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

page_text: Date of Application, 12th May, 1894
Complete Specification Left, 9th Feb., 1895-Accepted, 18th Mar., 1895
PROVISIONAT SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
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 to be as follows:-
My foreign correspondents have described in the Specification of Letters
Patent No. 4756, dated 4th March 1893, a process for producing azo dye-stuffs
suitable for dyeing cotton, and yielding shades capable of withstanding the action
of alkalies, which process consists in combining one molecular proportion of
a naphthol B, monosulphonic acid (OH: SO,H=1 : 3), or an alkaline salt thereof,
with one molecular proportion of the diazo derivatives of dehydrothioparatoluidine,
dehydrothiometaxylidine, dehydrothiopseudocumidine, primuline base, dehydro-
thioparatoluidine sulphonic acid, dehydrothiometaxylidine sulphonic acid, dehydro-
thiopseudocumidine sulphonic acid, primuline, or analogous thio amido compounds.
It is pointed out in the said Specification, that the fastness and purity of the
resulting bluish-red dye-stuffs are caused by the "meta" position of the hydroxylic
group relatively to the sulphonic group, and that, generally, naphtholmonosulphonic
acids, or naphtholpolysulphonic acids containing the hydroxylic relatively to a
sulphonic group in the so-called "meta" position, yield, when combined with diazo
compounds, azo dye-stuffs which are distinguished for their fastness against
alkalies, and in most cases also withstand the action of acids and light.
"T
This rule, it was found by my foreign correspondents, applied also to amido-
naphtholsulphonic acids, and they ascertained that amidonaphtholsulphonic acids
containing the hydroxylic group relatively to a sulphonic group in the "meta
position (such as B₁ amido a, naphthol ẞ, monosulphonic acid, B₁ amido a naphthol
a disulphonic acid, or the like) likewise yield, when combined with the diazo
derivatives of the aforesaid or similar thio amido compounds, colouring matters
which withstand the action of alkalies, acids, and light..
"
My foreign correspondents have now found, that chloronaphthol sulphonic acids,
or analogous halogen naphtholsulphonic acids containing a sulphonic group
relatively to the hydroxylic group in the "meta position, are, by coupling with
diazo compounds, converted into azo dye-stuffs which are capable of withstanding
in a high degree the action of alkalies, acids, and light. This property is
particularly possessed by those substantive cotton dye-stuffs which result from
the combination of diazotised dehydrothioparatoluidine, or analogous thio amido
compounds, or sulphonic acids thereof, with the said chloronaphtholsulphonic acids
or the like. These chloronaphtholsulphonic acids, or the like, may be considered
as halogen substitution derivatives, either of the hereinbefore mentioned
a naphthol ẞ, monosulphonic acid, or of polysulphonic acids derived from the
last named a, naphthol ẞ, monosulphonic acid.
Amongst chloronaphtholsulphonic acids, my foreign correspondents use, for
instance, the following, viz.: B, chloro a naphthol B, monosulphonic acid
(obtainable by acting with Cu, Cl, on the diazo derivative of ẞi amido a, naphthol

page_text: B. monosulphonic acid); B, chloroa, naphthol ẞ, monosulphonic acid, which can
be produced by treating the diazo compound of amidonaphtholmonosulphonic
acid G with Cu₂ Cl₂; 3, chloro a naphthol G, a, disulphonic acid obtainable by
the interaction of Cu, Cl, and diazotized 3, amido a, naphthol a, ẞ, disulphonic
acid; B, chloro a, naphthol ẞ, ẞ, disulphonic acid, which can be produced by acting
with Cu, Cl, on diazotised a, a, amido naphthol 3, 6, disulphonic acid.
.
Other chloronaphtholsulphonic acids containing the hydroxylic group relatively
to a sulphonic group in the "meta" position, or the corresponding analogous
halogen naphtholsulphonic acids, such as bromo naphtholsulphonic acids, likewise
containing the hydroxylic group relatively to a sulphonic group in the " meta
position, can also be used.
"
The thio azo coloring matters obtained from the combination of the herein before
defined halogen naphtholsulphonic acids, and the diazo derivatives of dehydro-
thioparatoluidine, or analogous thio amido compounds, or sulphonic acids thereof,
possess the property of dyeing unmordanted cotton with great readiness, and
produce very clear bluish-red shades, somewhat bluer than those obtained by means
of the dye-stuffs described in the Specification of the above named Letters Patent
No. 4756 of 1893. The shades thus produced almost perfectly withstand the
action of alkalies and acids.
One method of producing the coloring matters berein before described is
illustrated by the following example. The parts are by weight.
-DYE STUFF OBTAINED FROM DIAZOTISED DEHYDROTHIOMETAXYLIDINE AND
CHLORO NAPHTHOL B, MONOSULPHONIC ACID.
26-8 parts of dehydrothiometaxylidine are diazotised in the usual manner, and
the diazo compound thus formed is allowed to flow into a carefully cooled solution
prepared by dissolving 28.1 parts of the mono sodium salt of ẞ, chloro a naphthol
Bmono sulphonic acid, and rendered alkaline by means of sodium carbonate.
The formation of the dye which instantly begins, is preferably completed by
heating at about 90 degrees Centigrade. The finished coloring matter is isolate!
in the usual manner, pressed, and dried. It produces bluish-red shades ou
unmordanted cotton in an alkaline soap bath. The shades are distinguished by
their fastness against alkalies and acids.
"
The other dye-stuffs are obtained in au `aualogous manner, if either the
Bchloroa, naphthol B, monosulphonic acid used in the preceding example, is
replaced by the corresponding quantity of another chloronaphtholsulphonic acid
containing the hydroxylic group relatively to a sulphonic group in the "meta
position (OH: SOH = 1:3), or of analogous halogen naphtholsulphonic acids,,or
if other thio amido compounds, such as dehydrotbioparatoluidine, dehydrothiopseudo
cumidine, primuline. base, dehydrothioparatoluidine sulphonic acid, dehydrothio-
metaxylidine sulphonic acid, dehydrothiopseudo cumidine sulphonic acid, or
primuline or similar thio amido compounds, are used in place of dehydrothio-
*metaxylidine.
The coloring matters thus obtained generally produce bluish-red shades; and
have very great affinity for cotton fibre. The shades are almost absolutely 'fast
against alkalies and acids.
Dated this 10th den of Ma 1904

