The Manufacture or Production of Dye-stuffs.
Year: 1894

page_text: '
Date of Application, 6th Feb., 1894
Complete Specification Left, 6th Nov., 1894-Accepted, 8th Dec., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Dye-stuffs.
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 have found that valuable coloring matters, suitable
for dyeing unmordanted cotton, are obtained by means of the "thio bases
resulting from heating paratoluidine, meta xylidine, pseudo cumidine, or the like,
with sulphur, or the "sulpho acids of such thio bases," or analogous thio amido
compounds, viz.: by coupling the diazo products derived therefrom with an amine,
or substituted amine, of the benzene or naphthalene series," rediazotising the
amido azo products so formed, combining the resulting diazo derivatives with
hydroxylated compounds (such as phenols, cresols, dihydroxybenzenes, or
homolognes thereof, naphthols, dihydroxynaphthalenes, sulphonic or carboxylic
acids thereof), and subsequently alkylating the coloring matters thus produced,
which contain hydroxylic groups, owing to the hydroxylated compounds used as
last components.
My foreign correspondents mean by the above expression, "thio bases," and the
"sulpho acids of such thio bases," for instance, the following products :-Dehydro-
thiopara toluidine, melting at 191 degrees Centigrade, described in the Berichte
der Deutschen Chemischen Gesellschaft, volume 22, page 1064; dehydrothio-
metaxylidine, melting at 107 degrees Centigrade, and described in the aforesaid
Berichte, volume 22, page 583; dehydrothiopseudo cumidine, obtainable by heating
pseudo cumidine with sulphur; the so-called primuline base (see the above
Berichte, volume 22, page 1067), which results from heating paratoluidine with
sulphur, and is formed together with the aforesaid dehydrothioparatoluidine,
employing either the raw mixture or the primuline base isolated by means of the
process described in the Specification of the German Patent No. 47102, or in
another suitable manner; dehydrothioparatoluidine sulphonic acid, obtained by
sulphonating dehydrothiopara toluidine, and described in the said Berichte,
volume 22, page 971; dehydrothio meta xylidine sulphonic acid, which results from
sulphonating dehydrothio meta xylidine (Berichte, volume 22, page 585), dehydro-
thiopseudo cumidine sulphonic acid, obtainable by sulphonating dehydrothio
pseudo cumidine; primuline, which is the mixture of the sulphonic acids of the
raw product formed on treating paratoluidine with sulphur, and consisting, as
above mentioned, of dehydrothioparatoluidine and primuline base. Other thio
bases, or sulphonic acids thereof, however, can also be used, for instance, the
products known in commerce as chromine, polychromine, thiochromogene, or
the like.
My foreign correspondents employ, as second components, hereinbefore briefly
termed, "amines or substituted amines of the benzene or naphthalene series," all
amido compounds of these two series which, when combined with diazo products,
yield real amido azo products capable of further diazotisation, for instance, para
xylidine, orthoamidophenol ether, meta amido phenol ether, orthoamido para cresol
ether, meta amidopara cresol ether, a naphthylamine, a naphthylamine B₁ mono-
sulphonic acid, a, naphthylamine ẞ, monosulphonic acid, a, naphthylamine ẞ. mono-
sulphonic acid, amidonaphthols, amidonaphthol ethers, amidonaphtholsulphonic

page_text: acids, amidonaphtholethersulphonic acids, amidonaphthoxyacetic acid, amido-
naphthoxyacetic sulpho acid, or the like.
As last components, in general, hydroxylated compounds can be used, such as
phenol, cresols, dihydroxybenzenes, or homologues thereof, naphthols, dihydroxy-
naphthalenes, or sulphonic or carboxylic acids, or other derivatives thereof.
The coloring matters obtainable by coupling the last-named hydroxylated
compounds with the diazo derivatives of the first-formed amido azo products
(which coloring matters are partly described in the Specification of the English
Letters Patent No. 51122) are treated in the known manner with alkylating
agents. Direct-dyeing secondary disazo dye-stuffs are thus produced, which are
superior to all analogous products, by reason of their great fastness against the
action of light, alkalies, and acids.
One of the methods of producing these disazo coloring matters is illustrated by
the following example.
DYE STUFF OBTAINED BY ETHYLATING THE COLORING MATTER RESULTING
FROM DEHYDROTHIO PARA TOLUIDINE SULPHONIC ACID, a₁ NAPHTHYL-
AMINE MONOSULPHONIC ACID, AND PHENOL.
34-2 parts (the parts are by weight) of the sodium salt of dehydrothio para
toluidinė sulphonic acid are diazotised by means of a watery solution of 7 parts of
sodium nitrite, and the necessary quantity of muriatic acid. The diazo compound
thus obtained (which is soluble with difficulty) is filtered off, and introduced into
a watery solution prepared by dissolving 24.3 parts of the a₁ naphthylamine ẞ
mono sulphonate of sodium, and about 50 parts of sodium acetate. After stirring
during about 12 hours, the mass is heated at about 90 degrees Centigrade, and is
then rendered alkaline by means of soda lye. The resulting amido azo product
is isolated by salting out and filtering off. This intermediate amido azo product
is mixed with a small quantity of water, and after adding an excess of sodium
nitrite (say 15 molecules in place of i molecule), is diazotised by gradually adding
hydrochloric acid. The mass is allowed to remain during 12 hours, with repeated
stirring, and the complete diazo product, which is previously filtered off, is
introduced into a watery solution prepared by dissolving 9.4 parts of phenol, with
the addition of potassium carbonate or potassium hydroxide. While stirring,
such a quantity of dilute potassa lye is gradually added, as is necessary for
saturating the hydroxylic group which is contained in the phenol used, and is set
free during the combination. At the end of 12 hours, the mass is heated for
some time at from 60 to 70 degrees Centigrade, and the product, which is now to
he alkylated, is isolated by salting out and filtering off. For this purpose, it is
mixed with the proper quantity of ethyl bromide and potassa, and the resulting
mixture is heated during about 8 hours, at from 90 to 100 degrees Centigrade, in
a vessel capable of withstanding pressure. The dye-stuff isolated from the reaction
mixture yields, on unmordanted cotton, reddish-brown shades which are fast
against the action of acids and alkalies, and are superior, by reason of their
fastness against the action of light, to all cotton dyes hitherto known and yielding
similar shades.
Analogous dye-stuffs result in a similar manner if, on the one hand, the
coloring matter used in the above example, and produced from dehydrothio para
toluidine sulphonic acid, a naphthylamine (ẞ monosulphonic acid, and phenol, is
replaced by analogous dye-stuffs resulting from the employment of the components
herein before referred to, or if, on the other hand, the different coloring matters
are methylated, propylated, amylated, benzylated, or the like, in place of
ethylating them.
In order to produce these dye-stuffs, my foreign correspondents do not limit
themselves to the directions given in the above example, as the ethylating of the

