The Manufacture of the Sulpho Acids of a Red Basic Naphthaline- dyestuff.
Year: 1888

page_text: This Specification was, upon the 22nd day of September 1890, Amended under
Sections 18 to 21 of the Patents, Designs, and Trade Marks Act, 1883.
Date of Application, 23rd Oct., 1888
Complete Specification Left, 23rd July, 1889-Accepted, 14th Sept, 1889.
PROVISIONAL SPECIFICATION.
The Manufacture of the Sulpho Acids of a Red Basic Naphthaline-
dyestuff.
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 Ludwig-
shafen on Rhine, in the Empire of Germany, to be as follows:-
By heating anilidonaphtochinonanil (naphtochinondianilid, Beilstein 1st Edition
page 1724) with hydrochloride of aniline and aniline a red basic colouring matter is
produced, which can be converted into sulpho acids of useful qualities for dyeing
printing.
As is well known anilidonaphtochinonanil is produced by the action of aniline with
derivatives of Alpha-and Beta-naphtochinon and with nitroso and azo compounds of
the naphtalin group and the like. When the last named compounds are heated"
together with hydrochloride of aniline and aniline the formation of the anilidonaphto-
chinonanil and its conversion into the red colouring matter may be done in one
operation.
:
Suitable compounds for the formation of the anilidonaphtochinonanil are for

page_text: The following are examples of the production of the basic colouring matter and
also of the production of its sulpho-acids according to this Invention.
DXAMPLE 1.
10 parts by weight of anilidonaphtochinonanil
10
35
::
•
.
,, hydrochloride of aniline
aniline
are heated in an oil bath to about 130° to 140° Centigrade for about 6 hours or until
a sample will dissolve in ether with a red coloured solution-and another sample when
dissolved in concentrated sulphuric acid will give a green coloured solution. The green
solution in sulphuric acid being characteristic of the dyestuff.
The melt when cold is boiled with dilute hydrochloric acid. After cooling it is
filtered and the residue is rinsed with water until all the aniline salt and the like is
removed and then it is dried.
A further purifying of the dyestuff obtained can be done by means of suitable
solvents, in the most perfect manner by producing its crystallising base.
For that purpose 10 parts by weight of the raw dyestuff are treated repeatedly
with 30 parts by weight of toluol at a temperature of about 100° Centigrade until
the impurities which are dissolved by the toluol with a brown colour, are entirely
removed.
The undissolved residue is freed from the toluol and dissolved in about 30 parts by
weight of hot alcohol. To the red violet alcoholic solution thus obtained caustic soda
is added until an alkaline reaction is observed, thereon the base of the dyestuff will
settle. After filtering, washing, drying, and treating with a suitable solvent (for
instance hot toluol) the base can be obtained in glittering dark redish brown crystals
melting at a temperature of 233°-234° Centigrade.
By concentrated sulphuric acid the pure base of the dyestuff is dissolved with a
pure green colour. On adding water to this solution the sulphate of the dyestuff is
separated as a red precipitate, abundantly soluble in pure water. A similar solubility
is displayed by the hydrochloride, which may be easily obtained by macerating the
base of the dyestuff with hydrochloric acid.
The analyses hitherto made of the dyestuff are corresponding to the empirical
formula C H₂ N, and from its general behaviour it closely approaches the colouring
29 21
matters of the Induline series

page_text: to 135° Centigrade and kept at this temperature until the described reactions will be
observed. The formation of the colouring matter is in this case quicker than
in the last preceding example. The working up is done in the same manner as
before.

page_text: in ten times its quantity of water forms a red precipitate, which is completely soluble
when boiled in pure water. The mixture of the acids will then be introduced into
100 parts of ice water and filtered and pressed. The residue consisting of the
disulphoacid will be suspended in 400 parts of water and ammonia is added until-a
complete solution is effected. This solution is boiled until the ammonia salt of the.
disulpho-acid on cooling almost perfectly precipitates. The separated dyestuff is then
pressed, filtered and dried. In a similar manner the potash and soda salt of the
disulpho-acid may be produced, being obtained in red-bronze glittering crystals.
The free sulpho-acid may also be crystallized from hot water.
This disulphoacid produces on animal fibre a bright crimson when dyed in an acid
bath.
PRODUCTION OF THE SULPHO ACID EASILY SOLUBLE IN COLD WATER.
10 parts by weight of the aforesaid coloring matter or a corresponding quantity of
its nono- or disulpho-acid will be introduced into 60 parts by weight of fuming
sulphuric acid, containing 23% free anhydride while constantly agitating. Then the
mixture will be heated in a water bath until a sample is easily and completely soluble
in twenty times its quantity of cold water. The bulk then will be diluted with 1000
parts of water, neutralized with lime, filtered, evaporated and the lime salt converted
into the soda salt.
F
Having regard to the easy solubility of this sulpho acid and its salts, by which the
purification of the dyestuff is rendered difficult, it is of great advantage to begin the
sulphonating with pure materials.
By this sulpho acid a bright crimson color is produced on animal fibre, when dyed
an acid bath.
in an
22
1000
J. H. JOHNSON & Co.,.
Agents.
COMPLETE SPECIFICATION (AMENDED).
The Manufacture of the Sulpho Acids of a Red Basic Naphthalene-
dyestuff.
I
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 com-
municated to me from abroad by the Badische Anilin and Soda Fabrik of
Ludwigshafen on-the-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 :-
This Invention is based on the observation that the red basic colouring matter
which is produced by heating anilido-naphthoquinone anil (naphthoquinone-dianilide,
Beilstein's Handbook of Chemistry, Eirst Edition, page 1724) with hydrochloride
of aniline and aniline, and which has recently been named Kosinduline" (Journ.
Chem. Soc. No. CCCXIII. Dec. 1888. page 1291.) can be converted into Sulphoacids
of useful qualities for Dyeing and Printing.
As is well-known, Anilide-naphthoquinone-anil is produced by the action of aniline
upon derivatives of Alpha- and Beta-naphthoquinone and upon nitroso- and azo-
compounds of the Naphthalene-group. When the last named compounds are heated
together with hydrochloride of aniline and aniline. the formation of the Anilido-
naphthoquinone-anil and its conversion into the red, colouring matter may be effected
in-one:operation.

