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

page_text: Date of Application, 25th Mar., 1895
Complete Specification Left, 27th Dec., 1895-Accepted, 15th Feb., 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 ago that on heating meta
toluylenediamine (CH: NH2: NH₂ = 1:2:4) with primary aromatic amines, only
the amido group in the "para" position relatively to the methyl group is
substituted, whereas the amido group in the "ortho" position relatively to the
methyl group remains unaltered. Phenylparamidoorthotoluidine, or phenylmeta-
toluylenediamine, tolylparamidoorthotoluidine, or tolylmetatoluylene diamine, or the
like, are thus formed. My foreign correspondents term the resulting paramido-
orthotoluidines, or metatoluylene diamines, containing the radicle of an hydrocarbon
of the benzene series in place of one hydrogen atom of the one amido group, as
alphylparamidoorthotoluidines, or alphylmetatoluylenediamines. This nomenclature
is based on the proposition of Bamberger (see Berichte der Deutschen Chemischen
Gesellschaft, volume 27, page 2583), to term the radicles such as phenyl, tolyl, or
the like, as "alphyls," in contradistinction to the alkyls, viz., methyl, ethyl, benzyl,
or the like. My foreign correspondents have also attempted to prepare, by means
of the above defined reaction, alphylalkylamidoorthotoluidines, or alphylalkylmeta-
toluylenediamines of the general formula :-
viz., by heating with primary aromatic amines, such monoalkylmetatoluylene
diamines as contain the alkyl group in the amido group adjacent to the methyl
group, but these experiments have shewn that the reaction does not proceed in the
manner anticipated.
My foreign correspondents have now succeeded in obtaining the said alphyl-
alkylamidoorthotoluidines, or alphylalkylmetatoluylenediamines, which, owing to
their composition, are well adapted for the preparation of azine dyestuffs. This
process consists in alkylating the alphylparamidoorthotoluidines, or al; hylmeta-
toluylenediamines, and, according to the researches of my foreign correspondents,
the use of benzylating agents has given the best results amongst the alkylating
agents.

page_text: In order to produce the alphyl benzylmeta toluylenediamines, or alphyl
paramidobenzylorthotoluidines, for instance, the free bases, viz., alphylparamido-
orthotoluidines (or alphylmetatoluylenediamines) may be acted upon by benzyl-
chloride in or without the presence of solvents or diluents.
One method of producing these alphylbenzylmetatoluylenediamines, or alphyl-
paramidobenzylorthotoluidines, is illustrated by the following example, the parts
being by weight.
In order to produce the alphyl benzylmeta toluylenediamines, or alphyl
paramidobenzylorthotoluidines, for instance, the free bases, viz., alphylparamido-
orthotoluidines (or alphylmetatoluylenediamines) may be acted upon by benzyl-
chloride in or without the presence of solvents or diluents.
One method of producing these alphylbenzylmetatoluylenediamines, or alphyl-
paramidobenzylorthotoluidines, is illustrated by the following example, the parts
being by weight.
FIRST EXAMPLE.
PRODUCTION OF PHENYLBENZYLMETATOLUYLENEDIAMINE.
50 parts of phenylparaidoorthotoluidine are heated, by means of a water
bath, until the material used has melted.
13 parts of benzyl chloride are then
quickly stirred into the hot mass. The reaction begins at once, phenyl-par-
amidoorthotoluidinehydrochloride being separated. Heating is continued, until the
whole mass has become solid in the form of a crystal cake, and the odour of
benzylchloride is no longer distinguishable. At this stage, the resulting mass is
boiled with water containing muriatic acid, in order to remove the unaltered
phenylparamido-ortho-toluidine, which dissolves, and can be separated by filtration.
The residue, insoluble in water containing muriatic acid, is purified by crystal-
lization from alcohol. The so-formed phenylbenzylmeta toluylenediamine, or
phenylparamidomonobenzylorthotoluidine crystallizes from alcohol in beautiful
colourless star-shaped scales, melting at 102 degrees Centigrade. It possesses the
following formula :-
PRODUCTION OF PHENYLBENZYLMETATOLUYLENEDIAMINE.
50 parts of phenylparainidoorthotoluidine are heated, by means of a water
bath, until the material used has melted. 13 parts of benzyl chloride are then
quickly stirred into the hot mass. The reaction begins at once, phenyl-par-
amidoorthotoluidinehydrochloride being separated. Heating is continued, until the
whole mass has become solid in the form of a crystal cake, and the odour of
benzylchloride is no longer distinguishable. At this stage, the resulting mass is
boiled with water containing muriatic acid, in order to remove the unaltered
phenylparamido-ortho-toluidine, which dissolves, and can be separated by filtration.
The residue, insoluble in water containing muriatic acid, is purified by crystal-
lization from alcohol. The so-formed phenylbenzylmetatoluylenediamine, or
phenylparamidonionobenzy lorthotoluidine crystallizes from alcohol in beautiful
colourless star-shaped scales, melting at 102 degrees Centigrade. It possesses the
following formula :-
It is insoluble in water, soluble in concentrated muriatic acid, and is precipitated
again on diluting the muriatic acid solution with water. It dissolves with
difficulty in cold ligroin, with less difficulty in hot ligroin, and with comparative
ease in ether and cold alcohol. It is soluble with readiness in benzene and hot
alcohol.
The homologues of phenylparamidobenzylorthotoluidine, such as paratolyl-
paramidobenzylorthotoluidin, or the like, are obtained on using the homologous
paratoylparamidoorthotoluidine, or the like, in place of phenylparamido ortho-
toluidine mentioned above. These homologous disubstituted paramidoortho-
toluidines possess properties analogous to those of the aforesaid phenyl paramido
benzylorthotoluidine.
The process for producing these alphylparamidobenzylorthotoluidines, or
alphylbenzylmetatoluylenediamines, may be varied, for instance, by allowing
- benzylchloride to act on the aforesaid alphyl paramidoorthotoluidines, in the
presence of solvents or diluents. For this purpose, the last named alphyl-
paramidoorthotoluidines are dissolved in about the equivalent quantity of alcohol,
or glycerinol, or the like, and the benzylchloride, profitably diluted with an equal
volume of alcohol or the like, is then added. The resulting liquid mixture is heated,
until the benzylchloride is no longer distinguishable. After cooling, the benylated
compound crystallises out, and the phenyl paramidoorthotoluidine hydrochloride
remains in solution.

