The Manufacture or Production of Derivatives of Hydroxy- anthraquinone.
Year: 1894

page_text: Date of Application, 8th Dec., 1894
Complete Specification Left, 5th Sept., 1895-Accepted, 2nd Nov., 1895
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Derivatives of Hydroxy-
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:-
The present invention relates to the manufacture of new products and colouring-
matters, by allowing hydroxyanthraquinones to act in a suitable manner on organic
amido compounds, particularly monoamines and diamines of the aromatic series,
and to the conversion of these products or colouring-matters into new derivatives
thereof.
According to the researches of my foreign correspondents, the action of hydroxy-
anthraquinones on amido compounds takes place readily, for instance, on heating
the hydroxyanthraquinones with amines in the presence of such agents as are
capable of causing or facilitating the action. The researches of my foreign
correspondents have shewn that the following agents can be profitably used,
viz. boric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulphuric
acid, phosphoric acid, acetic acid, benzoic acid, zinc chloride, or the like. My
foreign correspondents do not, however, limit themselves to the use of the agents
hereinbefore enumerated, as all substances capable of acting in the same or a similar
manner can be employed. In place of the free acids, the derivatives thereof, for
instance, the corresponding salts of the amido-compounds, can be used. The
action proceeds with surprising readiness on using such agents, and in some cases
takes place even on heating by means of a water bath, whilst in other cases a
somewhat higher temperature (from about 130 to 200 degrees Centigrade) is
Decessitated.
The researches of my foreign correspondents have shewn that the following
hydroxyanthraquinones can be used riz., quinizarin, purpurin, hydroxyanthra-
purpurin, hydroxyflavopurpurin, anthrachryson, alizarinbordeaux, alizarinpenta-
cyanine, alizarinhexacyanine, hexahydroxyanthraquinone, but other hydroxyanthra-
quinones, and the derivatives of hydroxyanthraquinones, for instance, nitropurpurin,
amidopurpurin, beta nitro alizarinbordeaux, or the like, can also be used.
:
Amongst the amido compounds which can be used in the process hereinbefore
defined, the following have been found by my foreign correspondents to give
good results, viz. aniline, ortho- and paratoluidine, xylidine, cumidine, anisidines,
cresidines, alpha and beta naphthylamine, meta and paraphenylenediamine, meta
and paratoluylenediamine, dimethylmetaphenylenediamine, dimethylparaphenylene-
diamine, benzidine tolidine, diamidodiphenolether, paradiamidodiphenylmethane,
diamidocarbazol, but the process is not restricted to the use of these amines, as
generally all organic amido compounds, as such, or in the form of their salts or
derivatives, can be employed.
The method for producing the new products or dye-stuffs, in general, consists in
heating, at a suitable temperature, any hydroxyanthraquinone (say, one part by
weight thereof), together with a suitable quantity (say, from 1 to 5 parts) of the
agents capable of causing or facilitating the action (employing either the same or

page_text: A mixture prepared from 10 parts of dry pulverised purpurine, 50 parts of aniline
hydrochloride, and 50 parts of aniline, is (while being stirred) heated at 150 degrees
Centigrade, until any unaltered purpurine can no longer be distinguished in a
sample taken out, which is usually the case after heating during from 1 to 2 hours.
The original brownish-yellow colour of the mass turns into bluish-red. A portion
of the product formed separates during the operation, and a further and large
portion separates in brass-yellow needles, on cooling.
The aniline used in excess is driven off by means of steam, or withdrawn by
extraction with dilute acids, and the remaining part, which is insoluble in water, is
dried. It crystallises from hot aniline in long needles with metallic lustre, melting
at from 255 to 256 degrees Centigrade; is soluble with difficulty in cold aniline,
but readily in hot aniline, affording a bluish-red coloured liquid. Its solution in
concentrated sulphuric acid exhibits a violet-red colour, which turns to magenta-red
after some time, owing to sulphonation, and which becomes bluish-green on adding
boric acid. The product thus obtained, having the formula C,H,O,(NHC,H,), is
formed from one molecular proportion of purpurin and one molecular proportion
of aniline, whilst one molecular proportion of water is liberated, according to the
following equation :-
My foreign correspondents have observed, that the mother-liquors obtained on
crystallizing the last-named product from aniline, contain small portions of the
corresponding dianilido substitution derivative which is hereinafter described.