page_text: Di-brom-alphanaphthol (Chem. News XLIX, 146).
My foreign correspondents have found that the following compounds, the converting
of which into anilido-naphthoquinone-anil has hitherto not been known, will also
yield the red dye stuff, when heated with hydrochloride of aniline and aniline,
viz :—
Alpha-naphthoquinone
Monochlor-alpha-naphthoquinone (fusing point 109° to 111° Centigr.)
Oxy-alphanaphthoquinone
Anilido-alpha-naphthoquinone
Benzol-azo-dimethyl-alphanaphthylamine.
Although anilido-naphthoquinone anil is mentioned as occurring as an intermediate
product yet it is in practical working entirely immaterial whether it is formed or not and
no attention need be paid to its formation indeed it is believed notwithstanding the state-
ment in chemical literature to the contrary (Berichte XXI 679) that of the bodies
hereinbefore mentioned those which contain no oxigen viz-the amido-azo bodies Benzol-
azo-alphanaphthylamine; Benzol-azo-ethyl-alphanaphthylamine; Benzol-azo-phenyl-
alphanaphthylamine and Benzol-azo dimethylalphanaphthylamine yield rosinduline
without the intermediate production of anilido-naphthoquinone anil.
Although the above named compounds may all be used for the production of the
red basic Naphthalene-Dyestuff, the results obtained are of a variable nature in point
of economy and I therefore first describe a manufacturing process, which may be
conveniently employed in order to produce the said colouring matter or "Rosinduline"
for the purpose of the present invention.
I. PRODUCTION OF THE BASIC COLOURING MATTER.
About ten (10) parts by weight of the above nained Benzol-azo-alphanaphthy-
lamine, in the state of its Hydrochloride, are mixed and heated with about ten (10)
parts by weight of Hydrochloride of aniline and about thirty five (35) parts by
weight of aniline in an enamelled vessel, provided with an agitator and fitted up
within an oil bath. The temperature is gradually raised during about four hours to
about one hundred and thirty (130) degrees centigrade, and then it is steadily
increased during another four hours to about one hundred and seventy (170) degrees
centigrade, which temperature is maintained for about four hours or until the operation
appears to be finished. This point may be ascertained by taking from time to time
a sample of the mixture and dissolving the same in concentrated sulphuric acid.
The operation may be considered at an end, if the green colour of the solution no
longer increases in purity, the green colour of the solution in sulphuric acid being
characteristic of the red Dyestuff.
Throughout this operation the mixture is well agitated. At last it acquires a semi-
fluid condition and the appearance of a so-called melt." It is then allowed to cool
down and the said "melt" is boiled with dilute hydrochloric acid, in order to

page_text: eliminate the excess of unemployed aniline and other soluble constituents formed
during the reaction. After cooling, the result of the operation is filtered and the
residue is well washed with water until all the aniline salt and the like is removed.
The "melt" or "crude product," which after this treatment consists of the red
basic colouring matter in a semi-purified or partly separated condition, is then dried and
may in this state be conveniently employed for the purpose of this Invention, as
hereinafter described.
In order to obtain the red basic Dyestuff in its perfectly pure or isolated condition,
a further purification of the "melt" or "crude product" may be effected by means
of suitable solvents, and in the most perfect manner by producing its crystallized
base.
For this purpose about ten (10) parts by weight of the said crude product, partly
purified by treatment with hydrochloric acid and water, as above described, are
treated repeatedly with about thirty (30) parts by weight of toluol at a temperature
of about one hundred (100) degrees Centigrade until the impurities, which are dissolved
by the toluol with a brown colour, are entirely removed.
The undissolved residue is freed from the toluol and dissolved in about twenty (20)
parts by weight of hot alcohol. To the filtered reddish-purple alcoholíc solution thus
obtained, caustic soda liquor is added until an alkaline reaction is observed. The base
of the red basic colouring matter then separates out and may after filtering, washing,
drying and treating with a suitable solvent. (for instance: hot toluol)-be obtained in
glittering dark reddish-brown crystals melting at a temperature of 233 to 234 degrees
Centigrade.
By concentrated sulphuric acid the pare base of the Red basic Dyestuff is
dissolved with a pure green colour. On adding water to this solution the Sulphate
of the dyestuff is separated as a red precipitate. The Hydrochloride may also be easily
obtained by digesting the base of the Dyestuff with hydrochloric acid.
In an analogous manner the red basic dyestuff can be produced in a condition
suitable for the hereinafter described conversion into its Sulphoacids (that is, either
in the condition of the above named partly purified "Melt" or as pure base, Sulphate
or Hydrochloride) by using in lieu of the Bonzol-azo-alphanaphthylamine in the
hereinbefore described manufacturing process other suitable compounds for the
formation of Anilido-naphthoquinone-anil, and then treating the crude products or
melts thus obtained by the above described methods of separation or purification.

