The Manufacture or Production of Dye-stuffs, and Materials therefor.
Year: 1894

page_text: Date of Application, 20th Nov., 1894
Complete Specification Left, 5th Sept., 1895-Accepted, 5th Oct., 1895
[Communicated from abroad by THE FARBENFABRIKEN, Vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of 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 some time since discovered, that when heated with
aniline or its homologues or analogues in the presence of any acid, meta-toluylene
diamine is converted into phenyl paramidoorthotoluidine, or homologues or analogues
thereof, whilst the amido group in the "ortho" position relatively to the methyl
group contained in the meta-toluylene diamine used, is not substituted, alkyl meta
toluylene diamines being thus formed.
The products thus obtained possess the following general formula, in which any
aromatic radicle of the benzene series is understood by the expression R :-
The researches of my foreign correspondents have now shown that the naphtyl
radicle, or substituted naphtyl radicle, can be easily substituted for a hydrogen
atom contained in the free amido group of the alkylmetatoluylene diamines herein-
before referred to, if the said compounds, viz., phenyi paramido orthotoluidine, its
homologues or analogues, are heated with naphthols, or derivatives thereof (such as
naphtholsulphonic acids), in the presence of, or without condensing agents, such as
acids, calcium chloride, zinc chloride, or the like.
My foreign correspondents ascribe the following general formula to these new
compounds obtained, for instance, by means of naphthol, viz. :—

page_text: According to the researches of my foreign correspondents, the alkylated derivatives
of meta phenylene diamine (such as metamido diphenylamine, metamidophenyl-
tolylamine, the homologues or analogues thereof), when heated with naphthols or
naphthol derivatives, in the presence of, or without, condensing agents, show a
behaviour analogous to that possessed by the alkylated derivatives of metatoluylene
diamine hereinbefore referred to (such as phenylparamido orthotoluidine, tolylpar-
amido orthotoluidine, or the like). For instance, metamido diphenylamine, which
is an alkylated metaphenylene diamine, is, by heating with beta naphthol, converted
into the symmetrical phenyl naphthylmetaphenylene diamine having the formula :-
The process for producing these new symmetrically dialkylated derivatives of
meta phenylene diamine and metatoluylene diamine, is illustrated by the following
Examples (One and Two). The parts are by weight.
PRODUCTION OF PHENYLPARAMIDOBETANAPHTHYLORTHOTOLUIDINE
PHENYL PARAMIDOORTHOTOLUIDINE AND BETA NAPHTHOL.
FROM
A mixture prepared from 1 part of phenyl paramidoorthotoluidine and about
2 parts of betanaphthol, is heated, during about 20 hours, at from 230 to 240 degrees
Centigrade, whilst a current of carbon dioxide is allowed to pass through the
heated mass.
The mass, when cool, is first boiled with dilute soda lye, and
subsequently with dilute muriatic acid, in order to remove the betanaphthol added
in excess, and the unaltered phenylparamidoorthotoluidine, if any. The residue is
crystallised from alcohol, and the phenylparamido beta naphtbylorthotoluidine
having the formula-
separates from the cooling alcoholic solution, in the form of light gray scales, and,
by recrystallisation from alcohol, snow white crystals are obtained melting at from
119 to 120 degrees Centigrade.
This new base dissolves with difficulty in cold alcohol, and more readily in hot
alcohol. It is soluble in ether and benzene with readiness, but only slightly in
ligroine.

page_text: PRODUCTION OF PARATOLYL PARAMIDO BETANAPHTHYL ORTHOTOLUIDINE
FROM PARATOLYL PARAMIDOORTHOTOLUIDINE AND BETA NAPHTHOL.
.
1 part of paratolylparamido orthotoluidine hydrochlorate is introduced into
2 parts of beta naphthol, heated at from 270 to 280 degrees Centigrade. The
resulting mass is further heated until the disengagement of hydrochloric acid and
water is no longer distinguishable. The mass thus obtained is treated in the manner
described in the foregoing example.
