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

page_text: Date of Application, 16th Aug., 1894
Complete Specification Left, 30th Apr., 1895-Accepted, 1st June, 1895
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 ascertained some time ago that of the two amido groups
contained in the meta-toluylenediamine, only the one which is in the position
para" relatively to the methyl group, can be easily substituted by aromatic alkyl
groups, whilst the other amido group remains unaltered during the alkylating
66
process.
My foreign correspondents have now found that meta-toluylene-diamine is also
capable of reacting with resorcinol, for instance, on heating, at elevated tempera-
tures, metatoluylenediamine with resorcinol, in (or without) the presence of
condensing agents, such as acids, calcium chloride, zinc chloride, or other agents,
acting in the same or a similar manner, and the researches of my foreign
correspondents have shown that the amido group in the position "para" relatively
to the methyl group of the metatoluylenediamine, acts on the one hydroxylic
group contained in the resorcinol, water being split off, and meta hydroxyphenyl-
paraamidoorthotoluidine being thus formed, to which product my foreign corre-
spondents ascribe the following formula :

page_text: In order to illustrate one method of producing the aforesaid metahydroxyphenyl-
paraamidoorthotoluidine, the following example is given the parts are by weight.
:
MANUFACTURE OF METAHYDROXYPHENYLPARAAMIDOORTHOTOLUIDINE.
A mixture containing equal parts of resorcinol and metatoluylene diamine, are
heated by means of an oil bath during about 12 hours, at from 200 to 220 degrees
Centigrade, whilst a current of carbon dioxide is allowed to pass through the
heated mixture. After cooling, the resulting mixture is treated with hot water
and an excess of soda lye. The liquid so formed is filtered, and the filtrate being
carefully cooled by means of ice, is supersaturated with dilute muriatic acid.
Some by-products are thus precipitated, and can be removed by filtration. Dilute
soda-lye is then slowly added, under continual stirring, to the filtrate, until the
muriatic acid in excess is neutralised. By filtration, a clear yellow solution results,
which is finally mixed with a solution of sodium carbonate or sodium acetate.
The precipitate is filtered off and crystallised from dilute alcohol.
The metahydroxyphenylparaamidoorthotoluidine thus obtained, readily dissolves
in cold alcohol, very readily in hot alcohol, but dissolves with less readiness in
dilute alcohol. It is not readily soluble in water and benzene. When crystallised
from water, alcohol, or benzene, it forms scales with silver-like lustre, and melts at
from 177 to 178 degrees Centigrade. It dissolves but slightly in ligroine. It is
soluble to the same extent in dilute alkalies and dilute mineral acids, and can be
precipitated by adding acetic acid to its alkaline solutions. Its sodium salt is
separated on adding an excess of soda-lye to its solutions. It can be diazotised,
and the resulting diazo product combines with amines, phenols, or the like, to form
coloring matters. It can also be coupled at once with diazo bodies in acidulated
or alkaline solutions.
my
In order to produce the said metahydroxyphenylparaamidoorthotoluidine,
foreign correspondents do not limit themselves to the directions given in the preceding
example, as these can be varied; for instance, the reaction can be effected in the
presence of condensing agents, such as calcium chloride, zinc chloride, acids, or the
like. Salts of metatoluylene diamine can be used in place of adding acids to
the said mixture.
My foreign correspondents have further found that the aforesaid metahydroxy-
phenylparaamidoorthotoluidine is capable of being easily 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 coloring matters are thus obtained
which chiefly 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, have chiefly in mind quinone chlorimides, or azɔ products resulting
from 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 coloring matters herein before
defined can also be obtained by using, in place of chlorimides, or nitroso compounds,
the corresponding products obtainable therefrom by reduction, such as alkylated
paradiamines, or derivatives of alkylated paradiamines, containing a free amido
group. In the latter case, it is necessary to subject these alkylated diamines, or
derivatives thereof, together with metahydroxyphenylparaamidoorthotoluidine, 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.