page_text: coloring matter used therein, and, in general, the alkylating (viz.: methylating,
ethylating, propylating, amylating, benzylating, or the like) of the coloring
matters herein before referred to, can be effected by means of all methods known
and in use for analogous purposes.
The dye-stuffs thus obtained produce shades which are distinguished for their
fastness against the action of acids, alkalies, and light.
Dated this 6th day of February 1894.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Dye-stuffs.
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 have found that valuable coloring matters suitable for
dyeing unmordanted cotton, are obtained by alkylating the dye-stuffs which are
derived from the "thio bases" formed by heating paratoluidine, metaxylidine,
pseudo cumidine, or the like, with sulphur, or from the "sulphonic acids of such
thio bases," or analogous thioamido compounds, the which dye-stuffs can be
produced by coupling the diazo derivatives of the "thio bases" herein before referred
to, or sulphonic acids thereof, with an "amine or substituted amine of the benzene
or naphthalene series," rediazotising the amido azo compounds so formed, and
combining the diazo derivatives with hydroxylated compounds (such as phenol,
cresol, resorcinol, alpha naphthol).
:-
My foreign correspondents mean by the above expressions, "thio bases," and
"sulphonic acids of such thio base," for instance, the following products:
Dehydrothio para toluidine, melting at 191 degrees Centigrade, described in the
Berichte der Deutschen Chemischen Gesellschaft, volume 22, page 1064; dehydro-
thio-meta-xylidine, melting at 107 degrees Centigrade, and described in the
aforesaid Berichte, volume 22, page 583; dehydrothio pseudocumidine, obtainable
by heating pseudocumidine with sulphur; the so-called primuline base (see the
aforesaid Berichte, volume 22, page 1067), formed on heating para-toluidine with
sulphur together with dehydrothio-para-toluidine (using either the crude mixture,
or the primuline base isolated by means of the process described in the Specification
of the German Patent No. 47102, or in any other suitable manner); dehydrothio
para-toluidine sulphonic acid, obtained by sulphonating dehydrothio paratoluidine,
and described in the said Berichte, volume 22, page 971, dehydrothiometaxylidine
sulphonic acid, formed on sulphonating dehydrothiometa xylidine (Berichte,
volume 22, page 585); dehydrothiopseudo cumidine sulphonic acid, obtainable by
sulphonating dehydrothio pseudo-cumidine; primuline, which is the mixture of the
sulphonic acids of the crude product formed on heating paratoluidine with sulphur,
and consisting, as above mentioned, of dehydrothioparatoluidine and primuline base.
Other thio bases, or sulphonic acids thereof, however, can also be used, for instance,
the products known in commerce as chromine, polychromine, thiochromogene, or
the like.
ઃ
My foreign correspondents use, as second components, hereinbefore briefly termed
amines or substituted amines of the benzene or naphthalene series," all amido
compounds of these two series which, when combined with diazo derivatives, yield
true amido azo compounds capable of being further diazotised, for instance, para-
xylidine, orthoamidophenolether, metaamidophenolether, orthoamidoparacresolether,
metaamidoparacresolether, alphanaphthylamine, alpha,-naphthylaminebeta, mono-
sulphonic acid, alpha, naphthylaminebeta, monosulphonic acid, alpha, naphthylamine