page_text: On effecting the benzylating process in the presence of alkalies, equal molecular
proportions of the alphylmetatoluylene diamines and benzylchloride can be used
whereas two molecular proportions of alphylmetatoluylenediamines, and one
molecular proportion of benzylchloride, are necessary, if the process is carried
out without the presence of alkalies.
Naturally, benzyl bromide, or the like, can be used in place of benzylchloride,
that is to say; the benzylating process can be effected by means of the methods
known and in use for analogous purposes.
My foreign correspondents have further discovered, that the alphylparamido-
benzylorthotoluidines, or alphylbenzyl metatoluylenediamines, 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 dyestuffs, and that the same or analogous colouring matters
cau be produced, either by heating primary, secondary, or tertiaryaromatic amines
of the benzene or naphthalene series, with azo products such as are obtained by
coupling diazo derivatives of aromatic amines with the alphylbenzylmetatoluylene
diamines hereinbefore defined, or by subjecting to a joint oxidation, primary,
secondary, or tertiary amines of the benzene or naphthalene series, together with
the alphylbenzyltriamido toluenes obtained by reducing the lastnamed azo products,
or in any suitable manner.
The new dyestuffs thus obtained from the alphylbenzylmetatoluylene diamines
hereinbefore referred to, are, chemically, benzylated derivatives of the corre-
sponding colouring matters produced by my foreign correspondents from alphyl-
paramidoorthotoluidines, 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 by far superior to
the last-defined dyestuffs by reason of the brilliancy and beauty of the shades
produced therewith.
The processes for producing the colouring matters hereinbefore defined, on the
one hand, from alphylbenzylmeta toluylenediamines and nitroso compounds or azo
products, or quinoneimides or the like, on the other hand, by a joint oxidation of
the alphylbenzylmeta 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 PHENYLBENZYLMETATOLUYLENE
DIAMINE AND NITROSODIMETHYLANILINE HYDROCHLORIDE.
28 parts of nitrosodimethylaniline hydrochloride are gradually stirred into a
solution prepared by dissolving 29 parts of phenylbenzyl metatoluylenediamine, or
phenylparamidobenzylorthotoluidine, in 100 litres (iu 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 crystallizes out. It is purified by filtering
off and washing with alcohol. It produces on cotton mordanted with tannic acid
or the like, shades which are bluer & clearer than those of the analogous
colouring matter from phenylparamidoorthotoluidine and nitrosodimethylaniline-
hydrochloride.
DYESTUFF OBTAINED FROM
PHENYLBENZYLMETATOLUYLENEDIAMINE
NITROSOMONOMETHYLORTHOTOLUIDINEHYDROCHLORIDE.
AND
29 parts of phenylbenzylmetatoluylene diamine, or phenyl paramido benzyl
orthotoluidine, are dissolved in 100 litres (in case the parts are kilo's by weight)