page_text: similar acid character. Those sulpho acids are particularly useful as substitutes for
Archil.
The Monosulphoacid, on account of the facility with which it can be isolated or
separated in a practically pure condition (as hereinafter described) is of especial
value as a definite material, from which, by subsequent sulphonation, the above said
soluble Sulpho acids may be conveniently prepared without necessitating the
employment of the red basic dyestuff in a perfectly pure or isolated condition.
The following are examples of the manner in which the present Invention is or
may be practically carried out.
EXAMPLE I PRODUCTION OF THE MONOSULPHOACID.
About ten (10) parts by weight of the red basic dye-stuff or colouring matter
("Rosinduline") in the pure or isolated condition of its base, Hydrochloride or
Sulphate, as hereinbefore described, are mixed with about fifty (50) parts by weight
of concentrated sulphuric acid containing about from 95 to 96 per cent. of the
Monohydrate SO* H2, and while constantly agitating, the mixture is heated to about
one hundred (100) degrees Centigrade for about five hours or until a sample,
precipitated and washed with water, forms a practically clear solution upon the
addition of cold and dilute! caustic, soda-liquor. This point being arrived at, the
mixture is introduced into ten times the quantity of water, and the precipitate of
the practically pure Monosulphoacid thus produced is filtered, washed and well
pressed.
A further purification may be effected by producing the characteristic sodium salt
of the Monosulphoacid thus obtained. For this purpose the well pressed precipitate
is intimately mixed with or suspended in about eight hundre 1 (800) parts by weight
of cold water and then dissolved by adding gradually the requisite amount of caustic
soda liquor. If this solution be then heated to the boiling point and be rendered
strongly alkaline by adding thereto about twenty (20) parts by weight, of caustic soda
liquor, containing about thirty five (35) per cent. of sodium hydrate, a practically
complete separation of the sodium salt is effected. The mixture is then allowed to
cool down to about sixty degrees Centigrade and the crystalline precipitate thus obtained
is filtered. In order to produce the free Monosulphoacid, the said precipitate is
afterwards, without washing well pressed, suspended in water and finally decomposed
by diluted sulphuric acid, filtered washed and dried.
By employing caustic potash instead of caustic soda in the above described
purifying process a crystallised potassium salt will be obtained which is equally suitable
for the preparation of pure Monosulpho acid.
The hereinbefore described separation and purification of the Monosulphoacid
renders it possible, as above mentioned, to dispense with the employment of the red
basic dyestuff in its perfectly pure or isolated condition. An equally good result may
thus be obtained in an economical and simple manner by employing the red basic
dye-stuff in the state of the hereinbefore described "Melt or crude product,"
from which by a treatment with dilute hydrochloric acid and water the soluble con-
stituents (aniline salts and the like) have been eliminated.
If the red basic Dyestuff be employed in such semi-purified or partly separated
condition, a lesser proportion of concentrated sulphuric acid may also be used for its
sulphonation than in the above given example, say for instance, about thirty (30)
parts by weight of concentrated sulphuric acid containing about from 9 to 96 per
cent. of the Monohydrate for about ten parts by weight of the "melt" produced
preferably by beating the Hydrochloride of Benzol-azo-alphanaphthylamine with
hydrochloride of aniline and aniline, and subsequently extracting the same with
hydrochloric acid and water, as hereinbefore described. The sulphonation is then
carried out in the above described manner and the purification of the sulphonated
product, thus obtained, is finally effected by converting the same into the characteristic
sodium-salt of the Monosulphoacid and decomposing this saline compound by a mineral
acid, as herein before described.

