The Manufacture or Production of Derivatives of Hydroxyanthra- quinones.
Year: 1895

page_text: Date of Application, 8th Mar., 1895
Complete Specification Left, 9th Dec., 1895-Accepted, 11th Jan., 1896
PROVISIONAL SPECIFICATION.
Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.
The Manufacture or Production of Derivatives of Hydroxyanthra-
quinones.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents discovered some time ago a process for producing new
products or dye-stuffs derived from hydroxyanthraquinone, which process consists
in allowing hydroxy. derivatives of anthraquinone to act on organic amido
compounds, especially on primary monoamines or diamines of the aromatic series in a
suitable manner. This process very readily proceeds if the said hydroxy derivatives
of anthraquinone are heated with amido compounds in the presence of certain agents
capable of causing or facilitating the action, using, for instance, boric acid,
hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulphuric acid, phosphoric
acid, acetic acid, benzoic acid, zinc chloride, or the like. Other agents acting in
the same or a similar manner can also be employed. In place of the free acids, the
derivatives thereof, for instance, the corresponding salts of the amido compounds
can be employed. The action proceeds with surprising readiness on using such or
the like 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 necessitated.
Of hydroxy derivatives of anthraquinone, my foreign correspondents have used,
for instance, quinizarin, purpurin, hydroxyanthrapurpurin, hydroxyflavo purpurin,
anthrachryson, alizarin bordeaux, alizarin pentacyanine, alizarin hexacyanine,
hexahydroxyanthraquinone, but other hydroxyanthraquinones, and derivatives of
hydroxyanthraquinones, for instance, nitropurpurin, amido purpurin, betanitro
alizarin bordeaux, 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 paraphenylene diamine,
meta and paratoluylene diamine, dimethylmetaphenylenediamine, dimethylpara-
phenylenediamine, benzidine, tolidine, diamidodiphenolether, paradiamidodiphenyl-
methane, diamido carbazol, 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 researches of my foreign correspondents have now shown, that the
condensation herein before defined, of di, tri, or polyhydroxyanthraquinones, or the
like, with aromatic amido compounds, proceeds in such a manner that but one
hydroxy group of the hydroxyanthraquinones is at first substituted by the residue
of the aromatic amido compound used, and that in the further process, or on
applying stronger conditions of reaction, other hydroxy groups are substituted in
the last named manner. Owing to this fact, my foreign correspondents have now
found that, in place of using di, tri, or polyhydroxyanthraquinones, or the like,

page_text: those products can also be employed which result from one molecular proportion of
a di, tri, or polyhydroxyanthraquinone, or the like, and one molecular proportion
of an aromatic amine or diamine. The last named condensation products are then
allowed to act, at elevated temperatures, on aromatic amines or diamines in
the presence of suitable condensing agents, that is to say, agents causing or
facilitating the action.
Thus, for instance, in order to produce purpurin dianilide, the purpurin
monoanilide can be used in place of purpurin itself. The purpurindianilide is, for
example, obtained by heating purpurin monoanilide with aniline in the presence of
boric acid, aniline hydrochloride, or other agents capable of causing or facilitating
the action.
According to the researches of my foreign correspondents, the monosubstituted
hydroxyanthraquinones, or the like (such as purpurinmonoanilide), can also be
condensed with an aromatic amido compound other than that used for obtaining
the mono substituted product, disubstituted hydroxyanthraquinones being thus
formed which contain the radicles of two different amido compounds. In case the
hydroxyanthraquinone used is a symmetrical one (for instance, quinizarin), it is no
matter in what order the radicles of the different amido compounds are introduced,
as in either case the same disubstituted hydroxyanthraquinone results. Isomeric
disubstituted hydroxyanthraquinones, or the like, are however obtained on using
unsymmetrical hydroxyanthraquinones, and introducing the radicles of the two
different aromatic amido compounds in the one or other order.
Products are thus obtained which can be used at once as dye-stuffs or colors, or may
be converted into valuable dye-stuffs by a subsequent suitable treatment, by the
introduction of acid groups, such as the sulphonic, nitro group or the like.
The process is illustrated by the following two examples, which, however, are
merely typical. The parts are by weight.
J
с
FIRST EXAMPLE.
.
A mixture prepared from 10 parts of purpurin monoanilide, 100 parts of
betanaphthylamine, and. 10 parts of crystallized boric acid, is heated at 150 degrees
Centigrade until a change in color of the heated mass is no longer distinguishable.
The mass, when cold, is powdered, and boiled with dilute hydrochloric acid, in
order to remove the betanaphthylamine used in excess, and the boric acid. The
product thus obtained is purified by crystallisation from. pyridin. It then forms
dark brown lustrous scales.
SECOND EXAMPLE.
A mixture containing 10 parts of the condensation product from equal molecular
proportions of purpurin and betanaphthylamine, 100 parts of aniline, and 10 parts
of boric acid, is heated at 150 degrees Centigrade, until the blue color of the
heated mass no longer increases. The aniline used in excess, and the boric acid are
removed in any suitable manner, and the remaining product is crystallized from
pyridin. The pure product forms crystals with metallic lustre.
The isomeric products obtained by means of the processes described in the
foregoing two examples differ, in that the former product dissolves in aniline,
affording a bluish colored solution, and in concentrated sulphuric acid, with a blue
color, which turns into violet after some time, whereas the latter product dissolves
in aniline, yielding a violet blue colored solution, and in concentrated sulphuric
acid, affording a greenish-blue colored solution.
Unlike the original monosubstituted products, viz. purpurin monoanilide and
purpurin monobetanaphtalide, the color of the sulphuric solutions of the said two
disubstituted products is but slightly altered by boric acid. The sulphonic
derivatives obtained from these disubstituted purpurines, produce intense dark
blue shades.
'