page_text: EXAMPLE.
On employing beta naphthylamine in place of alphanaphthylamine used in the
Sixth Example, and on heating the mixture so formed at a somewhat higher
temperature (say, 170 degrees Centigrade), and for a longer period (say, 8 hours),
the corresponding beta-naphthyl compound results, which dissolves in concentrated
sulphuric acid, producing a violet colored solution with brownish fluorescence.
The other hydroxyanthraquinones act in a similar manner on the amido-
compounds, or derivatives thereof, herein before defined.
The proportions given in the foregoing examples, the temperature and other
conditions of operating, can be varied within wide limits. Other hydroxyanthra-
quinones, or derivatives of hydroxyanthraquinones, and other amido compounds
and agents capable of causing or facilitating the action, can be used. One
molecular proportion of hydroxyanthraquinone may be first combined with one
molecular proportion of an amido compound, and the so-formed products may
subsequently be combined with one molecular proportion of the same, or another
amido compound, or one molecular proportion of hydroxyanthraquinone may be
allowed to act on a mixture containing two, or several different amines. My
foreign correspondents have succeeded, by such or the like variations, in obtaining
products substituted by radicles of different amines.
According to the researches of my foreign correspondents, the products and
dye stuffs resulting, as herein before defined, from hydroxyanthraquinones and
amido compounds, are readily converted, by a treatment with sulphonating agents,
into sulphonic acids which possess a considerable technical value. In order to
effect this sulphonation, the agents known and in use for the like purposes can be
employed, for instance, concentrated or monohydrated or fuming sulphuric acid,
sulphuric chlorhydrine, mixtures of sulphuric and metaphosphoric acid, or the like.
In many cases, it suffices to allow sulphuric acid (66 degrees Baumé) to act at the
ordinary temperature on the hydroxyanthraquinones; in other cases, a stronger

page_text: chromated wool, shades which are similar to those obtained by means of the
corresponding product from aniline.
In order to illustrate the variety of shades which can be obtained by means of.
the sulphonic acids hereinbefore defined, the following table is given. In the first
column are indicated some typical sulphonic acids of the series hereinbefore
defined; in the second and third column, are the shades produced by these
sulphonic acids on unmordanted wool, and on wool mordanted with chromium salts,
respectively :

page_text: instance, the said sulphonic acid of the product from 1 molecular proportion of
purpurin and 2 molecular proportions of benzidine, yields bluish-violet shades on
unmordanted cotton in an alkaline soap bath.
According to the researches of my foreign correspondents, the products which
are obtained by the methods illustrated by the foregoing Examples One to Seven,
can also be converted into valuable products by introducing other acid radicles for
instance nitro groups. The production of these nitro derivatives is effected by
means of methods known and in use for producing other nitro compounds.
My foreign correspondents have described in the preceding Examples Eight and
Nine, some distinct methods of converting two of the condensation products
herein before defined into sulphonic acids, but they do not intend to limit themselves
to the directions given, as these can be varied without altering the nature of this
invention, which in general relates to the manufacture or production of products
and dye-stuffs from amido compounds and hydroxyanthraquinones, or derivatives.
thereof, and to the conversion of these products and dye-stuffs into new products
and dye-stuffs by a suitable treatment, in order to introduce acid groups, such as
the sulphonic or nitro group, or the like.
Dated this 8th day of December 1894.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Derivatives of Hydroxy-
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 same is to be performed, to be
particularly described and ascertained in and by the following statement :-
on
The present invention relates to the manufacture of new products and colouring-
matters, by allowing hydroxyanthraquinones to act in a suitable manner
organic amido compounds, particularly monamines and diamines of the aromatic
series, and to the conversion of the products or colouring-matters thus obtained
into other new derivatives thereof.