page_text: of alcohol. Under continuous stirring, 29 parts of nitrosomonomethylortho
toluidinehydrochloride are gradually added, and the so-formed mixture is heated
until the nitroso compound is no longer distinguishable. On cooling, the dyestuff
entirely crystallizes out. It is purified by filtering off and washing with alcohol.
It 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 S."
COLOURING MATTER OBTAINED FROM PHENYLBENZYLMETATOLUYLENE-
DIAMINE AND AMIDOAZOBENZENE.
4.1 parts of amidoazobenzene sulphate are added to a solution, in phenol, of
2.9 parts of phenylbenzyl metatoluylenediamine, or phenylparamidomonobenzyl-
orthotoluidine, and the resulting mixture, while being stirred, is heated by means
of a water bath, until the amido azo compound is no longer distinguishable. The
liquid is diluted with water, and subsequently supersaturated by meaus of soda-lye.
The precipitated mass is repeatedly treated with boiling water, until the dyestuff
contained therein has wholly dissolved. The resulting solutions are filtered and
acidulated with muriatic acid. The colouring matter is then precipitated by
salting out, and is isolated in the usual manner. It yields on cotton mordanted
with tannic acid, or the like, clear bluish-red shades distinguished by reason of
their fastness against the action of washing and light.
DYESTUFF
OBTAINED FROM
PHENYLBENZYLMETATOLUYLENEDIAMINE
BENZENEAZOALPHANAPHTHYLAMINE.
AND
A mixture containing 2.9 parts of phenylbenzylmetatoluylenediamine, or phenyl-
paramidobenzylorthotoluidine, and 4.3 parts of benzeneazoalphanaphthylamine
hydrochloride, is introduced into 20 parts of glacial acetic acid. The liquid is
heated by means of a water-bath, until the azo product is no longer distinguishable.
After adding about 2 litres (in case the parts are kilos. by weight) of muriatic acid
at 20 degrees Bauné and a sufficient quantity of water, the dyestuff is salted out.
It is purified by filtering off, redissolving in hot water, filtering again, and salting
It yields on cotton prepared with tannic acid or the like, bluish-red shades
distinguished by reason of their fastness against the action of alkalies, acids, and
light.
out.
COLOURING MATTER PRODUCED FROM PHENYLBENZYLMETATOLUYLENE
DIAMINE AND QUINONE DICHLORDIIMIDE.
1.8 parts of quinone dichlordiimide are gradually added to a gently heated
solution in alcohol of 2.9 parts of phenylparamidobenzylorthotoluidine.
The
mixture is gently heated, while stirring, until the quinone dichlordiimide is no
longer distinguishable. The alcohol is then distilled over, and 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 dye stuff 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 phenylbenzylmetatoluylenediamine and amido-
azobenzene.

page_text: DYE-STUFF OBTAINED FROM
PHENYLBENZYLMETATOLUYLENEDIAMINE AND
PARAMIDODIMETHYLANILINE.
2.9 parts of phenyl paramidomonobenzylorthotoluidine and 14 parts of
paramidodimethylaniline 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,
while stirring. The mixture is heated, until the colour has turned into pure
magenta red and the intensity of this colour no longer increases. The dyestuff is
salted out, filtered off, redissolved in water, and this solution is rendered alkaline
by means of soda lye. The filtrate obtained therefrom is acidulated with muriatic
acid, and the dyestuff is salted out, filtered off, pressed, and dried.
Other colouring 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 paramidodimethylaniline used
in the said example, or if the quinonedichlordiimide used in the sixth example is
replaced by other paraquinoneimides or chlorimides, or if the phenylbenzylmeta-
toluylenediamine is replaced by other alphyl paramidobenzylorthotoluidines
hereinbefore defined, such as paratolyl paramido benzylorthotoluidine 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 colouring matters thus obtained are similar in their properties to those
obtained as described in Examples 2, 3, 4, 5, 6, & 7.
In the production of all these dyestuffs, 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 dyestuffs 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 mentioned in the preceding examples.
66
As above stated, the same or analogous colouring 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 alphylbenzyltriamidotoluenes obtainable
from the alphylbenzylmetatoluylene diamines 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 alphylbenzylmetatoluylene diamines
hereinbefore referred to.
The said alphylbenzyltriamido toluenes have the general formula :-
:-

