of sodium dichromate can also be carried out by using other oxidising agents
suitable for these purposes.
The coloring matters thus obtained are similar in their properties to those-
obtained as described in Examples 2, 3, 4, 5, 6 and 7.
In the production of all these dye-stuffs, my foreign correspondents do not limit
themselves to the directions given in the above examples, which are merely typical.
All methods known and in use for producing analogous dye-stuffs can be used..
For instance, other solvents, such as glycerinol, or water alone, or the like, can be
used in place of the solvents or diluents employed in the preceding examples.
As above mentioned, the same or analogous coloring matters can also be produced,
if either primary, secondary, or tertiary aromatic amines not substituted in the
"para" position relatively to the amido group or alkylamido group, are subjected
to a joint oxidation together with the alphylalkyltriamidotoluenes obtained from
the alphylalkylmetatoluylenediamines herein before defined, or if primary, secondary,.
or tertiary amines are condensed with the azo products resulting from the
combination of diazo compounds with the alphylalkylmetatoluylenediamines herein--
before referred to.
The said alphylalkyltriamidotoluylenes have the general formula—

page_text: My foreign correspondents mean by the letter R in this formula, the radicles of
amidocompounds the diazo derivatives of which are coupled with the alphylalkyl-
metatolaylenediamines.
The alphylalkyltriamidotoluenes can be produced by nitrating alphylalky]-
metatoluylenediamines, and subsequently reducing the so-formed mononitro
compounds, and they can also be obtained by reducing the azo products possessing
the last given general formula, and resulting from the combination of any diazo
compounds with alphylalkylmetatoluylene diamines.
The process for producing azine dye-stuffs from the last named azo products, or
alphylalkylmeta toluylenetriamines, is illustrated by the following examples, the
parts being by weight :-
COLORING MATTER OBTAINED FROM PHENYLMETHYLTRIAMIDOTOLUENE
AND ALPHANAPHTHYLAMINE.
2-2 parts of phenylmethyltriamidotoluene and 14 parts of alphanaphthylamine
are dissolved in 20 parts of glacial acetic acid. A solution prepared by dissolving
3 parts of sodiumdichromate in the smallest possible quantity of water is allowed
to flow gradually into the above named liquid compound, while stirring. The
inixture is heated by means of a water bath, until the intensity of the color no
longer increases. An excess of muriatic acid is then added, and the dye-stuff is
salted out.
To purify it, it is dissolved in a small quantity of hot water, and the

page_text: filtered solution is mixed with muriatic acid. On cooling, the finished dye-stuff
crystallizes out. It is identical with the coloring matter obtained as described in
the preceding eighth and ninth examples.
Other dye-stuffs result in a manner analogous to that described in the preceding
eighth, ninth, and tenth examples, if the benzene sulphonic acid azophenylene-
methylmetatoluylenediamine, that is to say, the azo product from diazotised
parasulphanilic acid and phenylpȧraamidomethylorthotoluidine, is replaced by
other azo products obtained from diazo compounds and the alphylalkylmetatoluylene-
diamines hereinbefore defined, or if the phenylmethyltriamidotoluene is replaced
by paratolylethyltriamidotoluene, or other alphylalkyltriamidotoluenes, or if other
primary or secondary or tertiary amines of the benzene or naphthalene series are
substituted for the alphanaphthylamine. Instead of effecting the oxidation by
means of sodium dichromate or atmospheric oxygen, other oxidising agents, such
as potassium dichromate, chloride of lime, lead dioxide, manganese dioxide, or the
like, can be used. Other solvents or diluents, such as alcohol, glycerinol, water,
or the like, can be employed in place of the solvents or diluents, viz., phenol and
acetic acid, used in the last three examples. As a matter of course, the production
of the dye-stuffs by means of the processes illustrated by the last three examples
can be varied, and all methods known and in use for producing analogous coloring
matters can be used.
Dated this 16th day of May 1895.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Dye-stuffs, and Materials
therefor.
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 :-
66
My foreign correspondents some time ago discovered a new process for the
production of so-called "alphylparamidobenzylorthotoluidines,” or alphylbenzyl-
metatoluylenediamines" of the general formula:
35 The term "alphyl" is here used in the sense proposed by Bamberger (see
Berichte der Deutschen Chemischen Gesellschaft, vol. 27, page 2583), to indicate
phenyl, tolyl, or the like radicles in contradistinction to the alkyls, viz., methyl,
ethyl, or the like.