The paratolylparamidobetanaphthyl orthotoluidine thus produced has the
It dissolves with readiness in ether alcohol and benzene, but less readily in
ligroine. It crystallises in masses grouped in the shape of balls, on allowing its
solutions in a mixture of benzene and ligroine to evaporate slowly.
The process proceeds in a manner analogous to that described in the preceding
two examples, if the phenylparamidoorthotoluidine and the paratolylparamidoortho-
toluidine used therein are replaced by equivalent quantities of homologues or
analogues thereof, or of alkylated derivatives of metaphenylenediamine (such as
metamidodiphenylamine, metamidophenyltolylamine, or analogues or homologues
thereof), or if alphanaphthol, or derivatives of alpha or betanaphthol, for instance,
naphtholsulphonic acids, are used in place of beta naphthol.
A symmetrical phenylbetanaphthylmetaphenylenediamine, having the formula-
results from metamidodiphenylamine and betanaphthol in the manner hereinbefore
referred to. The metamidodiphenylamine prepared by my foreign correspondents,
crystallises from benzene or ligroine in white needles grouped in the shape of balls,
melting at from 74 to 75 degrees Centigrade. It can be distilled without being
decomposed. It dissolves with readiness in alcohol, ether, ligroine, and benzene,
and forms a hydrochlorate which is but slightly soluble in water.
The researches of my foreign correspondents have shewn that these symmetrically
dialkylated derivatives of metaphenylenediamine and metatoluylenediamine, which
are hereinafter briefly termed "naphthylated derivatives of metaphenylenediamine
and metatoluylene diamine," when acted on by nitroso derivatives of secondary or
tertiary aromatic amines, or substituted amines, yield valuable dyestuffs, in general
distinguished for their fastness.
According to the researches of my foreign correspondents the same or similar

page_text: dyestuffs are obtained on using, in place of the said nitroso compounds, all those
products which act in an analogous manner, for instance, paraquinonimides, chinon-
chlorimides of the benzene or naphthalene series, or paramidoazo compounds
obtainable by coupling primary or secondary or tertiary amines, or substituted:
amines, of the benzene or naphthalene series, with any diazo products.
In order to illustrate the production of these dyestuffs from nitroso compounds,
the following Examples (Three and Four) are given. The parts are by weight.
COLOURING
NITROSODIETHYLANILINE
HYDRO-
MATTER OBTAINED FROM
CHLORATE AND PHENYLPARAMIDOBETA-NAPHTHYL ORTHOTOLUIDINE.
3.3 parts of nitrosodiethylaniline hydrochlorate, mixed with alcohol, are gradually
stirred into a solution prepared by dissolving 3-2 parts of phenyl paramidobeta-
naphthylorthotoluidine in 50 litres (in case the parts are kilos. by weight) of
alcohol. The resulting mixture is stirred, with or without applying heat, until the
nitroso compound used is no longer distinguishable, about 1 litre of hydrochloric
acid (in case the parts are kilos. by weight) is then added, and the liquid thus
formed is diluted with water. The colouring matter is precipitated by an addition
of muriatic acid, and is filtered off and pressed. To purify this colouring matter,
it is dissolved in hot water, and the filtered solution is mixed with muriatic acid.
The dye-stuff thus precipitated is filtered off, pressed, dried, and reduced to a fine
powder. It dissolves easily in hot water, & particularly so in the presence of
acetic acid, but with difficulty in cold water. It produces bright blue shades on
cotton prepared with tannic acid or the like, and the resulting shades are distinguished
for their fastness against the action of washing and light.'
DYESTUFF OBTAINED FROM NITROSO DIMETHYLANILINE HYDROCHLORATE
AND PARATOLYL PARAMIDO BETANAPHTHYLORTHOTOLUIDINE.
3-3 parts of paratolylparamidobetanaphthylorthotoluidine are dissolved in
20 litres of alcohol (in case the parts are kilos. by weight) and 2-8 parts of nitroso-
dimethylaniline hydrochlorate (mixed with alcohol) are gradually stirred into
the resulting solution. The mixture is subjected to a moderate heat, and is
continuously stirred, until the nitroso compound is no longer distinguishable.
