The Manufacture or Production of Colouring-matters, and Materials therefor.
Year: 1894

page_text: Date of Application, 16th May, 1894
Complete Specification Left, 18th Feb., 1895-Accepted, 23rd Mar., 1895
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Colouring-matters, 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:-
It is known that meta phenylenediamine hydrochloride is, by heating with
aniline, paratoluidine, or other aromatic monoamido compounds at temperatures
from about 260 to 270 degrees Centigrade, converted into diphenyl meta phenylene
diamine, ditolyl-meta-phenylene diamine, or the like.
"
My foreign correspondents have now found that this reaction proceeds in
another manner, if meta toluylene diamine hydrochloride is used in place of meta-
phenylene diamine, monophenyl or monotolyl, or analogous monvalkyl derivatives
of meta toluyleue diamine, being thus formed. My foreign correspondents presume,
that one of the hydrogen atoms of the amido group being relatively in the "para
position to the methyl group contained in the meta-toluylene diamine used, is
displaced by phenyl, tolyl, or the like, that is to say, on heating meta-toluylene-
diamine hydrochloride, for instance, with aniline or paratoluidiue, products are
obtained which probably possess the respective formulæ :
PRODUCTION
OF
DIAMINE
FROM
META
TOLYL-META-TOLUYLENE
TOLUYLENE DIAMINE AND PARATOLUIDINE.
1 part of meta toluylene diamine hydrochloride, or the corresponding quantity
of another salt of meta-toluylene diamine, is mixed with 4 parts of paratoluidine,
and the resulting mixture is heated during about 20 hours in a vessel capable of
withstanding pressure at from 260 to 270 degrees Centigrade. After saturating
with soda lye in excess, the para toluidine not altered is distilled over by means of
.
A

page_text: steam. The remaining oil, whilst hot, is separated from the watery alkaline
solution, and then boiled with water, in order to remove the meta toluylene diamine
not altered, if any. The oil thus obtained is mixed with a slight excess of muriatic
acid and a large quantity of water! The mixture is then heated to the boiling
point, until a dissolution of the oily mass is no longer distinguishable.. A residue
remains which is paraditolylamine, formed during the said reaction. After filtering
off the latter insoluble product, the resulting filtrate contains merely the hydro-
chloride of paratolyl-meta toluylene diamine, or meta-amidoditolylamine, which,
owing to its small, degree of solubility in cold water, separates on cooling in the
form of brilliant scales, or flat needles, which dissolve. in alcohol with great
readiness, whilst they are insoluble in ether. In order to obtain the free base, the
hot watery solution of the said meta+amido ditolylamine hydrochloride; after adding
a small quantity of muriatic acid and treating with bone dust, is mixed with
ammonia. The free meta-amido ditolyl-amine is thus precipitated as an oil which
solidifier in crystalline state, on cooling, and being allowed. to.stand....The base
crystallises from ligroine in stiff, snow-white, prismatic crystals, melting at from 69
to 70 degrees Centigrade. It dissolves with great readiness in ether, methyl-
alcohol, ethylalcohol, and benzene, whilst it is soluble with difficulty in ligroine,
and insoluble in water. It can be diazotised in the presence of muriatic acid, and
the diazo compound thus obtained, forms dyestuffs, when it is allowed to act on
phenols or amines, or the like.
The process takes place in a manner analogous to that described in the foregoing
example, if aniline or other homologues thereof or substitution derivatives of
primary aromatic amines are used in place of metatoluylene diamine, and if these
amido. compounds are allowed to act on meta toluylene diamine hydrochloride,
or other salts of this diamine. The monoalkylated derivatives of metatoluylene
diamine thus obtained, in general shew the same properties as the above-named
para tolyl meta toluylene diamine or meta-amidoditolylamine.
According to the researches of my foreign correspondents, the process can also be
carried out by heating the salts of primary aromatic amines, or substituted amines,
with the free meta toluylene diamine, in place of heating, inversely, the salts of
meta toluylene diamine with the free primary aromatic amines. Or, a mixture
containing the free metatoluylene diamine and primary aromatic amines or sub-
stituted amines can, after adding any suitable acid, be heated at elevated
temperatures, in order to effect the formation of the said monoalkyl derivatives of
meta toluylene diamine. The researches of my foreign correspondents have also
shewn, that the production of these monoalkylated meta toluylene diamines can
generally be hastened by adding benzoic acid, or other agents facilitating the
action in a similar manner.