The said "alphylparamidobenzylorthotoluidines were produced by benzylating
0 alphylparamidoorthotoluidines, and new azo dye-stuffs were prepared from them...
Further researches of my foreign correspondents have now shewn that, on

page_text: alkylating alphylparamido orthotoluidines, alphylalkyl compounds are produced
which are
represented by the general formula
In order to produce the alphylparamidoalkylorthotoluidines (or alphylalkyl-
metatoluylenediamines), for instance, the bases (viz., alphylparamidoorthotoluidines
or alphylmetatoluylenediamines) may be acted on by alkyl haloids, such as methyl-
chloride, ethylchloride, methylbromide, ethylbromide, or the like alkylating agents,
either alone or in the presence of solvents or diluents, or substances capable of
facilitating the action.
A method of producing these alphylalkyltoluylendiamines, or alpbylparamido-
alkylorthotoluidines, is illustrated by the following example, the parts being by
PRODUCTION OF PHENYLETHYLMETATOLUYLENEDIAMINE.
A solution of 20 parts of phenylparamidoorthotoluidine and 11 parts of ethyl-
bromide in 40 parts of alcohol, is heated in a closed vessel capable of withstanding
pressure at 150 to 175 degrees Centigrade, during about 10 hours. The product
is mixed with a small quantity of muriatic acid, and is then dissolved in boiling
alcohol. The salt of the new base separates in a crystalline form as the liquid
.cools. On adding sodium carbonate, the base separates as an oil, which imme-
diately becomes crystalline. It is purified by crystallization from ligroin. The
pure base melts at from 59 to 60 degrees Centigrade. It is represented by the
formula-
The homologues or analogues of phenylparamidoethylorthotoluidine are obtained
either on substituting, for the ethylbromide used in the foregoing example, other
alkylhaloids, or other alkylating agents (such as methylbromide, methylchloride,
or the like), or on using equivalent quantities of the homologous paratolylpar- 3
amidoorthotoluidine, naphthylparamidoorthotoluidine, or the like, in place of the
phenylparamidoorthotoluidine used in the above first example, and treating these

page_text: alphylparamidoorthotoluidines with methylating, ethylating, or the like alkylating
agents. The alphylalkylparamidoorthotoluidines thus obtained possess properties
analogous to those of the aforesaid phenylparamidoethylorthotoluidine.
Instead of the alcohol prescribed in the example, another suitable solvent or
liluent may be used. The process may also be carried out without adding solvents
or diluents, and the quantities of the substances used in the foregoing example
may be varied within certain limits. Moreover, other alkylating agents may be
used instead of the alkyl-haloids, for instance, the alphylparamidoorthotoluidines,
or alphylmetatoluylenediamines, may be acted on by alcohols in the presence of
mineral acids. Such or the like modifications do not alter the nature of this part
of the invention, which, speaking generally, relates to the production of alphyl-
alkylmetatoluylenediamines represented by the general formula given above, by
treating alphylparamidoorthotoluidines with alkylating agents.
My foreign correspondents have further discovered, that the alphylparamido-
alkylorthotoluidines, or alphylalkylmeta toluylenediamines herein before defined,
yield valuable azine dye-stuffs when condensed with nitroso compounds, azo com-
pounds, quinone imides, or the like, and also when subjected to oxidation conjointly
with paradiamines, and that the same or analogous colouring matters can be
produced either by heating primary, secondary, or tertiary aromatic amines of the
benzene or naphthalene series, with azo compounds, such as are obtained by
coupling diazo derivatives of aromatic amines with the alphylalkylmetatoluylene-
diamines herein before defined, or by subjecting primary, secondary, or tertiary
amines of the benzene or naphthalene series to oxidation conjointly with the
alphylalkyltriamidotoluenes obtained by reducing the last-named azo compounds,
or in any other suitable manner.
The new dye-stuffs thus obtained from the alphylmetatoluylenediamines herein-
before referred to, are to be regarded as alkylated derivatives of the corresponding
coloring matters produced by my foreign correspondents from alphylparamido-
orthotoluidines, or alphylmetatoluylenediamines. They resemble the last-named
colouring-matters, and particularly in the manner in which they withstand exposure
to the action of light and alkalies, but are far superior to them on account of the
brilliancy and beauty of the shades which they afford.
