The Manufacture or Production of Colouring Matters Derived from Anthraquinone.
Year: 1893

page_text: Date of Application, 7th Dec., 1893
Complete Specification Left, 6th Sept., 1894-Accepted, 6th Oct., 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 Colouring Matters Derived from
Anthraquinone.
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:-
This invention relates to the production of dyestuffs derived from anthraquinone.
My foreign correspondents have described in the Specification of Letters Patent
No. 4871, dated 18th March 1891, a process for producing colouring matters
containing nitrogen, which process consists in treating certain polyoxyanthra-
In the said
quinones with oxidising agents, in the presence of ammonia.
Specification, the following polyoxyanthraquinones are mentioned, viz. :-alizarin
pentacyanine, alizarin hexacyanine, and hexaoxyanthraquinone, which is isomeric
with alizarin hexacyanine, and the oxidation is effected simply by the atmospheric
oxygen.
My foreign correspondents have now found that a new and simple method which
yields similar results, and is distinguished by its more general applicability. This
process consists in treating oxyanthraquinones in the presence of aminonia, or
primary or secondary amines, or substances or mixtures acting in a similar manner,
with ammonium persulphate (see Journal für Praktische Chemie, Neue Folge,
volume 48, page 185), or other salts of the supersulphuric acid, or other materials
acting in a similar manner, as oxidising agents. The reaction easily proceeds in
diluted watery solution at a low temperature, and is finished in a short time. My
foreign correspondents usually employ two molecular proportions of ammonium
persulphate or the like, and one molecular proportion of oxyanthraquinone. The
fact that in this manner the quantity of the oxygen to be employed can easily be
determined, renders this method more advantageous than that described in the
Specification of the above Patent dated 18th March 1891 No. 4871.
This method, which is capable of being employed very generally, is illustrated by
the following example. The parts are kilos, by weight.
COLOURING MATTER FROM ALIZARIN BORDEAUX, AMMONIA, AND THE
AMMONIUM SALT OF SUPERSULPHURIC ACID.
50 parts of an alizarin bordeaux paste (containing 20 per cent. of pure alizarin
ammonia
bordeaux) are dissolved in about 500 litres of water and 100 litres
solution (20 per cent.). A solution prepared by dissolving 8.5 parts of ammonium
persulphate in from 50 to 100 litres of water, is then gradually added. The
beginning of the reaction is evident from a rising of the temperature, and it is
advisable to cool the liquid by adding ice. The end of the reaction is observable
from the fact that a sample taken out, when treated with an acid, yields a
precipitate which dissolves in concentrated sulphuric acid with a cherry red colour..
When this stage is arrived at, the liquid is mixed with muriatic or sulphuric acid,
and the dyestuff, which is separated as a dark purple red precipitate, is filtered off,
and washed with water, in order to remove any adherent acid.
This colouring matter materially differs from that resulting (as described in the
Specification of Letters Patent No. 8702, dated 21st May 1891) by heating

page_text: alizarin bordeaux merely with ammonia. The latter product dissolves in concen-
trated sulphuric acid with a bluish-red colour, whilst the solutions of the new
product in concentrated sulphuric acid, possess a yellowish-red colour.
The
absorption spectra of the sulphuric acid solutions of both dyestuff's shew the same
bands, except that those bands which the new colouring matter shews, are much
nearer to the violet end of the spectrum.
The new dyestuff is soluble in soda lye, with a violet colour, and produces on
wool mordanted with potassium bichromate, intense greenish-blue shades, which are
of particular value, as they exhibit their colour in artificial light, for instance, in
gas-light.
The dyestuff's derived from other oxyanthraquinones are obtained in an analogous
manner, if, in place of alizarin bordeaux, employed in the above example, alizarin,
purpurine, flavo- or anthrapurpurine, oxychrysazin, or the bordeaux colouring
matters from these or similar oxyanthraquinones, or alizarin pentacyanine, alizarin
hexacyanine, hexaoxyanthraquinone, or the like, or sulpho acids thereof, or the
condensation products from anthradiquinones, and phenols, or phenolcarboxylic
acids, are used. The reaction can also be carried out, if oxyanthraquinoline
quinones, and sulpho acids thereof, or the products obtainable from dinitroanthra-
quinones, or the like, and sulphuric acid, with or without sulphur or sulphur
sesquioxide, or boric acid, or similar or analogous products, are used. For instance,
from alizarin blue, ammonia, and ammonium persulphate, a dye-stuff results which
yields bluish green shades with the aid of chromium mordants, whilst dihydroxy-
alizarin blue yields a colouring matter which produces from grey to black shades on
chromated materials.