My foreign correspondents have further found, that the monoalkyl derivatives
of meta toluylene diamine, hereinbefore defined, are capable of being easily and
evenly, condensed with the nitroso, derivatives of secondary or tertiary aromatic
amines or substituted amines, or, generally, with all those, substances which act in
a manner analogous to that of the said nitroso compounds. Valuable azine
colouring matters are thus obtained which, in chief, produce from red to violet
shades distinguished by their brilliancy and fastness against the action of washing
and light. My foreign correspondents-speaking of substances which act in a
manner analogous to that of nitroso derivatives-chiefly mean quinone chloroimides
or azo products resulting from the combination of diazo derivatives with primary
or secondary or tertiary amines or substituted amines of the benzene or naphthalenc
series.
According to the researches of my foreign correspondents, the colouring matters
hereinbefore defined can also be obtained by using, in place of chlorimides or nitroso
compounds, the corresponding products obtainable therefrom by reduction, such as
the alkylated paradiamines, or derivatives of alkylated paradiamines, containing a
free amido group. In the latter case, it is necessary to subject these alkylated
paradiamines, or derivatives thereof, together with the monoalkylated metatoluylene

page_text: liamines herein before defined, to a joint oxidation, for instance, by means of
ferric chloride, or bichromate or manganese dioxide, in the presence of acetic acid
or the like.
In order to illustrate the production of these azine dye-stuffs, the following
examples are given. The parts are by weight:
COLOURING MATTER OBTAINED FROM META-AMIDO PHENYLTOLYLAMINE
AND NITROSO DIMETHYLANILINE HYDROCHLORIDER
!.
23.5 parts of the hydrochloride of meta-amidophenyltolylamine, or phenyl
nieta toluylenediamine (obtainable by 'condensing meta tolaylenediamine hydro!
chloride with aniline) are dissolved in 100 litres of alcohol (in case the parts are:
kilos. by weight), and 27.7 parts of nitroso dimethylaniline: hydrochloriden are
gradually added to the resulting solution, while cold. Without applying heat, the
resulting mixture is stirred, until the nitroso compound is no longer distinguishable,
and the solution thus formed has assumed a deep blue colour. The liquid is then
heated in a vessel provided with a reflux condenser, until the colour of the liquid has
turned into a pure brilliant red. The alcohol is then distilled over, and the residue
is treated with hot water. After filtering, the hot filtrate is mixed with a solution,
in water, of common salt. On cooling, the dye-stuff separates in small scales,
which are subsequently filtered off and pressed. The colouring matter thus
obtained produces brilliant bluish-red shadesion cotton mordanted with tannic acid
the 1
DYE-STUFF: OBTAINED FROM META-AMIDO DITOLYLAMINE AND NITROSO
METHYLBENZYLANILINE SULPHONIC ACID. "
24-8 parts of meta-amido ditolylamine or para-tolyl-metatoluylenediamine (obtained
by condensing meta toluylene diamine hydrochloride with para-toluidine),, are
dissolved in 100 litres (in case the parts are kilos. by weight) of alcohol. The
resulting solution, when cold, is gradually mixed with 46 parts of nitroso methyl-
aniline sulphonic acid, and the liquid thus produced, while being gently heated, is
stirred until the nitroso compound is no longer distinguishable. The liquid is.
finally heated to the boiling point in a vessel provided with a reflux condenser,
until the original blue colour has changed into red. The greatest part of the
alcohol is then distilled off, and the remaining residue is boiled. up, after adding
water and an excess of a solution of sodium carbonate. The dyestuff thus produced,
which is soluble with difficulty, is finally filtered off. In order to convert it into a
product soluble with greater readiness, it is dissolved in muriatic acid, (containing
20 per cent. of pure acid), and the resulting blue solution is poured into a large
quantity of hot water. The colouring matter then separates in a crystalline state,
and dissolves in boiling water. It produces bluish-red shades on wool in neutral
or acidulated baths.