page_text: and the azo
products obtainable by coupling diazo derivatives with the alphyl-
benzylmetatoluylenediamines possess the general formula :-
My foreign correspondents mean by the letter R in the last formula, the radicles
of amido compounds, the diazo derivatives of which are coupled with the alphyl-
benzylmetatoluylenediamines.
The alphylbenzyltriamidotoluenes can be produced by nitrating alphylbenzyl-
metatoluylene diamines, 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, & resulting from the combination of any diazo
compounds with alphylbenzylmetatoluylene diamines.
The process for producing azine dye-stuffs from the last named azo products, or
alphylbenzylmetatoluylene diamines, is illustrated by the following examples, the
parts being by weight.
COLOURING MATTER PRODUCED FROM BENZENESULPHONIC ACID,
PHENYLBENZYLTOLUYLENEDIAMINE, AND ALPHANAPHTHYLAMINE.
AZO-
7.2 parts of benzenesulphonic acid azo phenylbenzylmetatoluylene diamine
(obtained by coupling diazotised parasulphanilic acid with phenylbenzylmeta-
toluylene diamine) are finely pulverised, and mixed with 14 parts of alpha-
naphthylamine and 20 parts of phenol. While stirring, the mixture is kept at
from about 90 to 110 degrees Centigrade, until the original brown colour has
turned into pure red, and the azo product used is no longer distinguishable. Au
excess of warm dilute soda lye is then added, and after cooling, the precipitated
dye stuff is filtered off and pressed. To purify, the press-cake is dissolved in hot
water containing muriatic acid, and the hot filtered solution is mixed with muriatic
acid. On cooling, the dye-stuff crystallises out. It is filtered off, pressed, and
dried.
It readily dissolves in water, and yields, on cotton prepared with tannic acid or
the like, brilliant bluish-red shades. It is identical with the colouring matter
obtained, as described in the preceding fifth example, from benzeneazoalpha-
naphthylamine and phenylbenzylmetatoluylenediamine.
DYESTUFF OBTAINED FROM PHENYLBENZYLTRIAMIDOTOLUENE AND
ALPHANAPHTHYLAMINE.
3 parts of phenylbenzyltriamidotoluene are thoroughly mixed with 1.8 parts of
alphanaphthylamine hydrochloride and 20 parts of phenol. While stirring, the
mixture (through which a current of air is allowed to pass) is heated by means of
a water bath, until the colour has turned into pure red, and the intensity of this

page_text: colour no longer increases. The dye-stuff is purified and isolated in the manner
described in eighth example with respect to the dyestuff obtained from benzene-
sulphonic acid, azophenylbenzyltoluylene diamine, and alphanaphthylamine.
According to the researches of my foreign correspondents, these two dyestuffs are
identical.
COLOURING MATTER OBTAINED FROM PHENYLBENZYLTRIAMIDOTOLUENE
AND ALPHANAPHTHYLAMINE.
3 parts of phenylbenzyltriamidotoluene and 14 parts of alphanaphthylamine are
dissolved in 20 parts of glacial acetic acid. A solution prepared by dissolving
3 parts of sodium dichromate in the smallest possible quantity of water is allowed
to flow gradually into the above liquid, while stirring. The mixture is heated by
means of a water bath, until the intensity of the colour no longer increases. An
excess of muriatic acid is then added, and the dyestuff is salted out. To purify
it, it is redissolved in a small quantity of hot water, and the filtered solution is mixed
with muriatic acid. On cooling, the finished dyestuff crystallises out. It is
identical with the colouring-matter obtained as described in the eighth and ninth
examples.
Other dyestuffs result in a manner analogous to that described in the eighth,
ninth, & tenth examples, if the benzenesulphonic acid azophenylbenzylmeta-
toluylenediamine, that is to say, the azo product from diazotised parasulphanilic
acid and phenylparamidobenzylorthotoluidine is replaced by other azo-products
obtained from diazo compounds, and the alphylbenzylmetatoluylenediamines
herein before defined, or if the phenylbenzyltriamidotoluene is replaced by para-
tolylbenzyltriamidotoluene, or other alphyltriamidotoluenes, or if other primary
or secondary or tertiary amines of the benzene or naphthalene series are substituted
for the alphanaphthylamine. In place 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 dyestuffs by means of the processesses illustrated by the last three examples
can be varied, and all methods known & in use for producing analogous colouring
matters can be used.
Dated this 25th day of March 1805
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Dye-stuffs, and Materials
therefor.
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 on heating salts of meta-toluylenediamine
(CH3:NH,:NH, 124) with primary aromatic amines, only the amido
group in the "para" position relatively to the methyl group is affected, the amido
group in the "ortho" position relatively to the methyl group remaining unaltered,