Similar products result, if ammonia used in the above example is replaced by
primary or secondary amines of the fatty series, or benzene or naphthalene series,
and if these are allowed to act on the aforesaid or similar oxyanthraquinones, under
the above defined conditions. The ammonia may be replaced by such substances
as are capable of yielding ammonia, and, in place of primary or secondary amines,
such products or mixtures can be employed which yield primary or secondary
amines during the reaction. The salts of supersulphuric acid can be replaced
by other oxidising agents which practically produce the same result.
The researches of my foreign correspondents have shewn, that the reaction
illustrated by the preceding Example A, when carried out in the presence of
sulphurous acid, or salts thereof, yields sulpho acids of anthraquinone dyestuffs
containing nitrogen. An introduction of nitrogen (so called "amidising") and
sulphonation thus takes place at the same time. Of course, sulpho acids of
oxyanthraquinenes can also be produced in this manner, that is to say, if oxyanthra-
quinones in an alkaline solution, but without the presence of ammonia, are treated
with supersulphuric salts in the presence of a sulphurous salt.
The "amidising" and sulphonation of the polyoxyanthraquinone dye-stuffs takes
place even in dilute solutions, and a high degree of dilution has been found to be
profitable in many cases. My foreign correspondents have ascertained that four
molecular proportions of ammonium persulphate, or the corresponding quantities of
substances acting in an analogous manner, are most profitably employed for one
molecular proportion of the different polyoxyanthraquinone derivatives. The
so-formed sulpho acids are isolated in the well-known manner, by salting out,
either from the alkaline or acidulated solution.
This process is illustrated by the following example. The parts are by weight.
EXAMPLE B.
DYESTUFF FROM ALIZARIN BORDEAUX, AMMONIA, AMMONIUM BISULPHITE,
AND AMMONIUM PERSULPHATE.
50 parts of an alizarin bordeaux paste (containing 20 per cent, of pure alizarin
bordeaux) are dissolved in 1500 parts of water and 300 parts of ammonia solution
(20 per cent.), 30 parts of ammonium bisulphite (obtained by saturating with

page_text: sulphur dioxide a 20 per cent. ammonia solution), and subsequently a solution
prepared by dissolving 18-parts of ammonium persulphate in 100 parts of water, are
added. The mixture is heated at from 40 to 50 degrees, until a sample, when
acidulated, yields a clear solution containing the formed sulpho acid, without a
precipitate being separated. The mass is then heated to boiling, and is acidulated
by means of sulphuric acid. After cooling, the sulpho acid is precipitated by
adding common salt or potassium chloride. The colouring-matter, when dried, is a
dark powder, easily soluble in water, with a wine-red colour. Its solution in
ammonia shews a violet colour, whilst it dissolves in soda lye with a pure blue
colour, and in concentrated sulphuric acid with a beautiful bluish-red colour.
It yields blue shades on wool mordanted with chromium salts.
Analogous sulpho acids result, if, in. the above Example B, in place of alizarin
bordeaux, corresponding quantities of purpurine bordeaux, flavopurpurine
bordeaux, or anthrapurpurine bordeaux, alizarin pentacyanine, alizarin hexa-
cyanine, hexaoxyanthraquinone, alizarin blue, mono- or dihydroxyalizarin or
analogues thereof, or of the products obtainable by acting with anthradiquinones
on phenols, or the like, are employed.
According to the researches of my foreign correspondents, colouring matters
similar to that which results as described in the above Example B, and likewise
representing sulpho acids of anthraquinone derivatives containing nitrogen, are
obtained either on treating with sulphonating agents the products resulting from
the action of ammonia on polyoxyanthraquinone derivatives, or on allowing
ammonia to act on sulpho acids of polyoxyanthraquinones.
The sulphonation of the products resulting from the action of ammonia on
polyoxyanthraquinone derivatives, can be effected by means of concentrated or
fuming sulphuric acid, sulphuric acid chlorhydrine, sulphuric acid and phosphoric
acid, or substances or mixtures acting in an analogous manner. This sulphonation
process in general takes place very readily (for instance) by employing from
2 to 5 parts of moderately strong fuming sulphuric acid, and heating on a water bath.