page_text: EXAMPLE LI. TRODUCTION OF THE DISULT HVACID
The most convenient material for the production of the Disulphoacid is the
Monsulpho acid as hereinbefore explained. The red basic Dyestuff may however
likewise be employed in its isolated or pure condition, preferably in the state of its
Sulphate.
In order to prepare the Disulphoacid from any of the aforesaid materials, about
ten (10) parts by weight of the same are mixed with about thirty (30) parts by
weight of fuming sulphuric acid, containing about twenty three (23) per cent. of free
or available anhydride, the mixture being, preferably, well cooled by the external
application of ice during the operation. The whole is then heated, while constantly
agitating, to about forty (40) degrees centigrade, until a sample, diluted with ten
times its quantity of water, forms a red precipitate, which is completely soluble when
boiled in pure water. This sulphonating process is effected by a gentle and moderate
action and generally requires from two to three hours to be completed. The result.
of the operation is then gradually introduced into about two hundred (200) parts by
weight of ice-water, whereby a precipitate is produced consisting of the Disulphoacid.
This precipitate is filtered, pressed and afterwards mixed with or suspended in about
Caustic ammonia liquor is then
four hundred (400) parts by weight of water.
gradually added, until a practically complete solution is effected. This solution is
boiled, until on cooling the ammonium salt of the Disulphoacid almost completely
separates out in a crystallized condition, which point may be ascertained by taking a
sample of the solution from time to time and cooling it. The separated Dye-stuff is
then filtered, pressed and dried.
In a similar manner the potassium- and sodium-salt of the Disulpho acid may be
produced, being obtained in red-bronze glittering crystals, but in their preparation
every excess of alkali should be carefully avoided, as it interferes to a certain extent
with the separation of the said salts. The addition of the chlorides of potassium or
sodium is likewise recommended in order to render the separation of the respective
saline compounds of the Disulphoacid more perfect.
The free Disulphoacid is prepared from the above salts and may be crystallized
from hot water.
On account of the hereinbefore described crystallizing properties of the potassium-
sodium and ammonium-salts of the Disulphoacid, these compounds may be also obtained
by sulphonating the red basic Dyestuff in its aforesaid semi-purified condition or
"melt" and then treating the sulphonated product as above described, but in practice
such variation of the process has not been found to be advantageous.
EXAMPLE III. PRODUCTION OF THE SULPHOACID EASILY SOLUBLE IN COLD WATER.
Having regard to the easy solubility of this Sulpho acid and its salts, by which
the purification of the same is rendered difficult, it is of great advantage to begin the
sulphonating process with pure materials. Such materials are the red basic Dye-
stuff in its isolated or pure condition, preferably in the state of its Sulphate, or the
Mono- and Disulpho acid, prepared and purified as hereinbefore described. The
Monosulphoacid is preferred. As an example, about ten (10) parts by weight of
the Monosulphoacid are gradually introduced into about sixty (61) parts by weight
of fuming sulphuric acid, containing about twenty three (23) per cent. of free or
available anhydride while constantly agitating. During this operation the mixture is
well cooled and then it is heated in a water-bath to about one hundred degrees
Centigrade until a sample is easily and completely soluble in about twenty times its
quantity of cold water." The entire product is then diluted with about one thousand
(1000) parts by weight of water, neutralized with milk of lime, filtered and the
solution of the lime salt thus obtained is decomposed by carbonate of soda in order to
prepare the sodium salt of the Sulpho acid, which may then be obtained in a solic
condition by evaporating the filtered liquor.

page_text: "
I do not claim the production of the hereinbefore named Red basic Naphthalene-
dyestuff or Rosinduline," as this colouring matter (or products containing the same
as their principal constituent) may be prepared by the action of aniline and its salts
upon a great number of Napthalene-derivatives with the intermediate production-of
Anilido-naphthoquinone anil, as hereinbefore described.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what 1
claim is:-
First. The process of preparing the Monosulphoacid of the red basic Naphthalene-
dyestuff, which process consists in heating the said colouring matter either in its
pure or isolated condition (such as Base, Hydrochloride or Sulphate) or in its semi-
purified or partly separated condition (such as the hereinbefore described "melt" or
"crude product" after elimination of the aniline salts) with concentrated sulphuric
acid until the result is soluble in cold diluted caustic alkali, then precipitating with
water, and if necessary purifying the Monosulphoacid thus obtained by conversion
into its crystallized alkaline salts, all substantially as hereinbefore described.
Second. The process of preparing the Disulphoacid of the red basic Naphthalene-
dyestuff, which process consists in gently treating the said colouring matter or, by
preference, its above-named Monosulphoacid with faming sulphuric acid until the
result is soluble in boiling pure water, then precipitating with water and if necessary
purifying the Disulphoacid thus obtained by conversion into its crystallized alkaline
or ammonium salts, all substantially as herein before described.
Third. The process of preparing a Sulphoacid of the Red basic Naphthalene Dyestuff,
soluble in cold water, which process consists in heating the said colouring matter in
its pure or isolated condition, or its aforesaid Disulphoacid or, by preference, its
above named Monosulphoacid with fuming Sulphuric acid until the result is easily
soluble in cold water, then removing the excess of sulphuric acid and preparing an
alkaline salt, all substantially as herein before described.
Fourth. As a new manufacture, the herein before named Sulphoacids of the Red
basic Naphthalene Dyestuff, produced by direct sulphonation, substantially as
hereinbefore described.
Dated this 23rd dow of July 1880
J. H. JOHNSON & Co.,
Agents.