page_text: compounds such as phenylparamido ortho toluidine or phenyl metatoluylene
diamine, and tolylparamido orthotoluidine, or tolylmetatoluylene diamine, or the
like, being formed. My foreign correspondents term such parainido-ortho-
toluidines, or metatoluylene diamines, containing the radicle of a hydrocarbon of
the aromatic series, in place of a hydrogen atom of the one amido group, alphyl-
paramido-orthotoluidines, or alphylmeta tolylenediamines. This nomenclature is
based on the proposal made by Bamberger (see Berichte der Deutschen Chemis-
chen Gesellschaft, volume 27, page 2583) to term phenyl, tolyl, or the like radicles,
alphyls," in contra-distinction to the alkyls, viz., methyl, ethyl, benzyl, or the
like. My foreign correspondents have also attempted, by means of the above
defined method, to prepare alphyl amido-alkyl-ortho-toluidines, or alphylalkyl-
metatoluylene diamines of the general formula :-
66
:-
by the interaction of primary aromatic amines and monalkylmeta toluylene diamines
containing the alkyl group in the amido group adjacent to the methyl group, but
their experiments have shewn that the action does not proceed in the manner
anticipated.
My foreign correspondents have, however, now succeeded in obtaining new
alphyl amido benzyl ortho toluidines, or alphylbenzylmetatoluylene diamines,
which, from their composition, are well adapted for the preparation of azine dye-
stuffs. The process consists in benzylating the alphyl-paramido ortho toluidines
or alphylmeta toluylenediamines.
In order to produce the alphyl benzyl meta toluylene diamines, or alpbyl-
paramido benzylortho toluidines, the bases (viz., alphyl paramido ortho toluidines,
including naphthylparamido orthotoluidines) may be acted on by benzylchloride,
either alone, or in the presence of solvents or diluents.
One method of producing these alphylbenzylmetatoluylene diamines, or alphyl
paramido benzyl ortho toluidines, is illustrated by the following example, the parts
being by weight.
PRODUCTION OF PHENYLBENZYLMETATOLUYLENE DIAMINE.
40 parts of phenyl paramido ortho toluidine having been fused by means of a
water bath, 13 parts of benzyl chloride are quickly stirred into the hot mass.
Action at once takes place, and phenyl paramido ortho toluidine hydrochloride
begins to separate out. Heating is continued until the whole mass has become a
solid crystalline cake, and the odour of benzylchloride is no longer distinguishable.
At this stage, the mass is boiled with water containing muriatic acid, to remove
the unaltered pheny paramido ortho toluidine, which dissolves, and can be separated
by filtration. The insoluble residue is purified by crystallization from alcohol.
The phenyl-benzyl-meta-toluylene-diamine, or phenyl paramido-monobenzyl-ortho-
toluidine thus formed, separates from alcohol in beautiful colourless stellate