After adding about 1 litre of muriatic acid, the mixture is diluted with water, and
the dyestuff is completely precipitated by means of muriatic acid. In order to
purify the colouring matter, it is redissolved in water, and after filtering this
solution, the dyestuff is precipitated by means of muriatic acid, filtered off, pressed,
dried, and pulverised. It produces ou cotton prepared with tannic acid or the like,
clear blue shades fast against the action of light and washing.
Analogous dye-stuffs result if other nitroso derivatives of secondary or tertiary
aromatic amines, or substituted amines, are used in place of nitroso-dimethyl
aniline, or nitrosodiethylaniline, used in the two last examples, or if the basic
compounds used therein, viz., phenylparamidobetanaphthylorthotoluidine and
paratolyl paramidobetanaphthy lorthotoluidine are replaced by equivalent quantities
of other of the "naphthylated derivatives of metaphenylenediamine or meta-
toluylenediamine" hereinbefore defined.
In order to produce these colouring matters, my foreign correspondents do not
limit themselves to the directions given in Examples Three and Four, as these can be
varied; for instance, other solvents or diluents, such as acetic acid, glacial acetic
acid, glycerine, phenol, or the like, can be used in place of alcohol used in these
examples.

page_text: As above mentioned, all products which are capable of acting in the same or an
analogous manner can be used in place of the nitroso derivatives, for instance,
paraquinonediimides, paraquinone chlorimides of the benzene or naphthalene series,
or paramidoazo products resulting from the combination of primary or secondary
or tertiary aromatic amines, or substituted amines, with any diazo products, using,
for instance, dimethylamidoazobenzene. The production of the colouring matters
from the last-named materials, and the naphthylated derivatives of metaphenylene-
diamine and metatcluylene diamine herein before referred to, is effected in the
manner well known and in use for the production of analogous dyestuffs.
My foreign correspondents have also found that the same or similar colcuring
matters can be obtained by a joint oxidation of the "naphthylated derivatives of
metaphenylenediamine and metatoluylenediamine" with the alkylated paradiamines,
or substituted alkylated paradiamines, corresponding to the said nitroso compounds
(such as paramidodimethylaniline, paramido diethylaniline, or the like). This
oxidation is effected by means of all those methods known and in use for analogous
purposes.
The researches of my foreign correspondents have further shewn, that in place
of heating the "naphthylated derivatives of metaphenylenediamine, or meta-
toluylenediamine," with the amido azo products derived from primary or secondary
or tertiary aromatic amines, or in place of jointly oxidising the "naphthylated
derivatives of metaphenylenediamine or metatoluylenediamine," with the alkylated
paradiamines corresponding to the said nitroso compounds, the same or similar
dyestuffs can also be obtained by heating the azo derivatives of the "naphthylated
derivatives of metaphenylenediamine or metatoluylenediamine" (such as sulphanilic
acid-azo phenylparamidobetanaphthylorthotoluidine), with aromatic amido com-
pounds, or by jointly oxidising aromatic amido compounds with the amido products
(such as amidophenylparamidobetanaphthylorthotoluidine) obtainable by reducing
the azo derivatives of the said "naphthylated derivatives of metaphenylenediamine,
or metatoluylenediamine," or in any other suitable manner. These two processes
likewise are effected in the manner well known and in use for producing analogous
dyestuffs.
The products obtained by means of the processes herein before defined, which
are insoluble, or soluble with difficulty, may be sulphonated (for instance by means
of fuming sulphuric acid), in order to render them soluble, or soluble with greater
ease.
Dated this 20th 1.
AT
L
1304
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 aud by the following statement :-
My foreign correspondents have stated in the Specification of Letters Patent
No. 9610, dated 16th May 1894, that when metatoluylene diamine is heated with
aniline or its homologues in the presence of any acid, it is converted into phenyl-
paramido-ortho-toluidine, or homologues thereof, the amido group in the "ortho
position relatively to the methyl group contained in the meta-toluylenediamine
used, remaining unaltered, alkyl metatoluylenediamines being thus formed.