The resulting sulpho acids mostly dissolve in water with readiness, and are isolated
by salting out with common salt or potassium chloride. They yield, in general,
on mordanted wool, shades which are clearer, and possess a greener hue, than the
products not sulphonated. Owing to their solubility in water, they are especially
suitable for printing on woollen materials.
In order to illustrate this process of producing sulpho acids of "amidised "
| polyoxyanthraquinones, the following example is given. the parts beinơ by weight.
COLOURING MATTER OBTAINED BY SULPHONATING THE PRODUCT RESULTING
FROM THE ACTION OF AMMONIA ON ALIZARIN PENTACYANINE.
10 parts of the dried product resulting from the action of ammonia on alizarin
pentacyanine, are mixed with from 30 to 40 parts of fuming sulphuric acid
(containing 20 per cent. of sulphuric anhydride), and this mixture is heated at from
90 to 100 degrees centigrade for such a time as that a sample poured into water,
easily dissolves therein without any residue remaining. When this stage is
arrived at, the mass is poured into 500 parts of water, and the dye-stuff (after
salting out by means of common salt) is filtered off, pressed, and dried. This
colouring matter is a black powder which assumes metallic lustre on grinding. It
dissolves in water with a reldish violet colour, in ammonia with a violet blue
colour, in soda lye with a greenish blue, and in pure concentrated sulphuric acid
with a cherry-red colour. It produces beautiful greenish-blue shades on wool
mordanted with chromium salts.
The sulpho acids of the products resulting from the action of ammonia on
alizarin bordeaux, purpurine bordeaux; flavopurpurine bordeaux, anthrapurpurine
bordeaux, alizarin hexacyanine, hexaoxyanthraquinone, Havo or anthrapurpurine
cyanine, or polyoxyanthraquinolines, or on the condensation products of anthradi-

page_text: ammonia. The sulpho acids resulting from dinitroanthraquinone or nitroamido
anthraquinone; and fuming sulphuric-acid, with or without the addition of sulphur
or sulphur sesquioxide, or boric acid, or the like, can be likewise employed in this
process.
My foreign correspondents have described in the above examples, some distinct
methods of practically producing some of the colouring matters hereinhefore
defined. Of course they do not limit themselves to the directions given, as these
can be varied, the nature of this invention, however, not being altered by these
nodifications.
Dated this 7th day of December 1893
The Manufacture or Production of Colouring Matters Derived from
Anthraquinone.
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 saine is to be performed, to be
particularly described and ascertained in and by the following statement :--
This invention relates to the production of dyestuff's derived from anthra-
quinone.
My foreign correspondents have described in the Specification of Letters
Patent No. 4871, dated 18th March 1891, a process for producing coloring matters
containing nitrogen, which process consists in acting on certain polyhydroxy-
anthraquinones with oxidising agents in the presence of ammonia. In the said
Specification, the following polyhydroxyanthraquinones are mentioned, viz. :-
alizarinpentacyanine, alizarinhexacyanine, and the hexahydroxyanthraquinone
isomeric with alizarinhexacyanine, and the oxidation is effected simply by
atmospheric oxygen.
My foreign correspondents have now discovered a new and simple method which
yields similar results, and is characterised by more general applicability. This
process consists in treating hydroxyanthraquinones, in the presence of ammonia, or
substances or mixtures acting in a similar manner, with ammonium persulphate
(see Journal für Praktische Chemie, Neue Folge, volume 48, page 185), or other
salts of persulphuric acid, or other materials acting in a similar manner as oxidising
agents. The action takes place readily in dilute aqueous solutions, at a low
temperature, and is finished in a short time. My foreign correspondents generally
use two molecular proportions of ammonium persulphate, or the like, and one
molecular proportion of hydroxyanthraquinone. The fact that in this manner the
quantity of the oxygen to be used can easily be determined, renders this method
more advantageous than that described in the Specification of the above Patent
dated 18th March 1891, No. 4871. This method, which may be very generally
used, is illustrated by the following example. The parts are kilos. by weight.
FIRST EXAMPLE.
