The Manufacture of New Sulpho Acids of Phenyl-rosinduline and Analogues and Homologues thereof.
Year: 1893

page_text: Date of Application, 22nd Apr., 1893
Complete Specification Left, 22nd Jan., 1894-Accepted, 24th Feb., 1894
PROVISIONAL SPECIFICATION.
The Manufacture of New Sulpho Acids of Phenyl-rosinduline and
Analogues and Homologues thereof.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen on Rhine in the Empire of Germany to be as follows :--
In the Specification of Letters Patent No. 15259 of 1888 granted to me there
are described the first known sulpho acids of phenyl-rosinduline. Certain of
these are known in commerce under the name of azocarmine and are widely used
for dyeing animal fibre.
Further inventions with reference to this group of dyes are described in the
Specifications of Letters Patents Nos. 6875, 14836 and 17168 of 1890 and
No. 11629 of 1891 all granted to me and to which I refer.
The present invention relates in the first place to the manufacture of isomers of
the said azocarmine which are dyestuffs possessing the valuable properties of
azo carmine while giving distinctly different shades of red when dyed on animal
fibre from the acid bath.
In the Specifications of Letters Patent No. 101389 and No. 10138B" there is
described the production of indulines by the combination of hydroxy-naphtho-
quinone-anil with diamines and alkylated diamines, also the production of induline
sulpho acids by the condensation of hydroxy-naphtho-quinone-anil-sulpho acid
with the same class of bodies.
According to the present invention suitably substituted sulphonated phenylene
ortho diamines are submitted to analogous condensations with hydroxy-naphtho-
quinone-anil and sulpho acids thereof.
Thus for instance if phenyl-ortho-phenylene diamine-sulpho-acid (also known as
ortho amido-diphenylamine-sulpho acid) be condensed with hydroxy-naphtho-
quinone anil, a new phenyl-rosinduline-mono-sulpho-acid is obtained. This sulpho
acid contains its sulpho-group attached to the benzene part of the naphtho-
phenazine nucleus. The new monosulpho acid serves as initial material for the
production of an iso-azocarmine for by treating it with concentrated sulphuric
acid it is converted into a soluble disulpho acid. This acid is hereinafter called
iso-azo-carmine I.
with
In an analogous manner the phenyl-ortho-phenylene-diamine-sulpho acid (ortho
amido-diphenylamine-para-sulpho acid) herein before mentioned can be condensed
hydroxy-naphtho-quinone-anil-para-sulpho acid whereby a disulpho acid is at
once obtained. This acid hereinafter called iso-azocarmine II is practically
identical with iso-azocarmine I though the position of one of the sulpho groups in
the molecule may be different.
The reactions above described can also be applied to analogous and homologous
initial materials whereby corresponding sulpho acids are obtained.
The following examples will serve to further illustrate the nature of this
invention, but they are merely intended to explain its application in certain
specific cases in other cases considerable variations are sometimes necessary and in
all cases the details can be varied. The parts are by weight.

page_text: SO,H
CH..NH,
NHCH 1
about ten parts of beta-hydroxy-naphthoquinone anil about 200 parts of alcohol and
about one hundred parts of water. Boil the mixture whilst stirring well. The
hydroxy-naphthoquinone anil disappears as the reaction advances and the new
induline sulpho acid separates out as a heavy crystalline powder. The reaction is
complete when a hot weakly alkaline solution of the precipitate is completely
reprecipitated by the addition of a slight excess of alkali and the mother liquor is
not coloured yellowish red by the presence of unchanged naphthoquinone anil.
When the test is satisfied collect press and dry the precipitate. The new phenyl
rosinduline-mono sulpho acid differs from the isomeric body described in the
Specification of Letters Patent No. 15259 of 1888 in yielding alkaline salts soluble
in both hot and cold water. It can best be distinguished from the corresponding
sulpho acids of the Specifications No. 6875 of 1890 by converting it into its
disulpho acid, the properties of which are hereinafter described.
EXAMPLE 2. SULPHONATION OF THE NEW MONO-SULPHO ACID OF PHENYL-
ROSINDULINE. PRODUCTION OF ISOAZOCARMINE I.
Stir about ten parts of phenyl-rosinduline-mono-sulpho-acid into about forty
parts of concentrated sulphuric acid (containing about ninety six per cent. real
sulphuric acid H₂SO). Heat the mixture to about one hundred degrees
centigrade, till a test portion is soluble in about fifty times the quantity of water.
To isolate the sulpho acid soluble in water so obtained, pour the whole melt when
cold into about four hundred parts of ice. The sulpho acid is but slightly soluble
in dilute sulphuric acid and therefore separates out. Collect and press. Dissolve
the press cakes in boiling water adding alkali, and precipitate the dye from the
boiling solution by adding common salt. Filter, press and dry.
Iso-azocarmine I thus obtained is in the form of its alkaline salts readily soluble
in water. It dyes wool from an acid bath giving bluer shades of red than the
disulpho acid of the Specification No. 15259 of 1888. It differs from the disulpho
acids of the Specification No. 6875 of 1890 in that the colour of the solutions of its
soda salt remain practically the same whether they be rendered acid with a mineral
acid or alkaline, whereas the disulpho acids of the said Specification show different
colours under these conditions. The new acid closely resembles or is practically
identical with sulpho acid B of Patent No. 1716800 in its properties.
EXAMPLE 3. PRODUCTION OF ISO-AZOCARMINE II.
Mix together about ten parts of hydroxy-naphthoquinone-anil-sulpho acid (see.
Specification No. 101382) about eight and a half parts of ortho-amido-diphenyl-
amine-para-sulpho acid and about one hundred litres of water. Boil the mixture;
a deep red solution results. Continue boiling until on working up test-portions of