"

page_text: The products thus obtained are represented by the following general formula,
R representing any aromatic radicle of the benzene series :-
The researches of my foreign correspondents have now shown, that the naphtyl
radicle can be easily substituted for a hydrogen atom contained in the unchanged
amido group of the alkyl-meta-toluylene diamines hereinbefore referred to, by
heating the said compounds, viz., phenyl paramido-ortho-toluuidine, or its homologues,
with naphthols, either alone, or in the presence of condensing agents, such as acids,
calcium chloride, zinc chloride, or the like.
My foreign correspondents ascribe the following general formula to these new
compounds obtained by means of naphthol, viz. :—
in which R represents any aromatic radicle of the benzene series.
According to the researches of my foreign correspondents, the behaviour of the
alkyl derivatives of meta phenylenediamine (such as metamidodiphenyl amine,
metamidophenyltolylamine, the homologues or analogues thereof), when they are
heated with naphthols in the presence of, or without, condensing agents, is analogous
to that of the alkyl derivatives of meta-toluylene diamine herein before referred to
(such as phenylparamido-ortho-toluidine, tolyl paramido-ortho-toluidine, or the
like). For instance, by heating metamido diphenylamine, which is an alkylated
metaphenylene diamine with beta naphthol, it is converted into the symmetrical
phenylnaphthylmetaphenylenediamine represented by the formula:

page_text: PRODUCTION OF PHENYL PARAMIDOBETANAPHTHYLORTHOTOLUIDINE FROM
PHENYL PARAMIDO-ORTHOTOLUIDINE AND BETANAPHTHOL.
A mixture of 1 part of phenyl paramido orthotoluidine and about 2 parts of
betanaphthol is heated during about 20 hours at from 280 to 320 degrees Centi-
grade, whilst a current of carbon dioxide is allowed to pass through the heated
mass. The cool product is then boiled with dilute soda-lye, and the residue having
been dried, is crystallised from a mixture of benzene and ligroine. After
recrystallization from alcohol, the phenyl paramido betanaphthylorthotoluidine.
represented by the formula:
PRODUCTION OF PARATOLYL PARAMIDO BETA NAPHTHYLORTHOTOLUIDINE
FROM PARATOLYLPARAMIDO ORTHO TOLUIDINE AND BETA NAPHTHOL.
1 part of paratolyl paramido orthotoluidine hydrochloride is introduced into
2 parts of betanaphthol heated at from 240 to 250 degrees Centigrade, and the
mixture is further heated until the disengagement of hydrogen chloride and water
is no longer perceptible. The mass thus obtained is treated in the manner described
in the foregoing example.
The paratolyl paramido betanaphthylorthotoluidine thus produced has the
This symmetrically dialkylated metatoluylene diamine dissolves with rediness
in ether, alcohol, and benzene, less readily in ligroine. It crystallises in spherical
0 masses on allowing its solutions in a mixture of benzene and ligroine to evaporate
slowly. It melts at from 82 to 83 degrees Centigrade.

page_text: The process proceeds in a manner analogous to that described in the preceding
two examples on using, instead of phenylparamidoortho toluidine and paratolyl
paramido ortho toluidine, equivalent quantities of homologues or analogues thereof,
or of alkylated derivatives of metaphenylenediamine (such as metamido diphenyl-
amine, metamidophenyl tolylamine, or analogues thereof), or if alpha naphthol is
used in place of beta naphthol.
Thus, for instance, when paratolylparamido ortho toluidine hydrochloride and
alpha naphthol are beated together in the manner described in the foregoing last
example, paratolylparamido alphanaphthyl ortho toluidine is produced, which
dissolves with readiness in ether, benzene, chloroform, and acetone. It dissolves
with great difficulty in ligroine, and in cold alcohol, but easily in hot alcohol,
separating from hot alcoholic solutions in colourless scales melting at 121 degrees
Centigrade.