page_text: crystals, melting at 102 degrees Centigrade. It is represented by the following
formula
-
It is insoluble in water, but soluble in concentrated muriatic acid, from which it
is precipitated on diluting the solution with water. It dissolves with difficulty in
cold ligroin, with less difficulty in hot ligroin, and with comparative ease in ether
and cold alcohol. It is readily soluble in benzene and hot alcohol.
The homologues of phenylparamido benzylortho-toluidine, such as para tolyl
paramido benzyl ortho-toluidine, naphthyl-paramido-benzyl-ortho-toluidine, or the
like, are obtained on using the homologues para-tolylparamido orthotoluidine,
naphthyl paramido orthotoluidine, or the like, in place of the above mentioned
phenyl paramido ortho toluidine. These homologous disubstituted paramido ortho
toluidines possess properties analogous to those of the aforesaid phenyl paramido
benzyl ortho toluidine.
The process for producing these alpbyl paramido benzylortho toluidines, or
alphylbenzylmetatoluylene diamines, may be varied, for instance, by allowing
benzylchloride to act on the aforesaid alphylparamido ortho toluidines in the
presence of solvents or diluents. For this purpose, the said alphyl paramido ortho
toluidines are dissolved in about an equal quantity of alcohol or glycerol, or the
like; the benzyl chloride, which may with advantage be diluted with about an
equal volume of alcohol, or the like, is then added, and the liquid mixture is heated
until benzylchloride is no longer distinguishable. The benzylated compound
crystallizes out as the liquid cools, the alphyl-parainido-ortho-toluidine hydro-
chloride remaining in solution.
If the benzylation be effected in the presence of alkalies, molecular proportions
of the alphylmetatoluylene diamines and benzylchloride are used.
Naturally, benzylbromide or the like can be used in place of benzylchloride,
that is to say, the benzylating process can be effected by means of the known
methods in use for analogous purposes.
My foreign correspondents have further discovered, that the alphylparamido
benzyl ortho toluidines, or alphylbenzylmeta toluylene diamines hereinbefore defined,
yield valuable azine dye-stuffs when condensed with nitroso compounds, azo
compounds, 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 alphylbenzyl metatoluylene
diamines herein before defined, or by subjecting primary, secondary, or tertiary
amines, of the benzene or naphthalene series to oxidation conjointly with the
alphylbenzyl triamido toluenes obtained by reducing the last named azo compounds,
or in any other suitable manner.
The new dye stuffs thus obtained from the alphylbenzylmetatoluylene diamines
hereinbefore referred to, are to be regarded as benzylated derivatives of the corre-
sponding colouring matters produced by my foreign correspondents from alphyl
paramido ortho toluidines, or alphylmetatoluylene diamines. They resemble the
last-named colouring matters, and particularly in the manner in which they
B

page_text: withstand exposure to the action of light and alkalies, but are by 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 alphylbenzyl meta toluylene diamines and nitroso compounds, or
azo compounds, or quinone imides or the like, on the other hand, by oxidation of
the said alphyl benzylmetatoluylene diamines conjointly with para diamines, are
illustrated by the following examples B, C, D, E, F, and G. The parts are by
weight.
COLOURING-MATTER OBTAINED FROM PHENYLBENZYLMETATOLUYLENE-
DIAMINE AND NITROSODIMETHYLANILINE HYDROCHLORIDE.
28 parts of nitrosodimethylaniline hydrochloride are gradually stirred into a
solution of 29 parts of phenyl-benzyl-metatoluylene diamine, or phenylparamido
benzyl ortho toluidine, 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 nitroso dimethylaniline is no longer distinguishable. The dye-stuff
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 ortho-toluidine and nitroso dimethylaniline hydro-
chloride.
DYESTUFF OBTAINED FROM PHENYLBENZYLMETATOLUYLENEDIAMINE. AND
NITROSO-MONO-METHYLORTHOTOLUIDINE HYDROCHLORIDE.
29 parts of phenybenzylmetatoluylene diamine, or phenylparamido benzyl ortho
toluidine are dissolved in 100 litres (in case the parts are kilos. by weight) of
alcohol; 29 parts of nitroso mono-methylortho-toluidine hydrochloride are then
gradually stirred in, and the mixture is heated until the nitroso compound is no
longer distinguishable. On cooling the liquid, the dye-stuff entirely crystallizes
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."
out.
COLOURING-MATTER OBTAINED FROM PHENYLBENZYLMETATOLUYLENE
DIAMINE AND AMIDOAZO BENZENE.
The
41 parts of amidoazo benzene sulphate are added to a solution, in phenol, of
2.9 parts of phenyl benzyl-meta-toluylene-diamine, or phenylparamido monobenzyl
orthotoluidine, and the mixture is heated by means of a water bath, being stirred
the while, until the amidoazo compound is no longer distinguishable. The liquid
is then diluted with water, and subsequently supersaturated with soda-lye.
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
is isolated in the usual manner. On cotton mordanted with taunic acid or the like,
it produces clear red shades, distinguished by their fastness on washing and
exposure to light.