COLORING MATTER FROM ALIZARIN BORDEAUX, AMMONIA, AND AMMONIUM
PERSULPHATE.
50 parts of an alizarin bordeaux paste (containing 20 per cent. of pure
alizarin
bordeaux) are dissolved in about 500 litres of water and 100 litres of ammonia
solution (20 per cent.). A solution prepared by dissolving 8.5 parts of ammonium
persulphate in from 50 to 100 litres of water, is then gradually stirred in. The
beginning of the action is indicated by a rise in the temperature, and it is advisable
to cool the liquid by adding ice. The action is at an end when, on adding acid to

page_text: a sample of the liquid, a precipitate is thrown down which dissolves in concentrated
sulphuric acid, affording a cherry-red colored solution. When this stage is arrived
at, the liquid is mixed with muriatic or sulphuric acid, and the dye-stuff which
separates as a dark purple-red precipitate, is filtered off and washed with water, in
order to remove any adherent acid.
This coloring matter materially differs from that formed (as described in the
Specification of Letters Patent No. 8702, dated 21st May 1891), by heating
alizarin bordeaux merely with ammonia. The latter product dissolves in con-
centrated sulphuric acid, affording a bluish-red colored solution, whilst the
solutions in concentrated sulphuric acid of the pure new product, are of a yellowish
red color. The absorption spectra of the sulphuric acid solutions of both dyestuffs
show the same bands, except that the bands in the spectrum of the new coloring
matter are much nearer to the violet end.
The new dye-stuff dissolves in soda lye, affording a violet colored solution, and
produces on wool mordanted with potassium bichromate, intense greenish-blue
shades which are of particular value, as they retain their color in artificial light,
for instance, in gas light.
The dye-stuffs derived from other hydroxyanthraquinones are obtained in an
analogous manner by using, in place of alizarin bordeaux in the above example,
alizarin, purpurin, flavo or anthrapurpurin, hydroxychrysazin, or the bordeaux
coloring matters from these or similar oxyanthraquinones or alizarin pentacyanine,
alizarin hexacyanine, hexahydroxyanthraquinone, or the condensation products from
anthradiquinones, and phenols or phenolcarboxylic acids, or the like, or sulphonic
acids thereof. The action can also be carried out if hydroxyanthraquinoline
quinones, and sulphonic acids thereof, or .the products obtainable from dinitro
anthraquinones, or the like, and sulphuric acid, with or without sulphur or sulphur
sesquioxide, or boric acid, or similar or analogous products, are used. Naturally,
mixtures of the said hydroxyanthraquinones, or mixtures from these products and
other anthraquinone derivatives, can also be used.
For instance, a dye-stuff yielding bluish-green shades with the aid of chromium
mordants, may be produced from alizarin blue, ammonia, and ammonium_per-
sulphate, whilst dihydroxyalizarin blue yields a coloring matter which produces
from grey to black shades on chromated materials.
The production of the said coloring matter from alizarin blue can be carried out
in the manner illustrated by the following second example. The parts are kilos.
by weight.
SECOND EXAMPLE.
DYE-STUFF FROM ALIZARIN BLUE, AMMONIA, AND
PERSULPHATE.
AMMONIUM
100 parts of a 20 per cent. paste of alizarin blue are mixed with 1000 litres of
water and 400 litres of a 20 per cent. ammonia solution, and to this is added a
solution prepared by dissolving 16 parts of ammonium persulphate in 400 parts of
water. The mixture is repeatedly stirred, and after about 12 hours is filtered, in
order to remove the unchanged alizarin blue, which, being difficultly soluble.
remains on the filter. The new dye-stuff is separated by adding hydrochloric or
sulphuric acid to the filtrate. It forms a dark greenish-blue precipitate, which
dissolves in ammonia solution, affording a greenish-blue colored liquid, whilst it
dissolves with difficulty in soda 1ye, affording a green colored solution. Unlike
alizarin blue, its solution in concentrated sulphuric acid possesses a brownish-yellow
color. Like alizarin blue, it combines with alkaline bisulphites, forming products
which are soluble in water. As above mentioned, it yields beautiful greenish-blue
shades on chromated wool.
In place of the ammonia used as hereinbefore defined, such substances or
mixtures as are capable of yielding ammonia may be used.
My foreign correspondents give in the following table the material properties
some typical dyestuff's of the above defined series.