A syinmetrical phenyl beta naphthylmetaphenylenediamine having the
may be produced from metamido diphenylamine and betanaphthol in the manner
herein before referred to. This symmetrical phenylbetanaphthylmetaphenylene
diamine crystallises from benzene or ligroine in spherical groups of needles melting
at from 74 to 75 degrees Centigrade. It dissolves with readiness in alcohol, ether,
ligroine and benzene, and forms a hydrochloride which is but slightly soluble in
water.
The researches of my foreign correspondents have shewn, that the symmetrically
dialkylated metaphenylene diamines and metatoluylenediamines hereinbefore
referred to, may be converted by means of nitroso derivatives of secondary or
tertiary aromatic amines, or substituted amines, into valuable azine dye stuffs,
generally distinguished for their fastness.
According to the researches of my foreign correspondents, the same or similar
dyestuffs are obtained on using, in place of the said nitroso compounds, all products
which act in an analogous manner, for instance, para quinoneimides, quinone-
dichlorimides of the benzene or naphthalene series, or paramido azo compounds
formed by the combination of diazo derivatives with primary or secondary or
tertiary amines, or substituted amines, of the benzene or uaphthalene series.
In order to illustrate the production of these dye stuffs from nitroso compounds,
the following Examples (Three and Four) are given. The parts are by weight.
COLOURING
OF
MATTER OBTAINED FROM MOLECULAR PROPORTIONS
NITROSODIETHYLANILINE HYDROCHLORIDE AND 1 MOLECULAR PROPOR-
TION OF PHENYL PARAMIDO-BETA-NAPHTHYL ORTHOTOLUIDINE.
10 parts of nitrosodiethylaniline hydrochloride are added to a solution of
10 parts of phenylparamido beta-naphthylorthotoluidine in 100 litres (in case the
parts are kilos. by weight) of alcohol. The mixture is stirred first at the ordinary
temperature, afterwards at a somewhat higher temperature, until the nitroso-
compound used is no longer distinguishable. The whole is then poured into hot
water, and after filtering the liquid, the dyestuff is salted out from the filtrate, and

page_text: isolated in the usual manner. It easily dissolves in hot water, and particularly so
in the presence of acetic acid, but with difficulty in cold water. It dyes cotton
prepared with tannic acid, or the like, bright indigo-blue shades which are
distinguished for their fastness both on washing and exposure to light.
NITROSO
PROPORTION
DYE STUFF OBTAINED FROM 3 MOLECULAR PROPORTIONS OF
DIMETHYLANILINE HYDROCHLORIDE AND 1 MOLECULAR
OF PHENYL PARAMIDO BETANAPHTHYLORTHOTOLUIDINE.
10 parts of phenyl paramido-betanaphthylortho toluidine are dissolved in 100 litres
of alcohol (in case the parts are kilo's. by weight), and 8.6 parts of nitroso-
dimethylaniline hydrochloride are gradually stirred into the solution,, and the
stirring is continued at the ordinary temperature, until the nitroso compound is no
longer distinguishable. 8-6 parts of nitroso dimethylaniline hydrochloride and
3.1 parts of zinc chloride are then added, and the mixture is boiled until the
nitroso compound is no longer distinguishable. The product is then treated with
hot water, and the dye-stuff is precipitated from the filtrate, either by salting out
or by acidulating with muriatic acid, and isolated in a suitable manner. This
dyestuff is very similar to that obtained according to the foregoing third example,
in dyeing and other properties, but is superior to the latter, owing to its greater
solubility.
Analogous dyestuff's are formed if other nitroso derivatives of secondary or
tertiary aromatic amines, or substituted amines, are used in place of the nitroso
dimethylaniline, or nitroso diethylaniline used in the two last examples, or if,
instead of the phenylparamidobetanaphthylorthotoluidine prescribed therein, the
equivalent quantities of another of the symmetrically "dialkylated metaphenylene
diamines, or meta toluylene diamines" herein before defined, is used.
In producing these colouring matters, however, my foreign correspondents do
not limit themselves to the directions given in examples three and four, as these
can be varied; for instance, other solvents or diluents, such as acetic acid, glacial
acetic acid, glycerine, phenol, or the like, can be used in place of alcohol mentioned
in the examples.