Analogous colouring matters result, if the nitroso compounds used in the pre-
ceding examples two and three, are replaced by the corresponding quantities of
nitroso derivatives of other tertiary or secondary amines or substituted amines, or
if orthotolyl, xylyl, or other monoalkyl derivatives of metatoluylenediamine are
used in place of, respectively, phenyl meta tolnylene diamine and para tolyl
meta toluylene diamine. Other solvents or diluents of neutral, basic, or acid nature,
can likewise be used in place of alcohol.
As above mentioned, the dye-stuffs hereiubefore defined can also be produced
by using, in place of nitroso compounds, all those substances which act in the same

page_text: or an analogous manner, such as quinone chloroimides, or the azo products resulting
from the combination of diazo derivatives with primary, secondary, or tertiary
aromatic amines, or substituted amines, of the benzene or naphthalene series. The
production of the colouring matters from the last named materials is carried out
according to the methods known and in use for the manufacture of analogous or
similar dyestuffs. Neutral, basic, or acid solvent can also be here used.
In order to produce the colouring matters hereinbefore defined by a joint
oxidation of alkylated paradiamines, or substituted alkylated para diamines,
containing a free amido group, with the above named monoalkyl derivatives of
meta toluylene diamine, all those processes can be used which are known and in
use for producing analogous dyestuffs.
My foreign correspondents have also found, that the dyestuffs obtainable as
herein before defined, can, by a subsequent treatment with suitable sulphonating
agents, be converted into colouring-matters which dissolve with greater readiness
than the original products.
Dated this 16th day of May 1894.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Colouring Matters, and Materials
therefor.
HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chaery Lane in the County of London, Patent Agent, do hereby declare the
natui 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 :-
It is known that when heated with aniline or paratoluidine, at temperatures from
about 260 to 270 degrees Centigrade, meta-phenylene diamine hydrochloride is
converted into diphenylmeta phenylene diamine, or ditolyl meta phenylene
diamine.
My foreign correspondents have now found that the action proceeds in another
manner, if metatoluylene diamine hydrochloride is used in place of metaphenylene
diamine hydrochloride, monophenyl or monotolyl metatoluylene diamine being thus
formed. My foreign correspondents presume that one of the hydrogen atoms of
the amido group in the para position relatively to the methyl group in the meta
toluylene diamine used, is displaced by phenyl or tolyl, that is to say, on heating,
for instance, meta toluylene diamine hydrochloride with aniline or para toluidine,
products are obtained which probably may be represented respectively by the
following formulæ :-

page_text: Naturally, other analogous alkyl derivatives of meta toluylene diamine are
obtained, on using the corresponding homologous amines in place of aniline or
paratoluidine.
One method of producing these monalkyl derivatives of meta toluylene diamine
is illustrated by the following example. The parts are by weight.
PRODUCTION OF PARATOLYL META-TOLUYLENE DIAMINE FROM META-
TOLUYLENE DIAMINE AND PARATOLUIDINE.
A mixture of 1 part of meta toluylene diamine hydrochloride (or the
corresponding quantity of another salt of meta toluylene diamine) with 4 parts of
para toluidine, is heated, during about 20 hours, at from 260 to 270 degrees
Centigrade, in a vessel capable of withstanding pressure. An excess of soda-lye
having been added, the unaltered paratoluidine is then distilled over by means of
steam. The remaining oil is separated, whilst hot, from the alkaline solution, and
is boiled with water, in order to remove unaltered metatoluylene diamine, if any be
present. The oil thus obtained is mixed with a slight excess of muriatic acid and
a large quantity of water, and the mixture is boiled until it is apparent that no
more of the oily mass will dissolve. The residue, consisting of para ditolylamine,
a bye-product of the said action, having been separated by filtration, a filtrate is
obtained containing merely the hydrochloride of paratolyl meta toluylene diamine
(paratolylparamidoorthotoluidine, or meta amidoditolylamine), which, owing to its
slight solubility in cold water, separates in the form of brilliant scales, or flat
needles, as the liquid cools. This salt dissolves in alcohol with great readiness, but
is insoluble in ether. When dissolved in water, it decomposes, undergoing
dissociation.