According to the researches of my foreign correspondents, the action of hydroxy-
anthraquinones on amido compounds readily takes place, for instance, on heating
the hydroxyanthraquinones with amines in the presence of such agents as are
capable of causing or facilitating the action. The researches of my foreign
correspondents have shewn that, for example, the following agents are especially
suitable, viz., boric acid, hydro-chloric acid, hydrobromic acid, hydrofluoric acid,
sulphuric acid, phosphoric acid, acetic acid, benzoic acid, zinc chloride, or the like.
My foreign correspondents do not, however, limit themselves to the use of the
agents hereinbefore enumerated, as all substances capable of acting in the same
or a similar manner can be used. In place of the free acids, the derivatives
thereof, for instance, the corresponding salts of the amido compounds, can be
used. The action proceeds with surprising readiness on using such agents, and, in
some cases, takes place even on heating by means of a water bath, whilst in other
it is necessary to heat to a somewhat higher temperature (from about 130
to 200 degrees Centigrade).
cases,
The researches of my foreign correspondents have shewn, that the following
hydroxyanthraquinones can be used, viz., quinizarin, purpurin, hydroxyanthra-
purpurin, hydroxyflavopurpurin, anthrachrysone, alizarin bordeaux, alizarin-
pentacyanine, alizarinhexacyanine, and hexahydroxyanthraquinone, but other
hydroxyanthraquinones, and derivatives of hydroxyanthraquinones, for instance,

page_text: nitro purpurin, amido purpurin, beta nitro alizarin bordeaux, or the like, can also-
be used.
Of the amido compounds which can be used in the process herein before defined,
the following have been found by my foreign correspondents to give good results,
viz, aniline, ortho and para toluidine, xylidine, cumidine, anisidines, cresidines,
alpha and beta naphthylamine, meta and para phenylene diamine, meta and para
tuluylene diamine, benzidine, tolidine, diamidodiphenolether para diamidodiphenyl-
methane, but the process is not restricted to these amines, as a very great number
of organic amido compounds can be used.
The method for producing the new products or dye-stuffs, in general, consists in
beating at a suitable temperature any hydroxyanthraquinone (say, one part by
weight thereof) together with a suitable quantity (say, from to 5 parts) of the
agent capable of causing or facilitating the action (using either one or several),
and, for instance, 10 parts of au amido compound, or a mixture of amido compounds,
until unaltered hydroxyanthraquinone can no longer be detected, or until it can
be ascertained that the action is at an end, by either of the methods hereinafter
mentioned.
According to the researches of my foreign correspondents, a uniform product is
not generally obtained by means of the process hereinbefore defined, but the crude
products can be readily separated, for instance, by crystallization, or by suitable
treatment with certain chemical agents, such as alkaline solvents (for instance, soda
lye, sodium-carbonate, or the like), several products being thus obtained which are
derivatives of hydroxyanthraquinones, substituted in different degrees. My foreign
correspondents have found, that, generally, such a separation of the crude products
is not necessary for practical purposes.
The researches of my foreign correspondents have also shown that the process
can be managed in such a manner, particularly by using suitable agents capable of
causing or facilitating the action, or by allowing the action to take place at the
suitable temperature, and during a suitable time, that the one or other substitution
derivative is formed almost exclusively. As hereinafter mentioned, for instance,
purpurin, when heated with aniline and aniline hydrochloride, yields, as chief
product, a monosubstitution derivative, a di substituted derivative being chiefly
obtained on using boric acid in place of aniline hydrochloride, though the other
conditions of the operation are not further altered.
The products, some of which can be directly used as dye-stuffs or colours, are
converted into valuable products or dye-stuffs by introducing acid groups, such as
the sulphonic group, by treating them in a suitable manner.
In order to illustrate the process hereinbefore defined, the following are given as
merely typical examples. The parts are by weight.
FIRST EXAMPLE.