page_text: quantity that the maximum precipitation of the sodium salt of the dye is obtained
and a further addition causes no further precipitate. Allow to cool, separate the
precipitate from the mother liquor which should be of a brown yellow colour and
press. To purify the dye, dissolve the press cakes in hot water and precipitate
with caustic soda.
As aforesaid isoazocarmine I and II resemble one another so closely as to be
practically identical.
Dated this 22nd dow of Amil 1902
COBILLIE DIEUITTOAIJUN.
The Manufacture of New Sulpho Acids of Phenyl-rosinduline and
Analogues and Homologues thereof.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin & Soda Fabrik
of Ludwigshafen-on-Rhine in the Empire of Germany) and in what manner the
same is to be performed to be particularly described and ascertained in and by
the following statement :-
In the Specification of Letters Patent No. 15259 of 1888 granted to me on a
communication from my foreign correspondents there is described the first known
sulpho acids of phenyl-rosinduline. Certain of these are known in commerce under
the name of azo-carmine and are widely used for dyeing animal fibre.
Further inventions with reference to this group of dyes are described in Letters
Patents Nos. 6875, 14836 and 17168 of 1890 and No. 11629 of 1891 all granted to
me on communications from my foreign correspondents and to which I refer.
The present invention relates in the first place to the manufacture of isomers of
the said azocarmine, which isomers are dyestuffs possessing the valuable properties
of azocarmine while giving when dyed on animal fibre from the acid bath shades of
red distinctly different from those given by azocarmine.
The process by which the said new iscazocarmines are produced is based upon
principles similar to those which underly the invention described by my foreign
correspondents in the Specifications of Letters Patent No. 101389 and in particular
in No. 10138B⁹.
In the said Specifications there is described the production of indulines by the
combination of hydroxy-naphthoquinone-anil with diamines and alkylated diamines
also the production of induline sulpho acids by the condensation of hydroxy-
naphthoquinone-anil-sulpho acid with the same class of bodies.
According to the present invention suitably substituted sulphonated phenylene-
ortho diamines are submitted to analogous condensations with hydroxy-naphtho-
quinone-anil and sulpho acids thereof.
Thus for instance if phenyl-ortho-phenylene diamine-sulpho acid (also known as
ortho amido diphenylamine-sulpho acid) be condensed with hydroxy-naphtho-
quinone-anil, a new phenyl-rosinduline-mono-sulpho acid is obtained. This sulpho
acid contains its sulpho group attached to the benzene part of the naphtho-phenazine
nucleus. The new mono-sulpho acid serves as the initial material for the production
of an iso-azocarmine for, by treating it with concentrated sulphuric acid, it is
converted into a soluble disulpho acid. This acid is hereinafter called "iso-
azocarmine I."
In an analogous manner the phenyl-ortho-phenylene-diamine-sulpho acid (ortho-
amido-diphenylamine-para-sulpho acid) hereinbefore mentioned can be condensed
with hydroxy-naphthoanil-para-sulpho acid, whereby a disulpho acid is at once