page_text: Date of Application, 23rd Oct., 1888
Complete Specification Left, 23rd July, 1889-Accepted, 14th Sept., 1839
EXAMPLE I.
10 parts by weight of anilidonaphtochinonanil
22
10
hydrochloride of aniline
".
"
35
aniline
"
32

page_text: a sample will dissolve in ether. with a red coloured solution-and another sample when
dissolved in concentrated sulphuric acid will give a green coloured solution. The green
solution in sulphuric acid being characteristic of the dyestuff.
The melt when cold is boiled with dilute hydrochloric acid. After cooling it is
filtered and the residue is rinsed with water until all the aniline salt and the like is
removed and then it is dried.
A further purifying of the dyestuff obtained can he done by means of suitable
solvents, in the most perfect manner by producing its crystallising base.
For that purpose 10 parts by weight of the raw dyestuff are treated repeatedly
with 30 parts by weight of toluol at a temperature of about 100° Centigrade until
the impurities which are dissolved by the toluol with a brown colour, are entirely
removed.
The undissolved residue is freed from the toluol and dissolved in about 30 parts by
weight of hot alcohol. To the red violet alcoholic solution thus obtained caustic soda
is added until an alkaline reaction is observed, thereon the base of the dyestuff will
settle. After filtering, washing, drying, and treating with a suitable solvent (for
instance hot toluol) the base can be obtained in glittering dark redish brown crystals
melting at a temperature of 233°-234° Centigrade.
By concentrated sulphuric acid the pure base of the dyestuff is dissolved with a
pure green colour. On adding water to this solution the sulphate of the dyestuff is
separated as a red precipitate, abundantly soluble in pure water. A similar solubility
is displayed by the hydrochloride, which may be easily obtained by macerating the
base of the dyestuff with hydrochloric acid.
The analyses hitherto nade of the dyestuff are corresponding to the empirical
forinula C H N3 and from its general behaviour it closely approaches the colouring
matters of the Luduline series.
10 parts by weight of hydrochloride of benzol-azo-alpha-naphty lamin
hydrochloride of aniline
10
35
11
"
"
27
are heated in an oil bath and the temperature raised in about an hour to about 100°
to 135° Centigrade and kept at this temperature until the described reactions will be
observed. The formation of the colouring matter is in this case quicker than
in the last preceding example. The working up is done in the same manner as
before.
4
are heated in an oil bath and the temperature raised in about an hour to about 100°
to 135° Centigrade and kept at this temperature until the described reactions will be
observed. The formation of the colouring matter is in this case quicker than
in the last preceding example. The working up is done in the same manner as
before.
are heated in
an oil bath to about 150° to 160° Centrigrade for about 8 hours or unti

page_text: by the above described reactions the formation of the colouring matter is completed
and will then be treated as before.
The quantities applied in the above describod examples will I believe give the best
results. The effect of the increase or decrease of the free aniline is the corresponding
protraction or acceleration of the reaction.
11. PRODUCTION OF THE SULPHOACIDS.
When directly sulphonated the red basic colouring matter may be converted into
three sulpho-acids, well distinguished by their solubility and well characterised.
When using concentrated sulphuric acid, even if acting energetically, mono-sulpho
acid only is obtained which is nearly insoluble in water.
When applying fuming sulphuric acid, mono-chlorhydrine-sulphuric acid or similar
compounds, the effect of which is due to their containing Anhydride, at first from the
monosulpho acid and from the un-sulphonated dye-stuff disulpho acid is produced,
which is distinguished by its ability for crystallisation and is soluble in hot water.
When increasing the action of the fuming sulphuric acid a probably higher sulphonated
acid is obtained which is easily soluble in cold water but does not crystallise.
Those sulpho acids which are soluble in water are especially suitable for dyeing
animal fibre.
By the following examples the production of the sulpho acids will be demonstrated.
EXAMPLE I.
PRODUCTION OF THE MONOSULPHO-ACID.
10 parts by weight of the herein before described coloring matter (base, Hydro-
chloride or Sulphate) are mixed with 50 parts by weight of Sulphuric acid of
66° Beaumé and while constantly agitating, the mixture is heated to about 95° to 100°
Centigrade until a sample, precipitated and washed with water, is entirely dissolved
by cold and diluted soda lye. Then the mixture is introduced into ten times the
quantity of water and the precipitate will be filtered, washed and pressed. For
purifying this monosulpho-acid its indifferently soluble soda salt may be produced.
For this purpose the precipitate is well mixed with 800 parts by weight of cold water
and dissolved by adding gradually sola lye. If this solution is then heated to boiling
point and is made strongly alkaline by adding 20 parts by weight of soda lye of
40° Beaumé, a complete separation of the soda salt is effected. After cooling the
crystalline soda salt is filtered washed and decomposed by diluted sulphuric acid.
EXAMPLE II.
PRODUCTION OF THE DISULPHOACID.