:
As above mentioned, the same or similar dyestuffs can be obtained by using, in
place of the nitroso derivatives, for instance, paraquinonediimides, paraquinone-
chlorimides of the benzene or naphthalene series, or paramidoazo products formed
by the combination of diazo derivatives with primary or secondary or tertiary
aromatic amines, or substituted amines, using, for instance, dimethyl amido azo
benzene. The production of the colouring matters from the last named materials
and symmetrically dialkylated metaphenylene diamines and metatoluylene diamines
hereinbefore referred to, is effected in the well-known manner in use for the
production of analogous dyestuffs.
The following examples (five and six) may serve to illustrate the production of
the dyestuffs in the last defined manner. The parts are by weight.
COLOURING-MATTER
FROM PHENYLPARAMIDO
BETANAPHTHYLORTHO-
TOLUIDINE AND QUINONE DICHLORDIIMIDE.
3.2 parts of phenyl paramido betanaphthylorthotoluidiue are dissolved in alcohol,
and the moderately heated solution is gradually mixed with 18 parts of quinone
dichlordiimide, taking care that the mass is well stirred. Heating is continued
until the quinone dichlordiimide is no longer distinguishable. The alcohol is then
b

page_text: distilled off. After diluting with water, and super-saturating with soda lye, 'the
precipitate is filtered off and pressed. The press-cake is repeatedly boiled with
water and acetic acid, until dyestuff is no longer dissolved out from it. The
combined filtrates are acidulated by means of muriatic acid, and the dyestuff is
salted out, filtered off, pressed, and dried. The colouring matter thus produced
produces reddish violet shades on cotton prepared with tannic acid or the like.
COLOURING MATTER FROM PHENYLPARAMIDO BETANAPHTHYLORTHO-
TOLUIDINE AND BENZENE AZO ALPHA NAPHTHYLAMINE.
A mixture of 3.2 parts of phenyl paramidobetanaphthylorthotolnidine and
4.3 parts of benzene azo alphanaphthylamine hydrochloride, is introduced into
20 parts of phenol. The mixture is heated by means of a water bath, until the azo
compound is no longer distinguishable. After diluting with water and super-
saturating with soda-lye, the precipitate is filtered off and pressed. After adding
acetic acid, the press cake is repeatedly boiled with water, until dyestuff no longer
dissolves. The filtrates are acidulated with muriatic acid, and the dye-stuff is
salted out, filtered off, pressed, and dried. The colouring matter thus obtained
produces reddish-violet shades on cotton prepared with tannic acid or the like.
My foreign correspondents have also found, that the same or similar colouring
matters can be obtained by conjointly oxidising the symmetrically dialkylated
metaphenylenediamines, or metatoluylenediamines, and paradiamines, herein before
defined, or the alkylated paradiamines or substituted alkylated paradiamines
corresponding to the said nitroso compounds (such as paramidodimethylaniline,
paramidodiethylaniline, or the like). The oxidation, which can be effected by means
of all the well-known methods in use for analogous purposes, is illustrated by the
following example. The parts are by weight.
COLOURING MATTER OBTAINED BY SUBJECTING PHENYLPARAMIDO
BETA-
NAPHTHYLORTHO TOLUIDINE AND PARAMIDO DIETHYLANILINE TO A
JOINT OXIDATION.
3.2 parts of phenyl paramido betanaphthylorthotoluidine and 2 parts of paramido-
diethylaniline hydrochloride, are dissolved in about 50 parts of alcohol. A solution
of 3 parts of sodium dichromate in the smallest possible quantity of water is
gradually added to the liquid, which is kept constantly stirred and moderately
heated. The dye-stuff is afterwards salted out and purified by redissolving it, and
again precipitating. It is identical with the colouring matter obtained as described
in the preceding third example.