page_text: 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 described in the Specification of Letters Patent
No. 4756, dated 4th March 1893, a process for producing azo dye-stuffs suitable for
dyeing cotton, and yielding shades capable of withstanding the action of alkalies,
which process consists in combining one molecular proportion of alpha, naphthol.
beta, monosulphonic acid (OH: SO,H=1:3), or an alkaline salt thereof, with one
molecular proportion of the diazo derivative of dehydrothio paratoluidine, dehydro-
thiometaxylidine, debydrothiopseudo cumidine, primuline base, dehydrothio para-
toluidine sulphonic acid, dehydrothiometaxylidine sulphonic acid, dehydrothio-
pseudocumidine sulphonic acid, primuline, or analogous thio amido compounds. As
mentioned in the Specification of the said Letters Patent, my foreign corre-
spondents believe that the fastness and purity of the resulting bluish-red dye-
stuffs are caused by the "meta" position of the hydroxyl group relatively to the
sulphonic group, and that when combined with the aforesaid diazo compounds, the
naphtholmonosulphonic acids, or naphtholdisulphonic acids, generally, containing
the hydroxyl and a sulphonic group relatively in the "meta" position, yield azo
dye-stuffs which are distinguished for their fastness in presence of alkalies, and
which in most cases also withstand the action of acids and liglit.
"
This rule was found by my foreign correspondents to apply also to amido-
naphtholsulphonic acids, and it was stated in the Specification of their application
for Letters Patent No. 1062, dated 17th January 1894, that if amidonaphthol
sulphonic acids containing the hydroxyl group and a sulphonic group relatively in
the "meta
position (such as beta, amido alpha, naphthol beta, monosulphonic
acid and betai amido alpha, naphthol alpha, beta, disulphonic acid), were combined
with the diazo derivatives of the aforesaid or similar thio-amido compounds,
valuable coloring matters were formed, which, when dyed on cotton fibre, withstand
the action of acids and light, aud are but little altered by alkalies..
My foreign correspondents have now found, that when chloronaphthol sulphonic
acids, or analogous halogenated naphtholsulphonic acids, containing the hydroxyl
group and a sulphonic group relatively in the "meta" position, are coupled with
the diazo derivatives of thio amido compounds, azo dye-stuffs are produced which
are capable in a high degree of withstanding the action of alkalies, acids, and
light. This property is particularly possessed by the substantive cotton dye-stuffs
formed by the combination of such halogenated naphtholsulphonic acids, or alkaline
salts thereof, with the diazo derivatives of dehydrothioparatoluidine, dehydrothio-
metaxylidine, dehydrothiopseudocumidine, primuline'base, dehydrothioparatoluidine
sulphonic acid, dehydrothiometaxylidine sulphonic acid, dehydrothiopseudocumidine
sulphonic acid, primuline, or analogous thioamido compounds, or sulphonic acids
thereof. It is to be noted that the halogenated naphtholsulphonic acids herein-
before defined, and containing the hydroxyl group and a sulphonic group relatively
in the meta position, may be considered as halogen substitution derivatives, either
of the above mentioned alpha, naphthol beta, monosulphonic acid, or of poly-
sulphonic acids derived from this alpha, naphthol beta, monosulphonic acid.
The chloronaphtholsulphonic acids used by my foreign correspondents are, for
instance, the following, viz., beta, chloro alpha, naphthol beta, monosulphonic acid
(obtainable by acting with Cu, Cl, on the diazo derivative of beta, amido alpha