page_text: EXAMPLE III.
PRODUCTION OF THE SULPHO ACID EASILY SOLUBLE IN COLD WATER.
10 parts by weight of the aforesaid coloring matter or a corresponding quantity of
its mono- or disulpho-acid will be introduced into 60 parts by weight of funing
sulphuric acid, containing 23.% free anhydride while constantly agitating. Then the
mixture will be heated in a water bath until a sample is easily and completely soluble
in twenty times its quantity of cold water. The bulk then will be diluted with 1000
parts of water, neutralized with lime, filtered, ovaporated and the lime salt converted
into the soda salt.
Having regard to the easy solubility of this sulpho acid and its salts, by which the
purification of the dyestuff is rendered difficult, it is of great advantage to begin the
sulphonating with pure materials.
By this sulpho acid a bright crimson- color is produced on animal fibre, when dyed
in an acid bath.
COMPLETE SPECIFICATION.
The Manufacture of the Sulpho Acids of a Red Basic Naphthalene-
dyestuff.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been com-
municated to me from abroad by the Badische Anilin and Soda Fabrik of
Ludwigshafen on-the-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 :-
This Invention is based on the observation that the red basic colouring matter
which is produced by heating anilido-naphthoquinone anil (naphthoquinone-dianilide,
Beilstein's Handbook of Chemistry, First Edition, page 1724) with hydrochloride
of aniline and aniline, and which has recently been named "Rosinduline" (Journ.
Chem. Soc. No. CCCXIII. Dec. 1888. page 1291.) can be converted into Sulphoacids
of useful qualities for Dyeing and Printing.
As is well-known, Anilido-naphthoquinone-anil is produced by the action of aniline
upon derivatives of Alpha- and Beta-naphthoquinone and upon nitroso- and azo-
compounds of the Naphthalene- group. When the last named compounds are heated
together with hydrochloride of aniline and aniline the formation of the Anilido-
naphthoquinone-anil and its conversion into the red colouring matter may be effected
in one operation.
Suitable compounds for the formation of the Anilido-naphthoquinone-anil are for
example:-
:-
Amido-naphthoquinoneimide (Berichte XIII, 123, XV, 481)
Beta-naphthoquinone
Beta-napthoquinone-anilide } (Berichte XIV, 1493)
Ronzalara aluhonenhthulo

page_text: My foreign correspondents have found that the following compounds, the converting
of which into anilido-naphthoquinone-anil has hitherto not been known, will also
yield the red dye stuff, when heated with hydrochloride of aniline and aniline,
viz :—
Monochlor-alpha-naphthoquinone (fusing point 109° to 111° Centigr.)
Oxy-alphanaphthoquinone
Anilido-alpha-naphthoquinone.
Benzol-azo-dimethyl-alphanaphthylamine.
Although the above named compounds may all be used for the production of the
red basic Naphthalene-Dyestuff, the results obtained are of a variable nature in point
of economy and I therefore first describe a manufacturing process, which may be
.or "Rosinduline"
conveniently employed in order to produce the said colouring matter
for the purpose of the present invention.
I. PRODUCTION OF THE BASIC COLOURING MATTER.
About ten (10) parts by weight of the above named Benzol-azo-alphanaphthy-
lamine, in the state of its Hydrochloride, are mixed and heated with about ten (10)
parts by weight of Hydrochloride of aniline and about thirty five (35) parts by
weight of aniline in an enamelled vessel, provided with an agitator and fitted up
within an oil bath. The temperature is gradually raised during about four hours to
about one hundred and thirty (130) degrees centigrade, and then it is steadily
increased during another four hours to about one hundred and seventy (170) degrees
centigrade, which temperature is maintined for about four hours or until the operation
appears to be finished. This point may be ascertained by taking from time to time
a sample of the mixture and dissolving the same in concentrated sulphuric acid.
The operation may be considered at an end, if the green colour of the solution no
longer increases in purity, the green colour of the solution in sulphuric acid being.
characteristic of the red Dyestuff.
Throughout this operation the mixture is well agitated. At last it acquires a semi-
It is then allowed to cool
fluid condition and the appearance of a so-called "melt."
down and the said "melt" is boiled with dilute hydrochloric acid, in order to
eliminate the excess of unemployed aniline and other soluble constituents formed
during the reaction. After cooling, the result of the operation is filtered and the
residue is well washed with water until all the aniline salt and the like is reinoved.
The "melt or "crude product," which after this treatment consists of the red
basic colouring matter in a semi-purified or partly separated condition, is then dried and
may in this state be conveniently employed for the purpose of this Invention, as
hereinafter described.
"3
or
In order to obtain the red basic Dyestuff in its perfectly pure or isolated condition,
a further purification of the "melt" "crude product" may be effected by means
of suitable solvents, and in the most perfect manner by producing its crystallized
base.
For this purpose about ten (10) parts by weight of the said crude product, partly
purified by treatment with hydrochloric acid and water, as above described, are
treated repeatedly with about thirty (30) parts by weight of toluol at a temperature
of about one hundred (100) degrees Centigrade until the impurities, which are dissolved
by the toluol with a brown colour, are entirely removed.
The undissolved residue is freed from the toluol and dissolved in about twenty (20)
parts by weight of hot alcohol. To the filtered reddish-purple alcoholic solution thus
obtained, caustic soda liquor is added until an alkaline reaction is observed. The base
of the red basic colouring matter then separates out and may after filtering, washing,
drying and treating with a suitable solvent (for instance: hot toluol)-be obtained in
glittering dark reddish-brown crystals melting at a temperature of 233 to 234 degrees
Centigrade.
+