The processes for producing the colouring matters hereinbefore defined, on the
one hand, from alphylalkylmetatoluylenediamines and nitroso compounds, or azo
compounds, or quinone imides, or the like, on the other hand, by oxidation of the
said alphylalkylmetatoluylenediamines, conjointly with paradiamines, are illustrated
by the following examples B, C, D, E, F, and G. The parts are by weight.
COLOURING MATTER OBTAINED FROM PHENYLETHYLMETATOLUYLENEDIAMINE
AND NITROSO DIMETHYLANILINE HYDROCHLORIDE.
28 parts of nitrosodimethyl aniline hydrochloride are gradually stirred into a
solution of 23 parts of phenylethylmeta toluylenediamine, or phenylparamido-
ethylorthotoluidine, in 100 litres (in case the parts are kilos. by weight) of
alcohol. The mixture is gently heated in a vessel provided with a reflux condenser,
until the nitrosodimethylaniline is no longer distinguishable. The dye-stuff which
is formed crystallizes out on cooling the solution. It is purified by filtering it off
and washing with alcohol. On cotton mordanted with tannic acid or the like, it
produces shades which are bluer and clearer than those of the analogous colouring.
matter from phenyl paramido orthotoluidine and nitrosodimethylaniline hydro-
chloride.
The dye-stuff is identical with that which my foreign correspondents have
obtained by conjointly oxidising molecular proportions of paramidodimethylaniline,
monethylorthotoluidine, and aniline.

page_text: DYESTUFF OBTAINED FROM PHENYLETHYLMETATOLUYLENEDIAMINE AND
NITROSOMONOMETHYLORTHOTOLUIDINE HYDROCHLORIDE.
23 parts. of phenylethylmetatoluylene diamine, or phenylparamidoethylortho-
toluidine, are dissolved in 100 litres (in case the parts are kilos. by weight) of
alcohol. 29 parts of nitrosomonomethylorthotoluidine hydrochloride are then
gradually stirred in, and the mixture is heated until the nitroso compound is no
longer distinguishable. On cooling the liquid, the dyestuff entirely crystallises
out. It is purified by filtering off and washing with alcohol. On cotton prepared
with tannic acid or the like, it produces extremely beautiful brilliant red shades,
which are scarcely inferior to those obtainable with the aid of the dye-stuff known
in commerce as "Rhodamine S."
My foreign correspondents obtained this dye-stuff some time ago by oxidising
amidomonomethylorthotoluidine conjointly with monoethylorthotoluidine and
aniline in molecular proportions.
COLOURING MATTER OBTAINED FROM PHENYLETHYLMETATOLUYLENEDIAMINE
AND AMIDOAZO BENZENE.
41 parts of amidoazobenzene sulphate are added to a solution, in phenol, of
23 parts of phenylethylmeta toluylenediamine, or phenylparamidomonethylortho-
toluidine, and the mixture is heated by means of a water-bath, being stirred the
while, until the amido azo compound is no longer distinguishable. The liquid is
then diluted with water, and subsequently super-saturated with soda-lye. The
precipitated mass is repeatedly extracted with boiling water, until the dye-stuff
contained therein is wholly removed. The solutions are filtered, and acidulated
with muriatic acid. The colouring matter is then precipitated by salting out and
isolated in the usual manner. On cotton mordanted with tannic acid or the like, it
produces clear red shades, distinguished by their fastness on washing and exposure
to light.
This dye-stuff is identical with that which is obtained, as my foreign
correspondents have found, by oxidising paraphenylenediamine conjointly with
monoethylorthotoluidine and aniline in molecular proportions.
DYESTUFE OBTAINED FROM PHENYLMETHYLMETATOLUYLENEDIAMIME AND
BENZENEAZOALPHANAPHTHYLAMINE.
A mixture of 21 parts of phenylmethylmeta toluylenediamine, or phenylpara
midomethylorthotoluidine, and 43 parts of benzeneazoalphanaphthylamine hydro-
chloride, is introduced into 20 parts of glacial acetic acid. The liquid is heated
by means of a water bath, until the azo compound is no longer distinguishable.