A mixture of 10 parts of dry pulverised purpurin, 50 parts of aniline hydro-
chloride, and 50 parts of aniline, is heated at 150 degrees Centigrade, being
meanwhile stirred, until unaltered purpurin can no longer be distinguished in
a sample, which is usually the case after heating during from 1 to 2 hours. The
original brownish yellow colour of the mass turns into bluish-red. A portion of
the product separates during the operation, and a further large proportion
separates in brass-yellow crystals as the mass cools.
The aniline used in excess is driven off by means of steam, or withdrawn by
extraction with dilute acids, and the insoluble part is then dried. It crystallises
from hot aniline in long needles exhibiting a metallic lustre. It melts at from
255 to 256 degrees Centigrade, dissolves with difficulty in cold aniline, but readily
in hot aniline, affording a bluish-red coloured liquid. Its solution in concentrated
sulphuric acid exhibits a violet-red colour, which, owing to sulphonation, turns
to magenta red after some time, and which becomes bluish-green on adding
boric acid. The product thus obtained, having the formula C₁H,О(NHCH), is
formed from a molecular proportion of purpurin and a molecular proportion of

page_text: aniline, a molecular proportion of water being liberated, as expressed by the
following equation:
following equation:
G,H,O,(OH) + C,H,NH, = C,H,O,(OH),NHCH. + H,O.
14
My foreign correspondents have observed that the mother liquors obtained on
crystallising the product above described from aniline, contain small portions
of the corresponding dianilido-substitution derivative which is hereinafter
described.
The sulphonic acids obtained from the monoanilido derivative produce beautiful
bluish-red shades on ordinary wool in acid baths, and dark violet shades on wool
mordanted with chromium salts.
SECOND EXAMPLE.
A mixture of 10 parts of purpurin, 10 parts of crystallized boric acid or boric
acid dried at 100 degrees Centigrade, and 100 parts of aniline, is heated at
130-150 degrees Centigrade, until the mass has assumed a bluish-violet colour,
which is no longer altered on further heating. A considerable part of the product
separates in crystals during the heating, and the remainder on cooling. It is
purified by crystallization from aniline. It dissolves in hot aniline, affording
a bluish-violet coloured solution. Its solution in concentrated sulphuric acid
exhibits a greenish-blue colour, which, after some time, turns into violet, as
sulphonation takes place, whilst an addition of boric acid to the sulphuric acid
solution produces no considerable change in colour. The product thus formed has
the formula: CH¸O₂ (OH) (NHCH)-
-two hydroxylic groups of the purpuria
used being displaced by the anilido group.
2
The sulphonic acid of this dianilido compound produces from greyish-blue to
bluish-black shades on chromated wool.
Products similar to those obtained as described in the preceding examples are
formed if equivalent quantities of ortho or para toluidine, xylidines, cumidines,
anisidines, phenetidines, or the like, are used, in place of the aniline of the
preceding examples. The products obtained from para toluidine are distinguished
on account of the readiness with which they crystallise; the monotoluido-
derivative of purpurin melts at 220 degrees Centigrade, and the ditoluido compound
begins to soften at 235 degrees Centigrade.
THIRD EXAMPLE.
10 parts of quinizarin are mixed with 10 parts of crystallized boric acid and
150 parts of para-toluidine. The mixture is heated at from 130 to 140 degrees.
Centigrade, until a sample dissolves in aniline, affording a green liquid. The
product isolated in the manner hereinbefore mentioned crystallizes from glacial
acetic acid in dark violet indigo-like needles, which melt at about 200 degrees
Centigrade, and dissolve in aniline, affording a green coloured liquid, but, when
dissolved in concentrated sulphuric acid, afford a violet-blue coloured solution..
The product is the diparatoluido derivative of quinizarin. My foreign corre-
spondents have observed, that a small amount of the monoparatoluido compound is
simultaneously formed.
On varying the mode of working, the monoparatoluido derivative can also be
obtained as chief product.