page_text: COLORING MATTER FROM NITROSO DIMETHYLANILINE HYDROCHLORIDE AND
META HYDROXYPHENYLPARAAMIDOORTHOTOLUIDINE.
5.6 parts of nitrosodimethylaniline hydrochloride are introduced into a solution
prepared by dissolving 21 parts of metahydroxyphenylparaamidoorthotoluidine in
alcohol. The resulting mixture is gently heated, under stirring, until the nitroso
product is no longer distinguishable. At this stage, the solution exhibits a pure
magenta-red color. The alcohol is distilled over, and the residue is treated with
hot water. After filtering, the dye-stuff is precipitated by adding salt to the
filtrate. It is filtered off and redissolved, and precipitated again, in order to purify
the same.
It produces brilliant bluish-red shades on cotton prepared with tannic
acid or the like. The shades are distinguished by their fastness against the action
of alkalies and light..
DYE
STUFF FROM NITROSO METHYLBENZYLANILINE SULPHONIC ACID AND
METAHYDROXYPHENYLPARAAMIDO ORTHO TOLUIDINE.
4-6 parts of nitrosomethylbenzylaniline sulphonic acid, are added to an alcoholic
The
solution of 21 parts of metahydroxyphenylparaamido ortho toluidine.
resulting mixture is gently heated, under stirring, until the nitroso compound is no
longer distinguishable, and it is then heated in a vessel provided with a reflux
condenser, until the liquid mixture shows a pure red color. The alcohol is then
distilled over,
and the residue is boiled with water and an excess of a solution of
sodium carbonate. The dye-stuff, which is not readily soluble, is filtered off, and in
order to render it more soluble, it is dissolved in muriatic acid (containing
20 per cent. of pure acid), and the resulting solution is then poured into a large
quantity of hot water. The dye-stuff then separates in a crystalline state.
dissolves in boiling water, and produces bluish-red shades on wool in an acidulated
or neutral bath.
FOURTH EXAMPLE.
COLORING MATTER FROM PARA-NITROSO-DIPHENYLANILINE AND META
HYDROXYPHENYLPARAAMIDO ORTHOTOLUIDINE.
It
3 parts of paranitrosodiphenylamine are added to a solution prepared by dissolving
21 parts of metahydroxyphenylparaamido orthotoluidine in alcohol, and the
mixture so formed is heated until the nitroso compound is no longer distinguishable.
At this stage, the solution exhibits a violet-red color. The alcohol is distilled
over, and the residue is treated with hot water. The resulting solution is filtered,
and the dye-stuff thus formed separates in a crystalline state from the filtrate, on
cooling. It produces brilliant violet shades on cotton prepared with tannic acid
or the like; the shades are distinguished by their fastness against the action of
alkalies and light.
Analogous coloring matters result if the nitroso compounds used in the preceding
examples two, four, and three, are replaced by the corresponding quantities of
nitroso derivatives of other tertiary or secondary amines, or substituted amines.
Naturally, my foreign correspondents do not limit themselves to the directions
given in these examples, as these directions can be varied. For instance, other
solvents or diluents of neutral, basic, or acid nature can be used in place of alcohol.
As above mentioned, the coloring matters hereinbefore defined can also be
produced by using, in place of nitroso compounds, all those substances which act

page_text: in the same or au analogous manner, such as quinone chlorimides, or the azo
products resulting from the combination of diazo derivatives with primary or
secondary or tertiary aromatic amines, or substituted amines, of the benzene or
naphthalene series. The production of the coloring matters from the last-named
materials is carried out according to the methods known and in use for the
manufacture of analogous or similar dye-stuffs. Neutral, basic, or acid solvents
can also be used in this case.
In order to produce the coloring matters herein before defined by a joint oxidation
of alkylated paradiamines, or substituted alkylated paradiamines, containing a free
amido group, with the aforesaid metahydroxyphenylparaamido orthotoluidine, all
those processes can be used which are known, and in use, for producing analogous
dye-stuffs.
My foreign correspondents have also found that the coloring matters obtainable
as hereinbefore defined, can, by a subsequent treatment with suitable sulphonating
agents, be converted into coloring matters which dissolve with greater readiness
than the original products.
Doted this 10
.
J
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Dye-stuffs, and Materials
therefor.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
:
My foreign correspondents ascertained some time ago that of the two amido
groups contained in metatoluylenediamine (CH, NH, NH, 1:2:4), only the one
which is in the "para" position relatively to the methyl group, can easily have
aromatic alkyl groups introduced into it, the other amido group remaining almost
entirely unaltered during the alkylating process.
"
My foreign correspondents have now found that meta toluylene diamine is also
capable of interacting with resorcinol. For instance, on heating, at elevated
temperatures, metatoluylene diamine, either with resorcinol alone, or together with
condensing agents, such as acids, calcium chloride, zinc chloride, or other suitable
agents acting in the same or a similar manner, the amido group in the " para
position relatively to the methyl group of the metatoluylene diamine, enters into
action with one of the hydroxyl groups in the resorcinol; water is split off during
this operation, and a methydroxyphenylparamidoorthotoluidine is thus formed, to
which my foreign correspondents ascribe the formula :—