After adding about 2 litres (in case the parts are kilos. by weight) of muriatic
acid (20 degrees Baumé) and a sufficient quantity of water, the dyestuff is salted
out. To purify it, the precipitate is filtered off, dissolved in hot water, and after
filtering the solution, is salted out. On cotton prepared with tannic acid or the
like, it produces bluish-red shades distinguished by reason of their fastness on
exposure to the action of alkalies, acids, and light.
My foreign correspondents have also produced this colouring matter by oxidising
monomethylorthotoluidine conjointly with naphthylenediamine (1.4) and aniline in
molecular proportions.

page_text: COLOURING MATTER PRODUCED FROM PHENYLETHYLMETATOLUYLENEDIAMINE
AND QUINONEDICHLORDIIMIDE.
1.8 parts of quinonedichlordiimide are gradually added to a slightly warm
The
solution in alcohol of 23 parts of phenylparamidoethylorthotoluidine.
mixture is kept stirred, and gently heated, until the quinonedichlordiimide is
no longer distinguishable. The alcohol is then distilled off, and the residue is
digested with hot water. 'The filtered solution is rendered alkaline with soda-lye.
The precipitated mass is filtered off and extracted with boiling water, until the
whole of the dye-stuff contained therein is dissolved. The filtrates are acidulated
with muriatic acid, and the dyestuff is salted out, filtered off, pressed, and dried.
This colouring matter is identical with that obtained, as described in the
preceding example D, from phenylethylmetatoluylenediamine and amidoazobenzene.
DYE-STUFF OBTAINED FROM PHENYLETHYLMETATOLUYLENEDIAMINE AND
PARAMIDODIMETHYLANILINE.
2-3 parts of phenylparamidomonoethylorthotoluidine and 1-4 parts of paramido
dimethylaniline are dissolved in about 20 parts of glacial acetic acid, and a solution
of 3 parts of sodium dichromate, in the smallest possible quantity of hot water, is
gradually stirred into the liquid. The mixture is heated until it assumes a pure
magenta-red colour, which does not increase in intensity. The dyestuff having been
salted out, filtered off, and redissolved in water, the solution is rendered alkaline with
soda-lye, and filtered. The filtrate is acidulated with muriatic acid, and the dyestuff
is salted out, filtered off, pressed, and dried.
My foreign correspondents have also produced this dyestuff by oxidising
monethylorthotoluidine conjointly with paramidodimethylaniline, and aniline, in
molecular proportions.
Other colouring matters are formed in an analogous manner, if other nitroso or
azo compounds are used in place of those prescribed in the preceding examples, or
if other alkylated paradiamines, or alkylated paradiamine sulphonic acids, containing,
in one of their amido groups, either a single or two alkyl groups, or paradiamines
themselves, are substituted for the paramidodimethylaniline used in the last
mentioned example G; or if, instead of the quinonedichlordiimide prescribed in
the sixth example, other paraquinoneimides, or chlorimides, are used, or by sub-
stituting for the phenylethylmetatoluylene diamine, and the phenylemethyl meta-
toluylene diamine, other aphylparamido-alkylorthotoluidines herein before defined,
suchi
as paratolylparamidoethylortho toluidine, paratolylparamidomethylortho-
toluidine, or the like. The oxidation effected, in the case of Example G, by means.
of sodium dichromate, can also be carried out by using other oxidising agents
suitable for these purposes.
The coloring matters thus obtained are similar in their properties to those
obtained as described in Examples B, C, D, E, F, and G.
In producing all these dye-stuffs, my foreign correspondents do not limit them-
selves to the directions given in the above examples, which are merely typical. All
known methods in use for producing analogous dye-stuffs can be adopted. For
instance, other solvents, such as glycerol or the like, can be used in place of the
solvents or diluents prescribed in the preceding examples.
As above mentioned, the same or analogous coloring matters can also be
produced, if either primary, secondary, or tertiary.aromatic amines, unsubstituted in
the "para" position relatively to the amido group, or alkylamido group, are

page_text: subjected to oxidation conjointly with the alphylalkyl-triamido toluenes obtainable
from the alpha-alkylmetatoluylenediamines herein before defined, or if primary,
secondary, or tertiary amines are condensed with the azo compounds formed by the
combination of diazo compounds with the alphylalkylmetatoluylene diamines
hereinbefore referred to..