page_text: By concentrated sulphuric acid the pure base of the Red basic Dyestuff is
dissolved with a pure green colour. On adding water to this solution the Sulphate
of the dyestuff.is separated as a red precipitate. The Hydrochloride may also be easily
obtained by digesting the base of the Dyestuff with bydrochloric acid.
In an analogous manner the red basic dyestuff can be produced in a condition
suitable for the hereinafter described conversion into its Sulphoacids (that is, either
in the condition of the above named partly purified "Melt" or as pure base, Sulphate
or Hydrochloride) by using in lieu of the Benzol-azo-alphanaphthylamine in the
herein before described manufacturing process other suitable compounds for the
formation of Anilido-naphthoquinone-anil, and then treating the crude products or
melts thus obtained by the above described methods of separation or purification.
when directly sulphonated, the red basic colouring matter may be converted into
three sulpho acids, well distinguished from one another by their solubility and
crystallizing power and characterized by giving a green-coloured solution in
concentrated sulphuric acid.
If concentrated sulphuric acid be used for the purpose of sulphonation, even if
acting energetically, say, at temperatures up to one hundred and sixty (160) degrees
Centigrade, practically a Mono-sulphoacid only is obtained, which is nearly insoluble
in water.
When applying fuming sulphuric acid, monochlorhydrine sulphuric acid (SO³ H CI)
or similar compounds, the effect of which is due to their containing available sulphuric
anhydride, then, both from the said Monosulphoacid and from the unsulphonated
basic dyestuff, by carefully moderating the reaction, a Disulphoacid is produced,
which is soluble in hot water and distinguished by its crystallizing power.
If the action of the fuming sulphuric acid be increased, a probably higher
sulphonated acid is obtained, which is easily soluble in cold water, but does not
crystallise.
Those sulpho acids which are soluble in water, (that is the Di-sulpho acid and the
last named; probably higher, sulphonated compound) are especially suitable for dyeing
animal fibre, both producing a bright and even crimson dye, when applied in the
acid dye-bath, and capable of being associated with other colouring matters of a
similar acid character. Those sulpho acids are particularly useful as substitutes for
Archil.
The Monosulphoacid, on account of the facility with which it can be isolated or
separated in a practically pure condition (as hereinafter described) is of especial
value as a definite material, from which, by subsequent sulphonation, the above said
soluble Sulpho acids may be conveniently prepared without necessitating the
employment of the red basic dyestuff in a perfectly pure or isolated condition.
The following are examples of the manner in which the present Invention is or
may be practically carried out.
EXAMPLE I. PRODUCTION OF THE MONOSULPHOACID.
About ten (10) parts by weight of the red basic dye-stuff or colouring matter
("Rosinduline") in the pure or isolated condition of its base, Hydrochloride or
Sulphate, as herein before described, are mixed with about fifty (50) parts by weight
of concentrated sulphuric acid containing about from 95 to 96 per cent. of the
Monohydrate SO H², and while constantly agitating, the mixture is heated to about
one hundred (100) degrees Centigrade for about five hours or until a sample,
precipitated and washed with water, forms a practically clear solution upon the
addition of cold and diluted caustic soda-liquor. This point being arrived at, the
mixture is introduced into ten times the quantity of water, and the precipitate of
the practically pure Monosulphoacid thus produced is filtered, washed and well
pressed.

page_text: A further purification may be effected by producing the characteristic sodium salt
of the Monosulphoacid thus obtained. For this purpose the well pressed precipitato
is intimately mixed with or suspended in about eight hundred (800) parts by weight
of cold water and then dissolved by adding gradually the requisite amount of caustic
soda liquor. If this solution be then heated to the boiling point and be rendered
strongly alkaline by adding thereto about twenty (20) parts by weight of caustic soda
liquor, containing about thirty five (35) per cent. of sodium hydrate, a practically
complete separation of the sodium salt is effected. The mixture is then allowed to
cool down to about sixty degrees Centigrade and the crystalline precipitate thus obtained
is filtered. In order to produce the free Monosulphoacid, the said precipitate is
afterwards, without washing well pressed, suspended in water and finally decomposed
by diluted sulphuric acid, filtered washed and dried.
By employing caustic potash instead of caustic soda in the above described
purifying process a crystallised potassium salt will be obtained which is equally suitable
for the preparation of pure Monosulpho acid.
The hereinbefore described separation and purification of the Monosulphoacid
renders it possible, as above mentioned, to dispense with the employment of the red
basic dyestuff in its perfectly pure or isolated condition. An equally good result may
thus be obtained in an economical and simple manner by employing the red basic
dye-stuff in the state of the hereinbefore described "Melt" or "crude product,"
from which by a treatment with dilute hydrochloric acid and water the soluble con-
stituents (aniline salts and the like) have been eliminated.
If the red basic Dyestuff be employed in such semi-purified or partly separated
condition, a lesser proportion of concentrated sulphuric acid may also be used for its
sulphonation than in the above given example, say for instance, about thirty (30)
parts by weight of concentrated sulphuric acid containing about from 95 to 96 per
cent. of the Monohydrate for about ten parts by weight of the "melt" produced
preferably by heating the Hydrochloride of Benzol-azo-alphanaphthylamine with
hydrochloride of aniline and aniline, and subsequently extracting the same with
hydrochloric acid and water, as hereinbefore described. The sulphonation is then
carried out in the above described manner and the purification of the sulphonated
product, thus obtained, is finally effected by converting the same into the characteristic
sodium-salt of the Monosulphoacid and decomposing this saline compound by a mineral
acid, as hereinbefore described.
EXAMPLE II. PRODUCTION OF THE DISULPHOACID.
The most convenient material for the production of the Disulphoacid is the
Monsulpho acid as hereinbefore explained. The red basic Dyestuff may however
likewise be employed in its isolated or pure condition, preferably in the state of its
Sulphate.
In order to prepare the Disalphoacid from any of the aforesaid materials, about
ten (10) parts by weight of the same are mixed with about thirty (30) parts by
weight of fuming sulphuric acid, containing about twenty three (23) per cent. of free
or available anhydride, the mixture being. preferably, well cooled by the external
application of ice during the operation. The whole is then heated, while constantly
agitating, to about forty (40) degrees centigrade, until a sample, diluted with ten
times its quantity of water, forms a red precipitate, which is completely soluble when
boiled in pure water. This sulphonating process is effected by a gentle and moderate
action and generally requires from two to three hours to be completed. The result
of the operation is then gradually introduced into about two hundred (200) parts by
weight of ice-water, whereby a precipitate is produced consisting of the Disulphoacid.
This precipitate is filtered, pressed and afterwards mixed with or suspended in about
four hundred (400) parts by weight of water. Caustic ammonia liquor is then
gradually added, until a practically complete solution is effected. This solution is
boiled, until on cooling the ammonium salt of the Disulphoacid almost completely
separates out in a crystallized condition, which point may be ascertained by taking a