page_text: DYE-STUFF OBTAINED FROM PHENYL BENZYL-META-TOLUYLENE DIAMINE AND
BENZENE-AZO-ALPHA-NAPHTHYLAMINE.
A mixture of 2.9 parts of phenylbenzyl metatoluylene or phenyl paramido
benzylorthotoluidine and 4-3 parts of benzene azo alpha naphthylamine 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 dye-stuff 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 their fastness on exposure to
the action of alkalies, acids, and light.
COLOURING-MATTER PRODUCED FROM PHENYLBENZYLMETATOLUYLENE
DIAMINE AND QUINONE DICHLORDIIMIDE.
1-8 parts of quinonedichlordiimide are gradually added to a gently heated solution
in alcohol of 2.9 parts of phenyl paramido benzyl-ortho-toluidine. The mixture
is kept stirred and gently theated until the quinonedichlordi-imide 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 dye-stuff is salted out, filtered off, pressed, and dried.
This coloring matter is identical with that obtained, as described in the preceding
Example D, from phenylbenzylmetatoluylenediamine and amidoazo benzene.
DYESTUFF OBTAINED FROM PHENYLBENZYLMETATOLUYLENEDIAMINE AND
PARAMIDODIMETHYLANILINE.
2.9 parts of phenylparamidomonobenzylorthotoluidine 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 the color has turned
into pure magenta red, and the intensity of this color no longer increases. The
dye-stuff having been salted out, filtered off, and redissolved in water, the solution
is rendered alkaline with soda lyc, and filtered. The filtrate is acidulated with
muriatic acid, and the dyestuff is salted out, filtered off, pressed, and dried.
Other coloring 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 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 said Example G; or if, instead of the quinone
dichlordiimide prescribed in the foregoing Example F, other paraquinoncimides,
or chlorimides, are used, or by substituting, for phenyl benzylmetatoluylene
diamine, other alphyiparamido benzyl orthotoluidines hereinbefore defined, such as
paratolyl-paramido benzylorthotoluidine or the like. The oxidation effected in the
case of Example G by means of sodium dichromnie, can also be carried out by
using other oxidising agents suitable for these purposes.

page_text: 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 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 known methods in use for producing analogous dye-stuffs can be adopted. For
instance, other solvents, such glycerol or the like, can be used in place of the
solvents or diluents mentioned in the preceding examples.
As above stated, 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 subjected
to oxidation conjointly with the alphyl-benzyltriamidotoluenes obtainable from the
alphylbenzylmetatoluyleue diamines hereinbefore defined, or if primary, secondary,
or tertiary amines are condensed with the azo compounds formned by the combination
of diazo compounds with the alphylbenzylmetatoluylene diamines hereinbefore
referred to.
The said alphyl benzyltriamido toluenes åre represented by the general
foumule.
My foreign correspondents use the letter R, in the above formula, to indicate
radicles of amido compounds whose diazo derivatives are coupled with the
alphylbenzylmetatoluylene diamines.
The alphylbenzyltriamido toluenes can, for instance, be produced by nitrating
alphylbenzylmetatoluylene 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 alphylbenzylmetatoluylene diamine.
The process for producing azine dyestuffs from the last-named azo compounds,
or alphylbenzylmetatoluylene diamines, is illustrated by the following examples,
the parts being by weight.