The said alphylalkyltriamido toluenes are represented by the general formula―
My foreign correspondents use the letter R in the above formula to indicate
radicles of amido compounds whose diazo derivatives are coupled with the
alphylalkylmetatoluylene diamines.
The alphylalkyltriamidotoluenes can be produced by nitrating alphylalkylmeta-
toluylene diamines, and subsequently reducing the so-formed mononitro compounds,
or by reducing the azo compounds represented by the last of the above general
formulæ, produced by the combination of any diazo compound with an alplaylalkyl-
metatoluylene diamine.
The process for producing azine dye-stuffs from the last-named azo compounds,
or alphylalkylmetatoluylenetriamines, is illustrated by the following examples, the
parts being by weight
COLORING MATTER PRODUCED FROM BENZENE SULPHONIC ACID AZO PHENYL-
METHYLTOLUYLENEDIAMINE AND ALPHANAPHTHYLAMINE.
6-3 parts of benzene sulphonic acid azo-phenylmethyl metatoluylene diamine
(obtained by coupling diazotised parasulphanilic acid with phenylmethylmeta-
toluylene diamine) are finely pulverised, and mixed with 14 parts of alphanaph-
thylamine and 20 parts of phenol. The mixture is kept continually stirred at a
temperature from about 90 to 110 degrees Centigrade, until the original brown
color has turned into pure red, and the azo compound used is no longer
distinguishable. An excess of warm dilute soda-lye is then added, and after

page_text: cooling the liquid, the precipitated dye-stuff is filtered off and pressed. To purify
the press cake, it is dissolved in hot water containing muriatic acid, and the hot.
filtered solution is mixed with muriatic acid. The dye-stuff crystallizes out as the
liquid cools. It is filtered off, pressed, and dried.
It readily dissolves in water, and dyes cotton prepared with tannic acid or the
like brilliant bluish-red shades. It is identical with the coloring matter obtained,
as described in the preceding example E, from benzene-azo-alpha naphthylamine
and phenylmethylmetatoluylene diamine.
DYE STUFF OBTAINED FROM PHENYLMETHYLTRIAMIDOTOLUENE AND
ALPHANAPHTHYLAMINE.
2.2 parts of phenylmethyltriamidotoluene are thoroughly mixed with 1.8 parts of
alphanaphthylamine hydrochloride, and 20 parts of phenol. The mixture (through.
which a current of air is allowed to pass) is heated by means of a water-bath,
being stirred the while, until the color has turned into pure red, and the intensity
of this color no longer increases. The dye-stuff is purified and isolated in the
manner described in the Example H, in the case of the dye-stuff obtained from
benzene sulphonic acid azo phenylmethyltoluyene diamine and alpha paphthyl-
amine. According to the researches of my foreign correspondents, these two
dye-stuffs are identical.
COLORING MATTER OBTAINED FROM PHENYLMETHYLTRIAMIDOTOLUENE AND.
C
ALPHANAPHTHYLAMINE.
2.2 parts of phenylmethyltriamidotoluene and 1.4 parts of alphanaphthylamine
are dissolved in 20 parts of glacial acetic acid, and a solution of parts of sodium.
dichromate, in the smallest possible quantity of water, is gradually stirred into the
liquid. The mixture is heated by means of a water bath until the intensity of the
color no longer increases. An excess of muriatic acid is then added, and'
the dye-stuff is salted out. To purify it, the precipitate is dissolved in a small
quantity of hot water, and the filtered solution is mixed with muriatic acid.
the liquid cools, the finished dye-stuff crystallizes out. It is identical with the.
coloring matter obtained as described in the preceding examples H and I.
As
Other dye-stuffs are formed in a manner analogous to that described in the
Examples H, I and K, by using, instead of the benzene sulphonic acid, azo
phenylmethylmetatoluylene diamine, that is to say, the azo compound from
diazotised parasulphanilic acid and phenylparamidomethylorthotoluidine, other azo-
compounds obtained from diazo compounds, and the alphylalkylmetatoluylene.
diamines hereinbefore defined, or by using, instead of phenylmethyltriamidotoluene,.
paratolylethyltriamidotoluene, or other alphylalkyltriamido toluenes, or if other
primary or secondary or tertiary amines of the benzene or naphthalene series are
substituted for the alphanaphthylamine. Instead of effecting the oxidation by
means of sodium dichromate, or atmospheric oxygen, other oxidising agents, such
as potassium dichromate, chloride of lime, lead dioxide, manganese dioxide, or the
like, can be used. Other solvents or diluents, such as alcohol, glycerol, or the like,
can be substituted for the solvents or diluents, viz., phenol, and acetic acid, used in
the last three examples. As a matter of course, the production of the dye-stuffs
by means of the processes illustrated by the last three examples, can be varied, and
all known methods in use for producing analogous coloring matters can be used.