The sulphonic acid of the aforesaid diparatoluido derivative of quinizarin, dyes
ordinary and chromated wool a beautiful green.
Dye-stuffs similar to those obtained as described in the last example are
produced, when corresponding quantities of aniline or benzidine, or the like, are
used in place of paratoluidine.
FOURTH EXAMPLE.

page_text: 100 degrees Centigrade, and 100 parts of benzidine, is kept carefully stirred, whilst
it is heated, during from 1 to 2 hours, at from 150 to 160 degrees Centigrade..
The benzidine used in excess is withdrawn from the cold and pulverised mass by
boiling with hydrochloric or acetic acid. The remainder is dried. It chiefly
consists of the di-substitution derivative from benzidine and purpurin. It dissolves
in aniline, affording a blue coloured solution, and in concentrated sulphuric acid,
producing a greenish-blue coloured liquid. Its sulphonic acid yields bluish violet
shades on unmordanted cotton in alkaline baths, and dark blue shades on
chromated wool.
Dye-stuffs similar to that obtained as described, in the last example are formed
on using tolidine, diamido diphenolether, or the like, in place of benzidine.
The monosubstitution derivative from purpurin and benzidine is formed as chief
product, if, in the last example, benzoic acid is used instead of boric acid.
Colouring matters of pronounced basic nature are produced by the interaction
of hydroxyanthraquinones and diamido compounds of the benzene series, such as
paraphenylene diamine or the like. The salts of these condensation products
yield from violet to blue shades on cotton prepared with tannic acid. or the like.
10 parts of dry powdered alizarin bordeaux are mixed with 100 parts of aniline
and 10 parts of boric acid dried at 100 degrees Centigrade. The mixture is then
stirred, while it is heated, during about 1 hours, at froin 140 to 150 degrees
Centigrade. The crude product having been freed in the known manner from
excess of aniline, is mixed with 800 parts of water and 10 parts of soda lye.
(34 degrees Baumé). The mixture is boiled, in order to effect the separation of
the two colouring matters, which are simultaneously formed.A colouring matter
which my foreign correspondents term "dye stuff B" is dissolved, whilst the
sodium salt of the other hereinafter termed "dye stuff A" remains undissolved.
The insoluble sodium salt of the "dye-stuff A" is mixed with a small quantity
of water, and this mixture is acidulated with any acid. The dye-stuff thus
separated is filtered off, washed, dried, and crystallized from acetone. This "dye-
stuff A" dissolves with great readiness in aniline and pyridine, affording a greenish-
blue coloured solution, whilst its solutions in acetone and chloroform exhibit a
violet-blue colour. It dissolves with less readiness in alcohol and glacial acetic
acid. Its solution in concentrated sulphuric acid exhibits a green colour, which,
on heating, turns to greenish-blue as sulphonation takes place.
The "dye-stuff B" crystallizes from boiling aniline in long needles soluble in
concentrated sulphuric acid, forming a bright greenish-blue coloured liquid. This
sulphuric acid solution does not possess a distinct spectrum. It is almost insoluble
in hot solutions of sodium carbonate, but dissolves in soda-lye, affording a violet-
red coloured solution. Its solutions in hot aniline and glacial acetic acid exhibit
a beautiful bluish-red colour.
Dye-stuffs similar to those obtained as described in the last example, are
obtained, if, instead of the aniline used therein, equivalent quantities of ortho-
toluidine, paratoluidine, or xylidine, or the like, or the hydrochlorides or hydro-
bromides of these bases, are used in place of boric acid.
A mixture of 10 parts of alizarin bordeaux, 10 parts of boric acid dried at
100 degrees Centigrade, and 200 parts of alpha naphthylamine, is heated during about
5 hours at 150 degrees Centigrade. The cold mass is boiled with dilute muriatic
acid, in order to remove the naphthylamine present in excess. A bluish-black
product is thus obtained, which dissolves in concentrated sulphuric acid, affording
a bluish-green coloured solution. The dye-stuff thus formed can be isolated in a

page_text: pure state by repeated crystallization from aniline. The pure colouring matter
dissolves in aniline, affording a pure green liquid.