page_text: naphthol beta, monosulphonic acid), beta, chloro alpha, naphthol beta, mono-
sulphonic acid, which can be produced from the diazo compound of amidonaphthol
monosulphonic acid G, and Cu, Cl,; beta, chloroalpha, naphtholbeta, alpha,
disulphonic acid, obtainable by the interaction of Cu, Cl, and diazotised beta₁
amido alpha, naphthol alpha, beta, disulphonic acid; alpha, chloro alpha, naphthol
beta, beta, disulphonic acid, which can be produced by acting with Cu₂ Cl。 on
diazotised alpha, alpha, amidonaphthol beta, beta, disulphonic acid.
Other chloronaphtholsulphonic acids containing the hydroxyl group and a
sulphonic group relatively in the "meta" position, or the corresponding analogous
halogenated naphtholsulpbonic acids, such as the bromonaphtholsulphonic acids
containing the hydroxyl group and a sulphonic group relatively in the "meta
position, can also be used.
"
The thiazo coloring matters obtained from the herein before defined halogenated
naphtholsulphonic acids, and the diazo derivatives of dehydrothioparatoluidine, or
analogous thioamido compounds, or sulphonic acids thereof, possess the property of
dyeing unmordanted cotton with great readiness, producing very clear bluish-red
shades, somewhat bluer than those obtained by means of the dye-stuffs described in
the Specification of the above named Letters Patent No. 4756 of 1893. The
shades thus produced almost perfectly withstand the action of alkalies and acids.
One method of producing the coloring matters hereinbefore described is
illustrated by the following example. The parts are by weight.
DYE-STUFF OBTAINED FROM DIAZOTISED DEHYDROTHIOMETAXYLIDINE AND
BETA CHLORO ALPHA, NAPHTOL BETA, MONOSULPHONIC ACID.
.
26.8 parts of dehydrothiometa xylidine are diazotised in the usual manner, and
the diazo compound thus formed is allowed to flow into a carefully cooled solution
of 281 parts of the monosodium salt of beta, chloro alpha, naphthol beta, mono-
sulphonic acid, rendered alkaline by means of sodium carbonate. The formation of
the dye-stuff, which at once begins, is preferably completed by heating at about
90 degrees Centigrade. The finished coloring matter is isolated in the iisual
manner, pressed, and dried. It produces bluish-red shades on unmordanted cotton
in an alkaline soap bath. The shades are distinguished by their fastness in presence
of alkalies and acids.
The other dye-stuffs are obtained in an analogous manner, if, instead of the beta
chloro alpha, naphthol beta, monosulphonic acid used in the preceding example,
the corresponding quantity of another chloronaphthol sulphonic acid, containing
the hydroxyl group and a sulphonic group relatively in the "meta" position
(OH SO H=1:3), or of an analogous halogenated naphtholsulphonic acid be
used, or it the diazo derivatives of other thioamido compounds, such as dehydro-
thioparatoluidine, dehydrothiopseudocumidine, primuline base, dehydrothiopara-
toluidine sulphonic acid, dehydrothiometaxylidine sulphonic acid, dehydrothio-
pseudocumidine sulphonic acid, primuline, or similar thio amido compounds, are
coupled with the halogenated naphtholsulphonic acids hereinbefore referred to.
The coloring matters thus obtained generally produce bluish-red shades, and
have very great affinity for cotton fibre. The shades are almost absolutely fast in
presence of alkalies and acids.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed; as communicated to
me from abroad, I declare that what I claim is :-
1. The production of dye-stuffs from chloro or other halogenated naphthol
sulphonic acids, containing the hydroxyl and a sulphonic group relatively in the
meta position, and the diazo derivatives of the so-called thioamido compounds, or
sulphonic acids thereof.

page_text: 2. The process for producing dye-stuffs, which process consists in combining one
molecular proportion of the diazo derivatives of dehydrothioparatoluidine, dehy-
drothiometaxylidine, dehydrothiopseudocumidine, primuline base, dehydrothio-
paratoluidine sulphonic acid, dehydrothiometaxylidine sulphonic acid, dehydro-
thiopseudocumidine sulphonie acid, primuline, or analogous thioamido compounds,
or sulphonic acids thereof, with one molecular proportion of beta, chloro alpha,
naphtholbeta, monosulphonic acid, beta, chloroalpha, naphthol beta, monosulphonic
acid, beta, chloroalpha, naphthol beta, alphas disulphonic acid, alpha, chloro alpha,
naphthol beta, beta, disulphonic acid, or other halogenated naphthol sulphonic
acid containing the hydroxyl and a sulphonic group relatively in the meta
position, or an alkaline salt of such halogenated naphthol sulphonic acids.
3. As new products of manufacture, the new coloring matters produced by the
process hereinbefore defined, or by any other process affording the same result.
Dated this 30th day of January 1895.
NEWTON & SON,
Agents for the Applicant.