In order to obtain the base, the hot solution in water of the said meta-amido
ditolylamine hydrochloride is mixed with a small quantity of muriatic acid, digested
with animal charcoal, and then mixed with ammonia. The metamidoditolylamine
is precipitated as a light oil, which crystallises after a time. The base crystallises
from ligroin in star-shaped groups of snow-white prismatic crystals, melting at
from 69 to 70 degrees Centigrade. It dissolves with great readiness in ether,
methylalcohol, ethylalcohol, and benzene, but with difficulty in ligroin, and is
insoluble in water. It can be diazotised in the presence of muriatic acid, and the
diazo compound thus obtained forms dye-stuffs, when it is allowed to act on phenols
or amines, or the like.
The process takes place in a manner analogous to that described in the foregoing
Example A, if corresponding quantities of aniline, or other homologues thereof,
are used in place of para toluidine, and if these amido compounds are allowed to
act on metatoluylenediamine hydrochloride, or other salts of this diamine. The
monalkyl-meta toluylene diamines thus obtained, in general show properties similar
to those of the above-named paratolylmetatoluylene diamine (meta amidoditolyl-
amine or paratolylparamidoortho toluidine).
According to the researches of iny foreign correspondents, the process can also
be carried out by heating the salts of primary aromatic amines with meta tolaylene
diamine, instead of heating the salts of meta toluylene diamine with primary
aromatic amines. Or a mixture of meta toluylene diamine and a primary aromatic
amine, or substituted amine, with any suitable acid, may be heated at elevated
temperatures, in order to effect the formation of the said monalkylmetatoluylene
diamines. The researches of my foreign correspondents have also shown, that the
production of these monalkylmetatoluylene diamines can generally be facilitated by
adding benzoic acid, or other agents capable of producing a like effect.
Thus, for instance, the hydrochloride of phenylmetatoluylene diamine (phenyl-

page_text: paramidoorthotoluidine or amidotolylphenylamine) is formed on heating together
1 part of metatoluylene diamine, about 1 part and a half of aniline hydrochloride,
and 3 parts of aniline, during 10 hours, at from 240 to 250 degrees Centigrade,
in a vessel capable of withstanding pressure. The hydrochloride of phenylmeta-
toluylene diamine thus, formed can be isolated in the manner described in the above
example. It dissolves with difficulty in cold, bat readily in hot water, and to a
much greater extent than does the analogous hydrochloride of paratolylmeta-
toluylene diamine hereinbefore referred to. When treated in muriatic solution
with sodium nitrite, the said hydrochloride of phenylmetatoluyloue diamine also
yields a diazo compound which can be combined with amines or phenols to form
dye-stuffs. The base, viz., phenylmetatoluylenediamine exhibits properties
similar to those of the above mentioned paratolylmetatoluylene diamine. When
crystallized from ligroin, it forms stiff snow-white prismatic crystals grouped in
bundles or stars, and melting at from 76 to 77 degrees Centigrade.
My foreign correspondents have further found, that the monalkylmetatoluylene
diamines hereinbefore defined, may be easily and evenly condensed with the nitroso
derivatives of secondary or tertiary aromatic amines, or substituted amines, or,
generally, with all substances whose behaviour is analogous to that of the said nitroso
compounds. Valuable azine coloring matters are thus obtained, which mostly
produce from red to violet shades, distinguished by their brilliancy and fastness on
washing and exposure to light. In speaking of substances whose behaviour is
analogous to that of nitroso derivatives, my foreign correspondents chiefly mean
quinone chlorimides, quinonimides of the benzene or naphthalene series, or the like,
or paramido azo products formed by the combination of diazo derivatives with
primary or secondary or tertiary amines, or substituted amines, of the benzene or
naphthalene series.