page_text: The researches of my foreign correspondents have shown that if the action
illustrated by the preceding first and second examples is carried out in the presence
of sulphurous acid, or salts thereof, it yields sulphonic acids of anthraquinone dye-
stuffs containing nitrogen. The introduction of nitrogen (so-called "amidation")
and sulphonation thus take place at the same time.
The "amidation" and sulphonation of the polyhydroxyanthraquinone dye-stuff's
takes place even in dilute solutions, and a high degree of dilution has been found
in many cases to be desirable. My foreign correspondents have ascertained that it
is best to use four molecular proportions of ammonium persulphate, or the
corresponding quantities of other salts of persulphuric acid, to one molecular
proportion of the different polyhydroxyanthraquinone derivatives. The sulphonic
acids thus formed are isolated in the well-known manner, by salting out either from
the alkaline or acidulated solution.
This process is illustrated by the following example. The parts are by weight.
•
DYESTUFF FROM ALIZARIN BORDEAUX AMMONIA, AMMONIUM BISULPHITE,
AND AMMONIUM PERSULPHATE.
50 parts of an alizarin bordeaux paste (containing 20 per cent. of pure alizarin
bordeaux) are dissolved in 1500 parts of water and 300 parts of a 20 per cent.
ammonia solution. 30 parts of ammonium bisulphite (obtained by saturating a
20 per cent. ammonia solution with sulphur dioxide), and subsequently a solution
prepared by dissolving 18 parts of ammonium persulphate in 100 parts of water
are added. The mixture is heated at from 40 to 50 degrees, until, on acidulating
a sample, the liquid remains clear. The mass is then heated to boiling, and is
acidulated with sulphuric acid. After cooling, the sulphonic acid is precipitated
by adding common salt or potassium chloride. The dried coloring matter is a dark
powder, which easily dissolves in water, affording a wine-red colored solution. Its
solution in ammonia is of a violet color, its solution in soda lye being of a pure
blue, and that in concentrated sulphuric acid of a beautiful bluish red color.
yields blue shades on wool mordauted with chromium salts.
It
Analogous sulphonic acids are formed if corresponding quantities of purpurin
bordeaux, flavopurpurin bordeaux, or anthrapirpurin bordeaux, alizarinpenta-
cyanine, alizarinhexacyanine, hexahydroxyanthraquinone, alizarin blue, mono or
dihydroxyalizarin blue, or analogues thereof, or of the products obtainable by
acting with anthrodiquinones on phenols, phenol carboxylic acids, or the like, are
used in place of alizarin bordeaux used in the foregoing third example. The
sulphonic acids thus obtainable in general produce shades which are either greener
or bluer than those obtained by means of the respective original products.
According to the researches of my foreign correspondents, coloring matters
similar to that formed in the manner described in the preceding third example, and
which are also sulphonic acids of anthraquinone derivatives containing nitrogen,
are obtained either on sulphonating the products of the action of ammonia on
polyhydroxyanthraquinone derivatives, or on allowing ammonia to act on sulphonic
acids of polyhydroxyanthraquinones.
The sulphonation of the products of the action of ammonia on polyhydroxy-
anthraquinone derivatives, can be effected by means of concentrated or fuming
sulphuric acid, sulphuric chlorhydrin, mixtures of sulphuric acid and phosphoric
acid, or substances or mixtures acting in an analogous manner.
This sulphonating process in general takes place very readily (for instance) by
using from 2 to 5 parts of moderately strong fuming sulphuric acid, and heating on
a water bath. The resulting sulphonic acids mostly dissolve in water with
readiness, and are isolated by salting out with common salt or potassium chloride.
They yield in general, on mordanted wool, shades which are clearer, and possess &

page_text: COLORING. MATTER
OBTAINED BY SULPHONATING THE PRODUCT OF THE
ACTION OF AMMONIA ON ALIZARIN PENTACYANINE.
10 parts of the dried product of the action of ammonia on alizarin pentacyanine
are mixed with from 30 to 40 parts of fuming sulphuric acid (containing 20 per cent.
of sulphuric anhydride), and this mixture is heated at from 90 to 100 degrees centi-
grade, until, on pouring a sample into water, it easily dissolves therein, without
any residue remaining. When this stage is arrived at, the mass is poured into
500 parts of water, and the dye-stuff having been salted out by means of common
salt, is filtered off, pressed, and dried.