Having now particularly described and ascertained the nature of the said inven--

page_text: tion and in what manner same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
1. The production of alphylalkyl metatoluylene diamines represented by the
general formula-
NH alphyl
(in which formula the expression "alphyl" signifies phenyl tolyl, naphthyl, or the
like radicles, in contra-distinction to the expression alkyl," which indicates
methyl, ethyl, or the like radicles), from alphylmetatoluylenediamines, such as
phenylmetatoluylenediamine (CH, NH, NHC,H, 1:24), paratolyl-
metatoluylene diamine (CH, NH, NHC,H,-1: 2: 4), naphthylmetatoluy-
lene diamine, or the like.
:
2. The process for producing alphylalkylmetatoluylene diamines, such as
phenylmethyl (or ethyl) metatoluylene diamine, paratolylmethyl (or ethyl)
metatoluylene diamine, naphthylmethyl (or ethyl) metatoluylene diamine, or the
like, which process consists in alkylating alphylmetatoluylene diamines (such as
phenylmeta toluylene diamine, paratolylmetatoluylene diamine, naphthylmetatoluy-
lene diamine, or the like).
3. The production of azine dye-stuffs from the alphylalkylmetatoluylenediamines
hereinbefore defined, and nitroso derivatives of secondary or tertiary aromatic
amines or amidosulphonic acids.
4. The process for producing dye-stuffs by condensing nitrosomonomethylaniline,
nitrosomonomethyl orthotoluidine, nitrosodimethylaniline, nitroso diethylaniline,
nitrosodiphenylamine, or nitrosomethyldiphenylamine, or analogous nitroso com-
pounds or nitrosomethylbenzylanilinesulphonic acid, nitroso methyldiphenylamine
sulphonic acid, or analogous nitroso compounds, with phenylmethyl (or ethyl)
metatoluylene diamine, paratolylmethyl (or ethyl) metatoluylene diamine, naphthyl-
methyl (or ethyl) metatoluylene diamine, or analogous alphylalkylmetatoluylene
.diamines.
5. The production of azine coloring matters by acting with the alphylalkyl-
metatoluylene diamines hereinbefore defined, either on paramido azo compounds
formed by the combination of diazo derivatives with primary, secondary, or
tertiary amines, or substituted amines, of the benzene or naphthalene series, or on
para quinone imide, paraquinone chlorimides, or the like compounds of the
benzene or naphthalene series.
6. The process for producing azine dye-stuffs, which process consists in sub-
jecting the alphylalkylmetatoluylene diamines hereinbefore defined, together with
para diamines, or alkylated paradiamines, or alkylated paradiamine sulphonic
acids, containing, in one of their amido groups, either a single or two alkyl radicles,
conjointly to oxidation in the presence of suitable solvents or diluents.
7. The production of azine coloring matters from alphylalkyltriamidotoluenes
represented by the general formula-

page_text: which process consists in subjecting primary, secondary, or tertiary aromatic
amines, unsubstituted in the para position relatively to the amido or alkylamido
group, to oxidation conjointly with the alphylalkyl triamidotoluenes in the
presence of suitable solvents or diluents.
8. The process for producing azine dye stuffs from the azo compounds formed
by the combination of diazo derivatives with the alphylalkyĺmetatoluylene
diamines hereinbefore defined, and represented by the general formula—
which process consists in condensing primary, secondary, or tertiary aromatic
amines with the said azo compounds derived from alphylalkylmetatoluylene diamines.
9. As new products of manufacture, the new alphylalkylmetatoluylene diamines
(such as phenylmethyl (or ethyl) metatoluylene diamine, paratolyl methyl (or
ethyl) metatoluylene diamine, naphthylmethyl (or ethyl) metatoluylene diamine,
or the like, produced by the processes hereinbefore defined, or by any other means
affording the same result.
Dated this 19th day of Fahun 1906
NEWTON & SON,
Agents for the Applicant.