SEVENTH EXAMPLE.
On using beta naphthylamine in place of the alpha naphthylamine of the sixth
example, and on heating the mixture at a somewhat higher temperature (say,
170 degrees Centigrade), and for a longer period (say, 8 hours), the corresponding
beta naphthyl compound is formed. This dissolves in concentrated sulphuric acid,
producing a violet-coloured solution, with brownish fluorescence.
The other hydroxyanthraquinones act in a similar manner on the amido
compounds, or derivatives thereof, herein before defined.
The proportions given in the foregoing examples, the temperature, and other
conditions of operating, can be varied within wide limits. Other hydroxyanthra-
quinones, or derivatives of hydroxyanthraquinones, and other amido compounds,
and agents capable of causing or facilitating the action, can be used.
The following table contains the main characteristics of some of the products
obtainable as hereinbefore defined.

page_text: my foreign correspondents,
purpose are those containing a nitro group in the para position relatively to one
hydroxy group.
The production of colouring-matters from nitroxyanthraquinones and aromatic
amido compounds, which can be effected in the presence of, or without, condensing
agents, is illustrated by the following examples (eight and nine). The parts are
by weight.
EIGHTH EXAMPLE.
10 parts of para dinitroanthrarufin (obtained by dinitrating anthrarufin, and
separating the difficultly soluble dinitro derivative from the isomeric readily
soluble products simultaneously formed, are mixed with from 150 to 200 parts of
paratoluidine. The mixture is well stirred, while it is heated, at from 150 to
160 degrees Centigrade. An energetic action takes place, the heated mass
assuming after a short time a deep-blue colour. When the intensity of this blue
colour no longer increases, the mass is allowed to cool to 40 degrees Centigrade,
The
and is then poured into 150 parts of muriatic acid diluted with water.
condensation product separates as a deep-blue indigo-like precipitate. It is insoluble
in alkalies, but dissolves readily in chloroform, aniline, and pyridine, less readily
in alcohol and glacial acetic acid, affording deep blue coloured solutions. By
crystallization from glacial acetic acid, it is obtained in violet-blue crystals
glistering superficially like copper. These crystals dissolve in neutral solvents,
yielding pure blue liquids, whilst they dissolve in concentrated sulphuric acid,
affording a pure green liquid, which assumes a blue colour on the addition of boric
acid. Its solutions in alcohol exhibit a blue colour, which becomes green on
adding soda lye. It melts at from 200 to 205 degrees Centigrade; when heated
at higher temperatures, it is converted into a violet vapour.
Similar dyestuffs are formed, if, instead of the paratoluidine prescribed in' the
last example, equivalent quantities of aniline, orthotoluidine, xylidines, alpha or
betanaphthylamine, diamines, such as paraphenylenediamine, benzene, or the like,
are used.
NINTH EXAMPLE.
A mixture containing 10 parts of alphanitroalizarin and 200 parts of aniline, is
heated at from 160 to 170 degrees Centigrade. The cool melt is subsequently
introduced into dilute muriatic acid, and the precipitate is filtered off and washed.
In this manner a product is obtained which consists of two dye-stuffs, the one
soluble in hot dilute soda lye, affording a red coloured solution, the other insoluble
in hot dilute soda-lye. The former dissolves in aniline and concentrated sulphuric
acid, affording violet coloured liquids, whilst the solutions of the latter in aniline
and concentrated sulphuric acid exhibit a green and brownish-yellow colour
respectively.
Analogous colouring matters are obtained by using either instead of the aniline
prescribed in the last example, equivalent quantities of paratoluidine or other
aromatic amido compounds, or instead of alphanitro alizarin, dinitro anthra-
chrysone, or other nitrohydroxyanthraquinones.