The coloring matter thus obtained is a black powder which assumes metallic
lustre on grinding. It dissolves in water, affording a reddish-violet colored solution;
and it dissolves in ammonia, affording a violet-blue colored solution. Its solution
in soda-lye has a greenish-blue color, and that in pure concentrated sulphuric acid
a cherry-red color. It produces beautiful greenish-blue shades on wool mordanted
with chromium salts.
The sulphonic acids of the products of the action of ammonia on alizarin
bordeaux, purpurin bordeaux, flavo-purpurin bordeaux, anthrapurpurin bordeaux,
alizarinhexacyanine, hexahydroxyanthraquinone, flavo or anthrapurpurin cyanine,
or polyhydroxyanthraquinolines, or on the condensation products of anthradi-
quinones and phenols, or the like, are obtained in a manner analogous to that
described in the above fourth example. The sulphonic acids thus obtained, which
readily dissolve in water, in general produce greener shades than the corresponding
original materials.
In place of converting the polyhydroxyanthraquinones first into amido
derivatives, and subsequently sulphonating these "amidated polyhydroxyanthra-
quinones," as described in the preceding fourth example, the polyhydroxynathra-
quinones can, inversely, be first transformed into sulphonic acids, and the latter can
subsequently be treated with ammonia,-sulphonic acids of "anidated poly-
hydroxyanthraquinones" being likewise thus produced.
The first stage of the last defined process, viz., the production of the sulphonic.
acids of polyhydroxyanthraquinone dye-stuffs can be carried out, for instance,
according to the processes described in the Specifications of Letters Patent
No. 12715, dated 13th August 1890; No. 17712, dated 4th November 1890; and
No. 12580, dated 7th July 1892. Sulphonic acids derived from the condensation
products of anthradiquinones and phenols, or the like (which condensation products
are described in the Specification of Letters Patent No. 8702") are produced in an
analogous manner.
The second stage, that is to say, the treatment of these sulphonic acids with
ammonia, can be effected, for instance, according to the process described in the
Specification of Letters Patent No. 87029. This amidation" also takes place
very easily and conveniently; heating with a dilute ammonia solution at about
80 degrees centigrade, either in or without the presence of air, is sufficient in most
cases.
The isolation of the sulphonic acids of "amidated polyhydroxyanthraquinones
can be effected either by directly salting them out from the ammoniacal solution,
or by previously acidulating the ammoniacal solution with sulphuric, muriatic, or
acetic acid, and subsequently salting out. The ammoniacal solution is, with
advantage, acidulated at a low temperature, as, on acidulating at elevated
temperatures, the nitrogen contained in the said sulphonic acid of amidated
B

page_text: uye-stun often separave
The production of the last-named sulphonic acids of "amidated polyhydroxy-
anthraquinones," or the like, is illustrated by the following example. The parts
are by weight.
FIFTH EXAMPLE.
COLORING MATTER FROM HEXAHYDROXYANTHRAQUINONE.
10 parts of hexahydroxyanthraquinone are mixed with from 30 to 40 parts of
fuming sulphuric acid (containing 20 per cent. of sulphuric anhydride), and this
mixture is heated at from 90 to 100 degrees centigrade, until, on pouring a sample
into water, it entirely dissolves. At this stage, the whole mass is poured into
500 parts of water, and the liquid is mixed with a sufficient quantity of ammonium
chloride or common salt. The precipitated sulphonic acid is filtered off, and then
mixed with such a quantity of a 5 per cent. ammonia solution, as is sufficient to
dissolve it. This solution is heated at from 60 to 80 degrees centigrade, until,
when a sample is acidulated with acetic acid at a low temperature, it yields a
precipitate which dissolves in concentrated sulphuric acid, affording a yellow-
colored liquid. At this stage, the whole liquid is allowed to cool, and is then
acidulated with acetic acid, avoiding any rise of temperature. The "amidated
sulphonic acid separates in a crystalline state. It is filtered off, pressed, and
dried. The dye-stuff thus obtained is a bluish-black powder which easily dissolves
in water, forming a violet-colored solution. This violet color is changed into
bluish-red on adding sulphuric or muriatic acid. Its solution in ammonia is violet
colored, whilst that in soda-lye is blue, and that in concentrated sulphuric acid,
yellow. It yields on chromated wool, pure blue shades distinguished by their great
clearness, beauty, and fastness.