page_text: beta monosulphonic acid, amidonaphthols, amidonapbtholethers, amidonaphthol-
sulphonic acids, amidonaphtholether sulphonic acids, amidonaphthoxyacetic acid,
amidonaphthoxyacetic sulphonic acid, or the like.
As last components, hydroxylated compounds in general can be used, such as
phenol, cresol, resorcinol, alpha naphthol.
According to this invention, the coloring matters obtainable by coupling the
last-named hydroxylated compounds with the diazo derivatives of the first-formed
amido azo compounds (the which coloring matters are partly defined in the
Specifications of the English Letters Patent No. 5112" and 11533"), are treated
in a suitable manner with alkylating agents. Direct-dyeing secondary disazo dye-
stuffs are thus produced, which are distinguished by their great fastness or exposure
to the action of light, alkalies, and acids.
One of the methods of producing these alkylated disazo coloring matters is
illustrated by the following example
:-
DYE-STUFF OBTAINED BY ETHYLATING THE COLORING MATTER FROM DEHY-
DROTHIOPARATOLUIDINE SULPHONIC ACID, ALPHA₁ NAPHTHYLAMINE
BETA MONOSULPHONIC ACID, AND PHENOL.
34.2 parts (the parts are by weight) of the sodium salt of dehydrothiopara-
toluidine sulphonic acid, are diazotised by means of a solution of 7 parts of sodium
nitrite and the necessary quantity of muriatic acid. The diazo compound thus
obtained, which is difficultly soluble, is introduced into a solution prepared by
dissolving 24.5 parts of alpha, naphthylamine beta, monosulphonate of sodium, and
about 50 parts of sodium acetate, in water. After stirring during about 12 hours,
the mass is heated to about 90 degrees Centigrade, and is then rendered alkaline by
means of soda lye. The amido azo compound is separated, then salted out and
filtered off. This intermediate amido azo compound is mixed with a small quantity
of water, and after adding an excess of sodium nitrite (say 1.5 molecules in place
of 1 molecule), is diazotised by gradually adding muriatic acid. The mixture
having been allowed to remain during 12 hours, and having been repeatedly stirred
the while, the diazo compound is filtered off and introduced into a solution prepared
by dissolving 9.4 parts of phenol in water, with the aid of potassium carbonate or
potassium hydroxide. The mixture is thoroughly stirred, and such a quantity of
dilute potassa lye is gradually added, as is necessary to neutralise the phenolic
hydroxyl which is set free as the combination proceeds. At the end of 12 hours,
the mass is heated for some time at from 60 to 70 degrees Centigrade, and the
product to be alkylated is isolated by salting out and filtering off. For this
purpose, the pasty mass is mixed with the proper quantity of ethyl bromide,
potash, and ethyl alcohol, and the mixture is heated by means of a water bath,
during about 8 hours, in a closed vessel capable of withstanding pressure.
dyestuff isolated from the mixture yields, on unmordanted cotton, reddish-brown
shades which withstand the action of acids and alkalies, and are distinguished for
their fastness on exposure to light.
The
Analogous dye-stuffs are formed in a similar manner, if, on the one hand, instead
of the coloring matter used in the above example, and produced frum dehydrothio-
paratoluidine sulphonic acid, alpha, naphthylamine beta, monosulphonic acid, and
phenol, analogous dye-stuffs, formed by using the components hereinbefore referred
to, be taken, or if, on the other hand, instead of ethylating the different coloring
matters, they are methylated, propylated, amylated, benzylated,
or the like.
In order to produce these dye-stuffs, my foreign correspondents do not limit
themselves to the directions given in the above example, as the ethylation of the
coloring matter used therein, and, in general, the alkylation (viz., methylation,
ethylation, propylation, amylation, benzylation, or the like) of the coloring matters
herein before referred to, can be effected by means of all methods known and in use
for analogous purposes.

page_text: The dye-stuffs thus obtained produce shades which are distinguished for their
fastness on exposure to the action of acids, alkalies, and light.
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 alkylated coloring matters by treating, in the presence
of alkalies, with methyl, ethyl, propyl, amyl, or benzylhaloid, or by treating in
another manner adapted for converting hydroxylic groups into alkyloxy groups,
those disazo dye-stuffs which contain, as last components, hydroxylated products,
and which can be obtained by combining the diazo derivatives of dehydrothiopara-
toluidine, dehydrothiometaxylidine, dehydrothiopseudo cumidine, primuline base,
dehydrothioparatoluidine sulphonic acid, dehydrothiometa xylidine sulphonic acid,
dehydrothiopseudocumidine sulphonic acid, primuline, or analogous thio-amido
compounds, with such amines or substituted amines of the benzene or naphthalene
series, as, when combined with the said diazo compounds, yield true amido com-
pounds capable of being diazotised, rediazotising the amido azo compounds thus
formed, and subsequently coupling the diazoazo compounds with hydroxylated
compounds of the benzene or naphthalene series (such as phenol, cresol, resorcinol,.
alphanaphthol).
2. As new products of manufacture, the new alkylated coloring matters produced
by the process hereinbefore defined, or by any other process affording the same.
result.
Dated this 6th day of November 1894
NEWTON & SON,
Agents for the Applicant.