According the researches of my foreign correspondents, the products and dye-
stuffs formed, as hereinbefore defined, from hydroxyanthraquinones and amido
compounds, are readily converted by treatment with sulphonating agents into
sulphonic acids, which are of considerable technical value. In order to effect this
sulphonation, the known agents in use for the like purpose can be used, for instance,
concentrated or monohydrated or fuming sulphuric acid, sulphuric chlorhydrin,
mixtures of sulphuric and metaphosphoric acid, or the like. In many cases, it
suffices to allow sulphuric acid (66 degrees Baumé) to act at the ordinary
temperature on the said products or dyestuffs derived from hydroxyanthraquinones,

page_text: but, in other cases, a stronger monohydrated or fuming sulphuric acid is necessary,
or the process must be carried out at elevated temperatures. The sulphonic acids
thus formed are generally less soluble in dilute cold sulphuric acid, but dissolve
with readiness in pure water. They can be salted out from their solutions in
water. Products soluble in water with less or greater readiness, which probably
are less or more sulphonated, are formed, according as the sulphonation is effected
in a less or higher degree. The dyestuffs thus produced yield from red, violet,
blue, green, violet-black, to greenish-black shades, on unmordanted or chromated
wool, and the shades are distinguished for their intensity, and the manner in which
they withstand the action of light, fulling, and acids. The shades obtained on
unmordanted wool, in acid baths, can be varied, and shaded by a subsequent
treatment in solutions containing metallic salts.
The method of sulphonating is illustrated by the following two examples, the
parts being by weight."
TEXTH EXAMPLE.
10 parts of the product obtained by working, in accordance with the preceding
first example, from molecular proportions of purpurin and aniline, are dissolved in
from 100 to 150 parts of sulphuric acid at 66 degrees Baumé, and the solution is
kept at from 75 to 30 degrees Centigrade, until a sample dissolves in a large
quantity of boiling water, and likewise in alkalies, without leaving any residue.
At this stage, the mass is poured into cold water. The sulphonic acid which
separates, dissolves with difficulty in dilute sulphuric acid and in cold water; it is
filtered off, and washed with small portions of cold water. It dissolves in hot
water, affording a magenta-red coloured solution, which assumes a bright crimson-
red colour on the addition of ammonia, and a violet-red colour on the addition of
soda lye. Its solutions in concentrated sulphuric acid exhibit a magenta-red
colour, which turns into bluish-green on the addition of boric acid. It produces
dark violet shades on chromated wool, and bluish-red shades on unmordanted wool
in acid baths.
If the mixture used in the last example is heated at from 100 to 120 degrees
Centigrade, a sulphonic acid is formed, which is very similar to the sulphonic acid
obtained by working in accordance with the last example, but differs therefrom
by its greater solubility in cold water. This sulphonic acid is isolated from its
solutions by salting out, most profitably by means of potassium chloride.
ELEVENTH EXAMPLE.
A mixture prepared by dissolving 10 parts of the product obtainable as
described in the foregoing Second Example, from one molecular proportion of
purpurin, and two molecular proportions of aniline, in from 100 to 150 parts
of sulphuric acid at 66 degrees Baumé, is allowed to stand at the ordinary
temperature, until a test portion dissolves without any residue in hot water and
alkalies. The sulphonated mixture is then poured into water, and the sodium salt
of the sulphonic acid is salted out by means of common salt and filtered off.
The product thus obtained dissolves in water, affording a violet-blue coloured
solution, which assumes a bluish-green colour on the addition of soda lye. Its
solution in concentrated sulphuric acid is bluish-violet. It produces from bluish-
grey to blackish-blue shades on wool mordanted with chromium salts.
Similar dye-stuffs are formed by using, instead of the products used in the last
two examples, and obtained from purpurin and aniline, equivalent quantities of
the corresponding analogous products produced from purpurin and orthotoluidine,
paratoluidine, xylidine, cumidine, anisidine, phenetidine, or the like.