page_text: obtained. This acid hereinafter called "iso-azocarmine II" is practically identical
with iso-azocarmine I though the position of one of the sulpho groups in the
molecule may be different.
The reactions above described can also be applied to analogous and homologous
initial materials, whereby corresponding sulpho acids are obtained. Thus for
instance instead of hydroxy-naphthoquinone-anil the corresponding ortho- and
para-toluides can be used. These hydroxy-naphtho-quinone-toluides can be obtained
in the same way as the aniline derivative but using ortho- and para-toluidine
instead of aniline. On the other hand instead of the phenyl-ortho-phenylene-
diamine-sulpho acid (ortho-amido-diphenylamine-para sulpho acid) the homologues
ortho-tolyl-ortho-phenylene-diamine-sulpho acid and para-tolyl-ortho-phenylene-
diamine-sulpho acid can be used. These homologues can be prepared in the same
way as the phenyl-ortho-phenylene-diamine sulpho acid but using ortho or para
toluidine instead of aniline.
The following examples will serve to further illustrate the nature of the invention
and the manner in which it can be carried into practical effect, but they are mainly
intended to explain its application in certain specific cases in other cases
considerable variations are sometimes necessary and in all cases the details can be
varied without departing from the invention. The parts are by weight.
EYANDID 1 MANURACTURE OR THE NEW PHENYL ROSINDULLINE-MONO-
NHCH 1
about ten parts of beta-hydroxy-naphthoquinone-anil, about two hundred parts of
alcohol and about one hundred parts of water. Boil the mixture whilst well stirring.
The bydroxy-naphthoquinone-anil disappears as the reaction advances and the new
induline sulpho-acid separates out as a heavy crystalline powder. The reaction is
complete when a hot weakly alkaline solution of the precipitate is completely
reprecipitated by the addition of a slight excess of alkali and the mother liquor is
not coloured yellowish red by the presence of unchanged naphthoquinone-anil.
When this test is satisfied collect, press and dry the precipitate. The new
phenyl-rosinduline mono-sulpho-acid differs from the isomeric body described in the
Specification of Letters Patent No. 15259 of 1888 in yielding alkaline salts soluble
in both hot and cold water. It can best be distinguished from the corresponding
sulpho acids of the Specification No. 6875 of 1890 by converting it into its disulpho
acid, the properties of which are hereinafter described.
EXAMPLE 2. SULPHONATION OF THE NEW MONO-SULPHO-ACID OF PHENYL-
ROSINDULINE. PRODUCTION OF ISO-AZOCARMINE I.
Stir about ten parts of phenyl-rosinduline-mono-sulpho acid into about forty
parts of concentrated sulphuric acid (containing about ninety-six per cent. real
sulphuric acid H,SO,). Heat the mixture to about one hundred degrees centigrade
till a test portion is soluble in about fifty times the quantity of water. To isolate
the sulpho acid soluble in water so obtained, pour the whole melt, when cold, into
about four hundred parts of ice. The sulpho acid is but slightly soluble in dilute
sulphuric acid and therefore separates out. Collect and press. Dissolve the press-
cakes in boiling water adding alkali and precipitate the dye from the boiling solution
by adding common salt. Filter, press and dry.

page_text: Iso-azocarmine I thus obtained is in the form of its alkaline salts readily soluble
in water. It dyes wool from an acid bath giving bluer shades of red than the
disulpho acid of the Specification No. 15259 of 1888. It differs from the disulpho-
acids of the Specification No. 6875 of 1890 in that the colour of the solutions of its
soda salt remains practically the same whether they be rendered acid with a
mineral acid or alkaline, whereas the disulpho acids of the said Specification
show different colours under these conditions. The new acid closely resembles
or is practically identical with sulpho acid B of Patent No. 1716800 in its
properties.
EXAMPLE 3. PRODUCTION OF ISO-AZOCARMINE II.
Mix together about ten parts of hydroxy-naphtho-quinone-anil-sulpho acid (see
Specification No. 10138) about eight and a half parts of ortho-amido-diphenyl-
amine-para-sulpho acid and about one hundred litres of water. Boil the mixture;
a deep red solution results. Continue boiling until on working up test portions
of the solution in the manner hereinafter described for the whole quantity no
increase in the quantity of dye, but slightly soluble in dilute caustic soda, is
noticeable.
To isolate the iso-azocarmine II from the entire product add caustic soda solution
(containing say about 35 per cent. NaOH) to the hot solution in such quantity that
the maximum precipitation of the sodium salt of the dye is obtained and a further
addition causes no further precipitate. Allow to cool, separate the precipitate from
the mother liquor (which should be of a brown yellow colour) and press. To
purify the dye, dissolve the press cakes in hot water and precipitate with caustic
soda.
As aforesaid iso-azocarmine I and II resemble one another so closely as to be
practically identical. The homologous dye obtainable from the homologous initial
materials closely resemble iso-azocarmine in properties and in colour.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of new sulpho acids of phenyl-rosinduline and homologues
thereof by the condensation of phenyl-ortho-phenylene-diamine-sulpho acid or its
homologues on the one hand with hydroxy-naphthoquinone-anil or its homologues
or sulpho acids on the other hand all substantially in the manner hereinbefore
described.
2. The manufacture of a new mono-sulpho-acid of phenyl-rosinduline substantially
in the manner hereinbefore described under Example 1.
3. The manufacture of iso-azocarmine I a new sulpho acid of phenyl-rosinduline
by first preparing a new mono-sulpho acid in the manner hereinbefore described and
claimed in the second claiming clause and then further sulphonating the said mono-
sulpho acid.
4. The manufacture of iso-azocarmine II a new disulpho acid of phenyl-rosinduline
substantially in the manner described under Example 3.
5. As articles of manufacture the new sulpho acids of phenyl-rosinduline and its
homologues such as can be obtained substantially as hereinbefore described and
claimed.
Dated this 22nd day of January 1894.
JOHNSONS & WILLCOX,
Agents.