page_text: If the said action be effected at not too elevated temperatures, and an excess of
metatoluylenediamine be not used, no other condensation product is formed in any
considerable amount.
In order to illustrate one method of producing the aforesaid metbydroxyphenyl-
paramidoorthotoluidine, the following example is given. The parts are by weight.
EXAMPLE A.
MANUFACTURE OF METHYDROXYPHENYLPARAMIDOORTHOTOLUIDINE.
A mixture of equal weights of resorcinol and metatoluylene diamine is heated
by means of an oil bath, during about 12 hours, at from 200 to 220 degrees Centi-
grade, whilst a current of carbon dioxide is allowed to pass slowly through the
heated mixture. When cool, the product is treated with hot water and an excess
of soda lye, and the liquid having been filtered, the filtrate is carefully cooled by
means of ice, and then supersaturated with dilute muriatic acid. Insoluble by-
products are thus precipitated, and can be removed by filtration. Sufficient dilute
soda-lye is then gradually mixed with the filtrate, to neutralise the excess of
muriatic acid; the liquid is then filtered, and the clear yellow solution which is
obtained is mixed with a solution of sodium carbonate or sodium acetate. The
precipitate is filtered off and crystallised from dilute alcohol.
The methydroxyphenyl paramido orthotoluidine thus obtained dissolves with
difficulty in cold alcohol, readily in hot alcohol, but with less readiness in dilute
alcohol. It does not readily dissolve in water and benzene. When crystallised
from water, alcohol, or benzene, it forms lustrous scales melting at from 177 to
178 degrees Centigrade. It dissolves but slightly in ligroin. It is soluble to the
same extent in dilute alkalics and dilute mineral acids, and can be precipitated by
adding acetic acid to its alkaline solutions. Its sodium salt is separated on adding
an excess of soda lye to its solutions. It can be diazotised and the diazo derivative
combines with amines, phenols, or the like, forming coloring matters.
It can be
coupled with diazo compounds, either in acid or alkaline solutions.
In order to produce the said methydroxyphenylparamidourthotoluidine, my
foreign correspondents do not limit themselves to the directions given in the
preceding example, as these can be varied; for instance, the action can be effected
in the presence of condensing agents such as calcium chloride, zinc chloride, acids,
or the like. Salts of metatoluylenediamine can be used directly, instead of adding
acids to the said mixture.
My foreign correspondents have further found, that the aforesaid methydroxy-
phenylparainidoorthotoluidine may be easily condensed with the nitroso derivatives
of secondary or tertiary aromatic amines, or substituted amines, or, generally,
with all substances which act in a manner analogous to that in which the said
nitroso compounds act. Valuable coloring matters are thus obtained which produce
bright shades on cotton prepared with tannic acid, and on wool. The shades are
distinguished by their fastness on washing and on exposure to light.
My foreign correspondents, in speaking of substances which act in a manner
analogous to that in which nitroso derivatives act, have chiefly in mind quinone
dichlordiimide, or analogous products, or azo compounds, such as are obtainable by
coupling 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 same or similar coloring matters can
also be obtained, if, in place of the chlorimides, or nitroso compounds, the corre-
sponding products obtainable therefrom by reduction, such as alkylated para-
diamines, or derivatives of alkylated paradiamines, containing a free amido group,
are used. In the latter case, it is necessary to subject these alkylated diamines,
or derivatives thereof, together with methydroxyphenylparamidoorthotoluidine,
a joint oxidation, for instance, by means of ferric chloride or bichromate, or
manganese dioxide, in the presence of acetic acid or the like.
to