The researches of my foreign correspondents have further shewn that instead of
heating the "symmetrically dialkylated metaphenylenediamines or metatoluylene-
diamines "bereinbefore defined, with the amidoazo products derived from primary
or secondary or tertiary aromatic amines, or instead of conjointly oxidising the
"symmetrically dialkylated metaphenylenediamines or metatoluylene diamines,"
and the paradiamines or alkylated paradiamines corresponding to the said nitroso
compounds, the same or similar dyestuffs can also be obtained by heating the azo
derivatives of these "symmetrically dialkylated metaphenylenediamines or meta-
toluylenediamines" (such as sulphanilic acid azophenylparamido betanaphthylortho-
toluidine), with aromatic amido compounds, or by subjecting to a conjoint oxidation
aromatic amido compounds and the amido compounds (such as amidophenyl-
paramidoletanaphthylorthotoluidine) obtainable by reducing the azo derivatives of

page_text: the said "symmetrically dialkylated metaphenylenediamines or metatoluylen -
diamines," or in any other suitable manner. These two processes are carried out
in the well-known manner in use for producing analogous dyestuffs.
Having now particularly described and ascertained the nature of the said inven-
tion 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 "symmetrically dialkylated metaphenylenediamines," such
as phenylnaphthylmetaphenylenediamine, paratolylnaphthylmetaphenylenediamine,
or similar compounds, represented by the general formula
(in which formula, R signifies any aromatic alkylic radicle), by heating, at elevated
temperatures, phenylmetaphenylenediamine, paratolylmetaphenylene diamine, or
the like monoalkylated metaphenylene diamines, with alpha or beta naphthol in the
presence of, or without, condensing agents.
2. The production of "symmetrically dialkylated metatoluylenediamines," such
as phenylnaphthylmetatoluylenediamine or phenylparamidonaphthylorthotoluidine,
paratolylnaphthylmetatoluylenediamine, or paratolylparamidonaphthylorthotolui-
dine, or the like compounds represented by the general formula
(in which formula, R signifies any aromatic alkylic radicle), by heating, at elevated'
temperatures, phenylmetatoluylenediamine, paratolylmetatoluylenediamine, or the
like monalkylated metatoluylene diamines, with alpha or betanaphthol, in the
presence of, or without, condensing agents.
"
3. The process for producing azine dyestuffs from the "symmetrically dialkylated
metaphenylenediamines" or "symmetrically dialkylated metatoluylenediamines"
berein before defined, and nitroso derivatives of secondary or tertiary aromatic
amines or substituted amines.
4. The process for producing azine colouring matters, which process consists in
acting with the " symmetrically dialkylated metaphenylene diamines or meta
toluylene diamines" hereinbefore defined, either on paraquinone imides, para-
quinone chlorimides, or the like compounds of the benzene or naphthalene series,
or an paramidoazo products formed by the combination of diazo compounds with
primary, secondary, or tertiary amines, or substituted amines, of the benzene or
naphthalene series.
5. The production of azine dyestuffs by conjointly oxidising, in the presence of
suitable solvents or diluents, the "symmetrically dialkylated metaphenylenediamines
or metatoluylenediamines" hereinbefore defined, and paradiamines, or alkylated

page_text: paradiamines, or paradiaminesulphonic acids, containing, in one of their amido
groups, either a single or two alkyl radicles.
6. The process for producing azine colouring matters by heating the azo
derivatives of the "symmetrically dialkylated metaphenylenediamines or meta-
toluylene diamines" herein before defined, with aromatic amido compounds, or by
conjointly oxidising, in the presence of suitable solvents or diluents, aromatic
amido compounds, and the compounds derived from the "symmetrically dialkylated
metaphenylene diamines or metatoluylene diamines" hereinbefore defined, and
obtainable, for instance, by reducing the azo derivatives of the said "symmetrically
dialkylated metaphenylene diamines or metatoluylenediamines."
7. As new products of manufacture :-
a.) The new "symmetrically dialkylated metaphenylenediamines and meta
toluylene diamines"; and
b.) The new dye-stuffs produced by the processes hereinbefore defined, or by
any other means affording the same result.
Dated this 20th do of Au 1905
NEWTON & SON,
Agents for the Applicant.