According to the researches of my foreign correspondents, the colouring matters
herein before defined cau also be obtained by using, in place of chlorimides, or nitroso
compounds, the corresponding products obtainable therefrom by reduction, such as
the alkylated paradiamines or paradiaminesulphonic acids, containing either a
single or two alkyl radicles in one of the amido groups. In the latter case, it is
necessary to subject these alkylated paradiamines, or paradiamine sulphonic acids,
together with the monalkylated meta toluylenediamines hereinbefore defined, to a
joint oxidation, for instance, by means of ferric chloride, or bichromate or
manganese dioxide, in the presence of acetic acid or tlie like.
The production of the coloring matters from nitroso compounds, and the monalkyl
metatoluylene diamines above referred to, in general consists in allowing the nitroso
derivatives of secondary or tertiary aromatic amines to act, in the presence of a
suitable solvent or diluent, on phenylmetatoluylene diamine, or the analogous
monalkyl metatoluylene diamines, at ordinary temperature, and in subsequently
converting the so-formed indamines in the corresponding azine dye-stuff in a
suitable manner, profitably by heating. The said mixtures containing the nitroso
compound and the monalkylinetatoluylene diamine, can also be heated at once, as
it is not necessary to previously effect the complete formation of the indamine
compounds. It is also to be noted that in some cases the formation of the azine
dye-stuffs can be effected by allowing the aforesaid mixtures to stand during some
time at the ordinary temperature.
In order to illustrate the production of these azine dye-stuffs from nitroso
compounds, the following Examples B and C are given. The parts are by weight.
COLORING MATTER OBTAINED FROM META AMIDO PHENYLTOLYLAMINE AND
NITROSO DIMETHYLANILINE HYDROCHLORIDE.
23-5, parts of the hydrochloride of metamidophenyltolylamine or phenyl meta-

page_text: toluylene diamine (obtainable by condensing meta tolnylene diamine hydrochloride
with aniline), having been dissolved in 100 litres of alcohol (in case the parts are
kilos, by weight), 28 parts of nitroso-dimethylaniline hydrochloride are gradually
added to the cold solution, and the mixture is stirred until the nitroso compound is
no longer distinguishable, and the solution has assumed a deep blue color. The
liquid is then heated in a vessel provided with a reflux condenser, until it acquires a
pure bright-red color. At this stage, the alcohol is distilled off, the residue is
mixed with hot water, and the hot liquid is then mixed with a solution of common.
salt. As the liquid cools, the dye-stuff separates in small scales, which are filtered
off and pressed. The coloring matter thus obtained dissolves with readiness in
water, affording a red colored solution. It produces bright violet red shades on.
cotton mordanted with tannic.acid or the like.
DYE-STUFF OBTAINED FROM METAMIDODITOLYLAMINE AND NITROSOMONO-
METHYLORTHOTOLUIDINE.
28 parts of the hydrochloride of nitrosomonomethylorthotoluidine are gradually
added to a cold solution prepared by dissolving 24-8 parts of metamido ditolyl-
amine hydrochloride in 100 litres of alcohol (in case the parts used are kilos. by
weight), and the mixture is gently heated until action begins. It is then
unnecessary to continue heating, as an energetic action takes place, heat being
spontaneously given out. The dye-stuff entirely separates as the liquid cools, and
is filtered off and washed with alcohol. It is thus obtained sufficiently pure for
practical use. It produces red shades on cotton prepared with tannic acid or
the like.
•
- Analogous coloring matters are formed, if, instead of the nitroso compounds used
in the preceding Examples B and C, the corresponding quantities of nitroso
derivatives of other tertiary or secondary amines, or substituted amines, are taken,
or if equivalent quantities of orthotolylmeta toluylene diamine, or other nonalkyl-
metatoluylene diamines, are used in place of phenylmetatoluylene diamine, and
paratolylmetatoluylene diamine, respectively. Other solvents or diluents, such as
glacial acetic acid, dilute acetic acid, phenol, glycerol, or the like, can likewise be
used in place of alcohol.
In place of the hydrochlorides of the said monalkylmetatoluylene diamines, the
bases themselves can be used, alcohol being advantageously used as solvent in this
case.

page_text: In order to illustrate the variety of coloring matters thus obtainable, and the
shades which are produced by them on cotton prepared with tannic acid or the
like, or on wool in acid baths, the following table is given.