page_text: COLORING MATTER PRODUCED FROM BENZENE SULPHONIC ACID AZOPHENYL-
BENZYLTOLUYLENE DIAMINE AND ALPHANAPHTHYLAMINE.
72 parts of benzene sulphonic acid azophenylbenzylmetatoluylene diamine
(obtained by coupling diazotised parasulphanilic acid with phenylbenzylmeta-
toluylene diamine) are finely pulverised and mixed with 14 parts of alphanaphthyl-
amine and 20 parts of phenol. The mixture is kept constantly 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
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 crystallises 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 azoalphanaphthylamine
and phenylbenzylmetatoluylenediamine.
DYE-STUFF OBTAINED FROM PHENYLBENZYLTRIAMIDO TOLUENE AND
ALPHANAPHTHYLAMINE.
3 parts of phenylbenzyltriamido toluene 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
manuer described in the Example H, in the case of the dye-stuff obtained from
benzene sulphonic acid azo phenylbenzyltoluylene diamine and alphanaphthylamine.
According to the researches of my foreign correspondents, these two dye-stuffs are
identical.
COLORING MATTER OBTAINED FROM PHENYLBENZYLTRIAMIDO TOLUENE AND
ALPHANAPHTHYLAMINE.
3 parts of phenylbenzyltriamido toluene and 14 parts of alphanaphthylamine
are dissolved in 20 parts of glacial acetic acid, and a solution of 3 parts of sodium
dichromate in the sinallest 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 sinall quantity
of hot water, and the filtered solution is mixed with muriatic acid. As 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.
Other dye-stuffs are formed in a manner analogous to that described in the
Examples H, I and K, by using, instead of benzene sulphonic acid azo-phenyl-
benzylmetatoluylene diamine, that is to say, the azo compound from diazotis:d
parasulphanilic acid and phenylparamidobenzylorthotoluidine, other azo compounds
obtained from diazo compounds, and the alphylbenzylmetatoluylene diamines herein-
before defined, or by using, instead of phenylbenzyltriamidotoluene, paratolylbenzyl-

page_text: triamido toluene, or other alphylbenzyltriamido 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, aud all
known methods in use for producing analogous coloring matters can be used.
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 alphylbenzylmetatoluylene diamines represented by the
(in which formula the expression "alphyl" signifies phenyl, tolyl, naphthyl, or the
like) from alphylmetatoluylene diamines, such as phenylmetatoluylene diamine
(CH, NH, NHCH, = 1:2:4), paratolylmetatoluylene diamine (CH, NH₂ :
NHC,H, = 1:24), or the like.
:
2. The process for producing alphylbenzylmetatoluylene diamines (such as
phenylbenzylmetatoluylene diamine, paratolylbenzylmetatoluylene diamine,
naphthylbenzylmetatoluylene diamine, or the like), which process consists in
benzylating alphylmetatoluylene diamines (such as phenylmetatoluylene diamine,
paratolylmetatoluylenediamine, naphthylbenzylmetatoluylenediamine, or the like).
3. The production of azine dye-stuffs from the alphylbenzylinetatoluylene
diamines herein before defined, and nitroso derivatives of secondary or tertiary
aromatic amines, or amidosulphonic acids.
4. The process for producing dyestuffs by condensing nitrosomonomethyl aniline,
nitrosomonomethylorthotoluidine, nitrosodimethylaniline, nitroso diethylaniline,
nitroso diphenylamine, or nitrosomethyl diphenylamine, or analogous nitroso
compounds, or nitrosomethylbenzylaniline sulphonic acid, nitrosomethyldiphenyl-
amine sulphonic acid, or analogous nitroso compounds, with phenylbenzylmeta-
toluylenediamine, paratolylbenzylmetatoluylene diamine, naphthylbenzylmeta-
toluylenediamine, or analogous alphylbenzylmetatoluylene diamines.
5. The production of azine coloring matters by acting with the alphylbenzyl-
metatoluylene diamines hereinbefore defined, either on paramidoazo 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-
quinoneimide, paraquinone chlorimides, or the like compounds of the benzene or
naphthalene series.
6. The process for producing azine dye-stuffs, which process consists in subjecting
the alphylbenzylmetatoluylene diamines hereinbefore defined, together with
paradiamines 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.

page_text: 7. The production of azine coloring matters from alphylbenzyltriamidotoluenes
represented by the general formula-
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 alphylbenzyltriamidotoluenes, 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 alphylbenzylmeta toluylene
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 alphyl benzylmetatoluylene
diamines.
9. As new products of manufacture,―
(a) The new alphylbenzylmetatoluylene diamines, such as phenylbenzylmeta-
toluylene diamine, paratolylbenzylmetatoluylene diamine, naphthylbenzyl-
metatoluylene diamine, or the like; and
(b) The new azine coloring matters produced by the processes hereinbefore
defined, or by any other means affording the same result.
NEWTON & SON,
Agents for the Applicant.