The sulphonic acid obtained from one molecular proportion of purpurin and two
molecular proportions of paratoluidine, is distinguished by the readiness with which
it crystallises. On pouring the acid mixture into water, it separates in the form of
needles, which dissolve in pure water, producing a bluish-violet colour, which is

page_text: changed into green by an addition of soda-lye. This sulphonic acid produces, on
chromated wool, shades which are similar to those obtained by means of the
corresponding product from aniline.
In order to illustrate the variety of shades which can be obtained by means of
the sulphonic acids hereinbefore defined, the following table is given, in which are
indicated, in the first column, some of the typical sulphonic acids of the series
herein before defined, and, in the second and third columns, the shades produced by
these sulphonic acids on unmordanted wool and on wool mordanted with chromiuin
salts respectively :-
:-

page_text: instance, the said sulphonic acid of the product from 1 molecular proportion of
purpurin and benzidine, yields bluish-violet shades on unmordanted cotton in an
alkaline soap bath.
In the preceding Examples Ten and Eleven, my foreign correspondents have
described distinct methods of converting two of the condensation products herein-
before defined into sulphonic acids, but they do not intend to limit themselves to
the directions given, as these can be varied without altering the nature of this
invention, which, in general, relates to the manufacture or production of products
and dyestuffs from amido compounds and hydroxyanthraquinones or derivatives
thereof, and to the conversion of these products and dyestuffs into new products
and dyestuffs by a suitable treatment, in order to introduce acid groups, such as
the sulphonic or nitro group or the like.
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 manufacture of new products or dyestuffs of the anthracene series
containing nitrogen, from hydroxyanthraquinones, or derivatives thereof, and
primary aromatic monamido or diamido compounds.
2. The process for producing new products or dyestuffs of the anthracene series
containing nitrogen, which process consists in allowing hydroxyanthraquinones,
Anthrachrysone,
Alizarinbordeaux,
Alizarinpentacyanine,
Alizarinhexacyanine,
Hexahydroxyanthraquinone,.
or the like, to act on aniline, orthotoluidine, paratoluidine, alpha or betanaph-
thylamine, paraphenylenediamine, benzidine, diamidodiphenylmethane, or mixtures
thereof, or the like primary aromatic monamido or diamido compounds, in the
presence of agents capable of causing or facilitating the action, such as hydrochloric,
hydrobromic, or hydrofluoric acid, sulphuric acid, phosphoric acid, boric acid,
zinc chloride, acetic acid, benzoic acid, or other agents acting in the same or a
similar manner.
3. The production of new dyestuffs of the anthracene series containing nitrogen,
by allowing derivatives of hydroxyanthraquinones, such as
Nitropurpurin,
Amidopurpurin,
Alphanitroalizarin,
Alphanitroflavopurpurin,
Alphanitroanthra purpurin,
Paradinitroanthrarufin,
Dinitroanthrachryson,
Betanitroalizarin bordeaux,
or the like, to act alone, or in the presence of condensing agents, such as are
hereinbefore defined, capable of causing or facilitating the action, on aniline,
orthotoluidine, paratoluidine, xylidine, alphanaphthylamine, betanaphthylamine,
metaphenylenediamine, paraphenylenediamine, metatoluylenediamine, benzidine, or
mixtures thereof, or the like primary aromatic monamido or diamido compounds.
4. The process for producing new dye-stuffs of the anthracene series, containing
nitrogen, which process consists in treating with sulphonating agents, the products

page_text: or dyestuffs which can be produced by means of the methods nereinbefore denned,
or are produced in any other manner.
5. As new products of manufacture,
a. The new products,
b. The new dyestuffs,
mended her the nesses hereinhofore defined
or in
any other manner affording
or dyestuffs which can be produced by means of the methods neremverore denneu,.
or are produced in any other manner.
5. As new products of manufacture,
a. The new products,
b. The new dyestuffs,
produced by the processes h inbefore defined, or in any other manner affording
the same result.
5. As new products of manufacture,
a. The new products,
b. The new dyestuffs,
produced by the processes
the same result.
hereinbefore defined, or in
any
other manner affording
NEWTON & SON,
Agents for the Applicant