In the first column are the components of several dye-stuffs of this series, and
the second column indicates tbe shades obtainable on cotton prepared with tannie
acid or the like, or on wool in an acid bath, respectively.

page_text: COLORING MATTER OBTAINED FROM QUINONE DICHLORODIIMIDE AND PARA-
TOLYLPARAMIDOORTHOTOLUIDINE.
1-8 parts of quinone dichlorodiimide are gradually stirred into a gently heated
alcoholic solution of 2-5 parts of paratolylparamidoorthotoluidine hydrochloride,
and the mixture is gently heated, until the quinone dichlorodiimide is no longer
distinguishable. At this stage, the alcohol is distilled off, and the residue is mixed
with hot water. The solution thus obtained is rendered alkaline with soda-lye, and
the precipitate which forms is filtered off and pressed. The press cake is
repeatedly extracted with boiling water, until all the soluble matter is dissolved,
and the filtrates are acidulated with muriatic acid. The dye-stuff is finally salted
out, filtered off, pressed, and dried. It produces on cotton prepared with tannic
acid, clear red shades distinguished by their fastness on exposure to light and on
washing.
The same coloring matter can be obtained by allowing amidoazo benzene
sulphate to act on paratolyl paramidoorthotoluidine hydrochloride in the presence
of a suitable solvent or diluent (such as phenol or the like).
DYE-STUFF OBTAINED FROM DIMETHYL AMIDOAZOBENZENE AND
PARAMIDOORTHOTOLUIDINE.
'
PHENYL-
23-4 parts of phenylparamido orthotoluidine hydrochloride are dissolved in
phenol, and 34 parts of dimethylamidoazobenzene are gradually stirred into the
solution. The mixture is heated until the amido azo compound is no longer
distinguishable. After diluting it with water, the liquid is rendered alkaline by
means of soda lye, and the dye-stuff is salted out, filtered off, washed with a
solution of common salt, and pressed. The erude dye-stuff is repeatedly boiled
with water until the soluble parts thereof are dissolved, and the filtrates are
acidulated with muriatic acid, and mixed with common salt. The dye-stuff thus
precipitated is filtered off, pressed, and dried. It produces bright violet-red shades
on cotton prepared with tannic acid, and is identical with the coloring matter
prepared, as described in the foregoing Example B, from nitrosodimethylaniline
hydrochloride and phenylparamidoorthotoluidine.
11

page_text: The process proceeds in an analogous manner on substituting, for the quinone
dichlorodiimide used in the above Example D, equivalent quantities of similar
products (paraquinonechlarimides, paraquinoneimides, or the like), or if corre-
sponding quantities of other monalklymetatcluylene diamines are used in place, of
paratolyl or phenylmeta toluylene diamine prescribed in the above Examples D
and E, or if the dimethylamido-azo benzene used in the preceding Example E, is
replaced by the corresponding quantities of other paramido azo products acting in
the same or a similar manner.
The particulars given in the above Examples D and E can be varied; thus,
for instance, other solvents: (such as dilute acetic acid, glacial acetic acid, glycerol,
or the like) can be used in place of alcohol and phenol used in these examples.
The dye-stuffs thus obtained are identical with, or similar to, those which can be
produced according to the processes illustrated by the above Examples B and C.
As bereinbefore mentioned, the process for producing the coloring matters above
referred to can also be modified by subjecting molecular proportions of the
monalkylmetatoluylene diamines and alkylated paradiamines, or paradiamine
sulphonic acids containing, in one of their amido groups, either a single or two
alkyl radicles, to a joint oxidation, in the presence of suitable solvents or diluents.
This latter process is illustrated by the following Example F.
د:
COLORING MATTER OBTAINED BY JOINT OXIDATION OF PARAMIDODIMETHYL-
ANILINE AND PHENYLPARAMIDOORTHOTOLUIDINE,
A solution prepared by dissolving 3 parts of sodium dichromate in. 10 parts of
water, is gradually added to, and well mixed with, a hot solution of 2 parts of
phenylparamidoorthotoluidine, and 1.4 parts of paramidodimethylaniline in acetic
acid (containing 50 per cent. of pure acetic acid). The liquid mixture is heated
until its color has changed into pure magenta red, and the intensity of this color no
longer increases. The dye-stuff is salted out, filtered off, and redissolved in water.