page_text: sample of the solution from time to time and cooling it. The separated Dye-stuff is
then filtered, pressed and dried.
In a similar manner the potassium- and sodium-salt of the Disulpho acid may be
produced, being obtained in red-bronze glittering crystals, but in their preparation
every excess of alkali should be carefully avoided, as it interferes to a certain extent
with the separation of the said salts. The addition of the chlorides of potassium or
sodium is likewise recommended in order to render the separation of the respective
saline compounds of the Disulphoacid more perfect.
The free Disulpboacid is prepared from the above salts and may be crystallized
from hot water.
On account of the herein before described crystallizing properties of the potassium-
sodium and ammonium-salts of the Disulphoacid, these compounds may be also obtained
by sulphonating the red basic Dyestuff in its aforesaid semi-purified condition or
"melt" and then treating the sulphonated product as above described, but in practice
such variation of the process has not been found to be advantageous.
b
EXAMPLE III. PRODUCTION OF THE SULPHOACID EASILY SOLUBLE IN COLD WATER.
Having regard to the easy solubility of this Sulpho acid and its salts, by which
the purification of the same is rendered difficult, it is of great advantage to begin the
sulphonating process with pure materials. Such materials are the red basic Dye-
stuff in its isolated or pure condition, preferably in the state of its Sulphate, or the
Mono- and Disulpho acid, prepared and purified as hereinbefore described. The
Monosulphoacid is preferred. As an example, about ten (10) parts by weight of
the Monosuiphoacid are gradually introduced into about sixty (60) parts by weight
of fuming sulphuric acid, containing about twenty three (23) per cent. of free or
available anhydride while constantly agitating. During this operation the mixture is
well cooled and then it is heated in a water-bath to about one hundred degrees
Centigrade until a sample is easily and completely soluble in about twenty times its
quantity of cold water. The entire product is then diluted with about one thousand
(1000) parts by weight of water, neutralized with milk of lime, filtered and the
solution of the lime salt thus obtained is decomposed by carbonate of soda in order to
prepare the sodium salt of the Sulpho acid, which may then be obtained in a solid
condition by evaporating the filtered liquor.
I do not claim the production of the herein before named Red basic Naphthalene-
dyestuff or Rosinduline," as this colouring matter (or products containing the same
as their principal constituent) may be prepared by the action of aniline and its salts
upon a great number of Napthalene-derivatives with the intermediate production of
Anilido-naphthoquinone-anil, as herein before described.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed I declare that what I
claim is -
First. The process of preparing the Monosulphoacid of the red basic Naphthalene-
dyestuff, which process consists in heating the said colouring matter either in its
pure or isolated condition (such as Base, Hydrochloride or Sulphate) or in its semi-
purified or partly separated condition (such as the hereinbefore described "melt" or
"crude product" after elimination of the aniline salts) with concentrated sulphuric
acid until the result is soluble in cold diluted caustic alkali, then precipitating with
water, and if necessary purifying the Monosulphoacid thus obtained by conversion
into its crystallized alkaline salts, all substantially as hereinbefore described.
Second. The process of preparing the Disulphoacid of the red basic Naphthalene-
dyestuff, which process consists in gently treating the said colouring matter or, by
preference, its above-named Monosulphoacid with fuming sulphuric acid until the
result is soluble in boiling pure water, then precipitating with water and if necessary
purifying the Disulphoacid thus obtained by conversion into its crystallized alkaline
or ammonium salts, all substantially as hereinbefore described.

page_text: Third. The process of preparing a Sulphoacid of the Red basic Naphthalene Dyestuff,
soluble in cold water, which process consists in heating the said colouring matter in
its pure or isolated condition, or its aforesaid Disulphoacid or, by preference, its
above named Monosulphoacid with fuming Sulphuric acid until the result is easily
soluble in cold water, then removing the excess of sulphuric acid and preparing an
alkaline salt, all substantially as hereinbefore described.
Fourth. As a new manufacture, the hereinbefore named Sulphoacids of the Red
basic Naphthalene Dyestuff, produced by direct sulphonation, substantially as
hereinbefore described.
1000
J. H. JOHNSON & Co.,
Agents.