"
The other coloring matters are obtained in an analogous manner by the action of
ammonia on the sulphonic acids of the corresponding polyhydroxyanthraquinone
derivatives. The sulphonic acids from dinitroanthraquinone, or nitro amido-
anthraquinone, and fuming sulphuric acid, with or without the addition of sulphur,
or sulphur sesquioxide, or boric acid, or the like, can also be used in this process.
(The process for producing mordant-dyeing coloring matters described in the
Specification of Letters Patent No. 15246, dated 24th August 1892, and the
process for producing mordant-dyeing dye-stuffs, as claimed in the 5th claim of
the Specification of Letters Patent No. 15325, dated 25th August 1892, are hereby
disclaimed.)
My foreign correspondents have described, in the above examples, distinct
methods of practically producing some of the coloring matters herein before defined.
Of course they do not limit themselves to the directions given, as these can be
varied, the nature of this invention not being altered by these modifications.
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 process for producing anthraquinone dye-stuffs containing nitrogen, which
process consists in allowing ammonium persulphate, or another salt of persulphuric
acid, to act, in the presence of ammonia, either on hydroxyanthraquinones, such as
alizarin, purpurin, flavopurpurin, anthra purpurin, hydroxychrysazin, or on hydroxy-
anthraquinone bordeaux, such as alizarin bordeaux, purpurin bordeaux,
flavopurpurin bordeaux, anthrapurpurin bordeaux, or the like, or
on alizarin
pentacyanine, alizarin hexacyanine, bexahydroxyanthraquinone, or on the con-
densation products obtained from anthradiquinones, and phenols or phenol carboxylic
acids or the like, or on hydroxyanthraquinoline quinones, or on the sulphonic
derivatives of all these, or the like hydroxylated products, or on the products

page_text: obtainable by treating dinitroanthraquinone, or the like, with sulphuric acid, in or
without the presence of sulphur, sulphur sesquioxide, or boric acid, or the like.
2. The production of sulphonic acids of anthraquinone dye-stuff's containing
nitrogen, which process consists in allowing ammonium persulphate, or other salts of
persulphuric acid, to act, in the presence of ammonia and salts of sulphurous acid,
on polyhydroxyanthraquinones, such as alizarin pentacyanine, alizarin hexacyanine,
hexahydroxyanthraquinone, or on hydroxyanthraquinone bordeaux, such as alizaria
bordeaux, purpurin bordeaux, flavopurpurin bordeaux, anthrapurpurin bordeaux, or
the like, or on alizarin blue, monohydroxyalizarin blue, dihydroxyalizarin blue, or
the like, or on the condensation products obtained from anthradiquinones and
phenols, or phenolcarboxylic acids, or the like.
3. The process for producing sulphonic acids of anthraquinone dye-stuffs con-
taining nitrogen, which process consists in sulphonating the dye-stuff's obtainable as
described in the Specification of Letters Patent No. 8702 of 1891, by the action of
ammonia on either alizarin bordeaux, purpurin bordeaux, flavo purpurin bordeaux,
anthrapurpurin bordeaux, alizarin pentacyanine, alizarinhexacyanine, hexahydroxy-
anthraquinone, flavopurpurincyanine, anthra purpurin cyanine, or the condensation
products from anthradiquinones and phenols or phenolcarboxylic acids, or the
like.
4. The production of sulphonic acids of anthraquinone aye-stuffs containing
nitrogen, by the action of ammonia on either sulphonic acids of polyhydroxy-
anthraquinones, or derivatives thereof, or the products obtainable by acting
on dinitroanthraquinone or nitroamidoanthraquinone, or the like, with fuming
sulphuric acid, in or without the presence of sulphur or sulphur sesquioxide, or
boric acid, or the like. (The process described in the Specification of Letters
Patent No. 15246, dated 24th August 1892, and the process claimed in the 5th
claim of the Letters Patent No. 15325, dated 25th August 1892, are hereby.
disclaimed.)
5. As new products of manufacture, the new dye-stuff's produced by the processes
bereinbefore defined, or by any other means affording the same result.
Dated this 29th day of August 1894.
NEWTON & SON,
Agents for the Applicant.