After rendering the liquid alkaline by. means of ammonia, it is. filtered, and the
filtrate is acidulated with muriatic acid. The dye-stuff is finally salted out,
pressed, and dried. It is identical with that obtainable, as described in the
preceding Example E, from dimethylamido azo benzene and phenyl paramido ortho
toluidine.
The process proceeds in an analogous manner, if, instead of the paramido-
dimethylaniline used in the preceding Example F, the corresponding quantities of
other alkylated paradiamines, or paradiaminesulphonic acids, containing in one of
their amido groups either a single or two alkyl radicles, be substituted, or if
corresponding quantities of other monoalkylmetatoluylene diamines are used in
place of the phenylmetatoluylene diamine prescribed in the 'above Example F.
In the production of the dye-stuffs by a joint oxidation, as hereinbefore defined,
my foreign correspondents do not limit themselves to the directions given in the
above Example F, as these can be varied. For instance, the oxidation can be
effected by means of oxidising agents other than sodium dichromate ; for instance,
potassium bichromate, chloride of lime, lead dioxide, manganese dioxide, or other
agents acting in the same or a similar manner.
Having now particularly described and ascertained the nature, of this 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
1. The production of monalkylmetatoluylene diamines (such as phenylmeta-
toluylene diamine, paratolylmetatoluylene diamine, or the like) from metatoluylene
diamine (CH, NH, NH₂ = 1:2:4) and primary aromatic amines.

page_text: =
2. The process for producing monophenylmetatoluylene diamine (CH: NH:
NH.CH, 1. 2. 4), monoparatolylmetatoluylene diamine (CH. NH, NH.
C,H,1. 2. 4), or analogous monalkylmeta toluylene diamines, which process
consists in heating, at elevated temperatures, either-
-
(a) Metatoluylenediamine hydrochloride, or another salt of metatoluylene
diamine, with aniline, paratoluidine, or another primary aromatic amine; or
(b) Metatoluylenediamine with aniline hydrochloride, paratoluidine hydro-
chloride, or the like, or another salt of primary aromatic amines; or
(c) Metatolnylenediamine with aniline, paratoluidine, or the like, in the
presence of any suitable acid,
in either case adding benzoic acid or some other agent capable of facilitating the
action, if desirable.
3. The process for producing azine dye-stuffs from the monalkylmetatoluylene
diamines hereinbefore defined, and nitroso derivatives of secondary or tertiary
aromatic amines, or amido sulphonic acids.
4. The production of dye-stuffs by condensing nitrosomonethylaniline, nitroso-
monomethylorthotoluidine, nitrosodimethylaniline, nitrosodiethylaniline, nitroso-
diphenylamine or nitrosomethyldiphenylamine, or analogous nitroso compounds, in
the form of their salts, such as hydrochlorides, or nitrosomethylbenzylaniline
sulphonic acid, or nitrosomethyldiphenylamine sulphonic acid, or analogous nitroso
compounds, with monophenylmetatoluylene diamine, monoparatolylmetatoluylene
diamine, or analogous monalkylmetatoluylenediamines.
5. The process for producing azine dye-stuffs, which process consists in acting
with the monalkylmetatoluylene diamines hereinbefore defined; either on paramido
azo products formed by combination of diazo compounds with primary, secondary,
or tertiary amines, or substituted amines of the benzene or naphthalene series, or
on paraquinone imides, 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 monalkylmetatoluylene diamines herein before defined, together with alkylated
paradiamines, or paradiaminesulphonic acids containing, in one of their amido groups,
either a single or two alkyl radicles, to a joint oxidation in the presence of suitable
solvents or diluents.
7. As new products of manufacture, the new dye-stuffs produced by the
processes hereinbefore defined, or by any other means affording the same result.
Dated this 15th day of February-1895.
NEWTON & SON,
Agents for the Applicant.