page_text: COLORING MATTER FROM NITROSO DIMETHYLANILINE HYDROCHLORIDE AND
METHYDROXYPHENYL PARAMIDO ORTHOTOLUIDINE.
2-8 parts of nitrosodimethylaniline hydrochloride are gradually stirred into a hot
solution prepared by dissolving 2.14 parts of methydroxyphenylparamidoortho-
toluidine in alcohol. The mixture is gently heated, being meanwhile stirred, until
the nitroso compound is no longer distinguishable, and the intermediate blue color
has turned into pure magenta red.
The dye-stuff crystallizes out on cooling the solution. It is filtered off, pressed,
washed with alcohol, and dried.
It easily dissolves in water, producing a magenta-red colored liquid, and yields
bright violet-red shades on cotton prepared with tannic acid or the like. The
shades withstand the action of alkalies and light.
COLORING MATTER FROM PARANITROSODIPHENYLAMINE HYDROCHLORIDE AND
METHYDROXYPHENYL PARAMIDO ORTHOTOLUIDINE.
35 parts of paranitrosodiphenylamine hydrochloride are gradually stirred into a
solution of 2-14 parts of methydroxyphenyl paramido orthotoluidine in alcohol.
The mixture is gently heated, being meanwhile stirred, until the nitroso compound
is no longer distinguishable, and the liquid has assumed a violet-red color; the
dye-stuff crystallises out as the liquid cools. It dissolves somewhat readily in
water, affording a violet-red colored liquid, and produces violet shades on cotton
prepared with tannic acid or the like. The shades withstand the action of alkalies
and light.
Analogous coloring matters are formed if, instead of the nitroso compounds
prescribed in the preceding Examples B and C, the corresponding quantities of
nitroso derivatives of other tertiary or secondary amines, or substituted amines,
are used. Thus, for instance, the coloring matter from nitroso diethylaniline
produces reddish-violet shades on cotton prepared with tannic acid; that obtained
from nitrosomonoethylaniline dyes a bluish-red, whilst the coloring matter from
nitroso monomethylorthotoluidine yields red shades of a bluish hue, and the dye-
stuff produced from nitrosoethyldiphenylamine a reddish-violet.
On using nitroso derivatives of secondary or tertiary aromatic amidosulphonic
acids, acid dye-stuffs are formed which are suitable for dyeing wool.
Naturally, my foreign correspondents do not limit themselves to the directions
given in these examples, as these directions can be varied. For instance, other
solvents or diluents, such as glacial acetic acid, glycerol, or the like, can be used,
in place of the alcohol used in the foregoing two Examples B and C.
As above mentioned, in place of the nitroso compounds, all those substances can
be used which act in the same or in a similar manner viz. quinonedichlordiimide, or
analogous products, or azo compounds formed by the combination of diazo deriva-
tives with primary or secondary or tertiary aromatic amines, or substituted amines,
of the benzene or naphthalene series, the same or analogous coloring matters being
thus obtained. The production of the coloring matters from the last-name l
materials is carried out according to the methods known and in use for the
manufacture of analogous or similar dye stuffs.
In order to produce the coloring matters hereinbefore defined, by conjointly
oxidising alkylated paradiamines, or substituted alkylated paradiamines, containing
a free amido group, and the aforesaid methydroxyphenylparamidoorthotoluidine,

page_text: all those processes can be used which are known and in use for producing analogous
dye-stuffs.
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. The process for producing methydroxyphenyl paramidoorthotoluidine, which
process consists in heating, at elevated temperatures, metatoluylenediamine
(CH, NH, NH₁ = 1:2:4) with resorcinol alone, or in the presence of suitable
condensing agents.
2. The production of dye-stuffs by allowing methydroxyphenyl paramido ortho-
toluidine to act on the paranitroso derivatives of secondary or tertiary aromatic
amines, or amido sulphonic acids.
3. The process for producing dye-stuffs, which process consists in allowing
methydroxyphenyl paramido orthotoluidine to act on quinone dichlordiimide, or
azo compounds formed by the combination of diazo compounds with primary,
secondary, or tertiary amines, or amido sulphonic acids, of the benzene or
naphthalene series.
4. The production of dye-stuffs by subjecting methydroxyphenyl paramido
orthotoluidine, together with alkylated paradiamines, or 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.
5. As new products of manufacture,
a) methydroxy phenylparamidoorthotoluidine
b) the new coloring matters
produced by the processes
hereinbefore defined, or by
any other means affording
the same result.
Dated this 10th day of April 1895.
NEWTON & SON,
Agents for the Applicant.
NEWTON & SON,
Agents for the Applicant.