page_text: A mixture prepared from 10 parts of dry alizarin blue, 200 parts of aniline, and
10 parts of crystallized boric acid, is heated during about 3 hours at 130 degrees
Centigrade. The aniline used in excess, and the boric, are removed in the known
manner, and the dried residue is dissolved in ten times its weight of concentrated
sulphuric acid. The resulting sulphuric acid solution is poured into a great
quantity of water, and the dye-stuff precipitated is filtered off. It forms a dark
green precipitate insoluble in soda-lye. It readily dissolves in aniline, affording
a brownish-yellow colored solution, and in concentrated sulphuric acid, affording
a brownish colored solution.
This dye-stuff, when boiled during a certain time with dilute acids or alkalies, is
decomposed, alizarin blue and aniline being thus recovered. It produces bluish-green
shades on chromated wool.
Similar dye stuffs result, if the corresponding quantities of other aromatic amido
compounds, such as ortho or paratoluidine, xylidine, or the like, are substituted for
aniline used in the preceding third example, or if other hydroxyanthraquinoline-
quinones (such as mono-, di-, trihydroxyalizarin blue), are used, and condensed with
aromatic amido compounds.
The sulphonic acids of hydroxyanthraquinones and hydroxyanthraquinoline-
quinones can also be condensed in either of the modes hereinbefore defined, with
aromatic amido compounds, especially with primary aromatic amines. In this
manner, either dye-stuffs result which are at once soluble in water, or products are
obtained (for instance, from purpurinsulphonic acid) which are insoluble.
The process can be carried out, again, in such a manner that disubstituted
products are at once produced, or that condensation products from one molecular
proportion of hydroxyanthraquinone sulphonic acid, or hydroxyanthraquinoline-
quinone sulphonic acid, and one molecular proportion of a primary aromatic amine
or diamine, are at first prepared, which are then allowed to act on aromatic amido
compounds (using either the same or a different one).

page_text: In order to illustrate this process, the following example is given, the parts
being by weight.
FOURTH EXAMPLE.
10 parts of quinizarin sulphonic acid are mixed with 100 parts of paratoluidine
and 10 parts of boric acid. The resulting mixture is heated at 130 degrees
Centigrade, until the green color of the heated mass no longer increases. After
removing the paratoluidine in excess, for instance, by distilling over with steam,
the remaining dye-stuff sulphonic acid is crystallized from dilute hydrochloric acid.
This sulphonic acid readily dissolves in pure water, affording a green colored
solution. It is soluble with difficulty in dilute acids.
It produces green shades on unmordanted and chromated wool.
Analogous products are obtained in a similar manner, on using either other
hydroxyanthraquinone sulphonic acids, or hydroxyanthraquinoline quinone sulphonic
acids, or other aromatic amido compounds.
The resulting products, when containing sulphonic groups, are valuable dye-
stuffs, but the insoluble products obtained from hydroxyanthraquinone sulphonic
acids, or hydroxyanthraquinoline quinone sulphonic acids and aromatic amido
compounds, can be partly converted by sulphonation into coloring matters
possessing likewise great value.
My foreign correspondents have also observed, that the condensation herein before
defined, of hydroxyanthraquinones, hydroxyanthraquinolinequinones, hydroxy-
anthraquinone sulphonic acids, and hydroxyanthraquinoline quinone sulphonic
acids, with aromatic amido compounds, can also be carried out without adding a
condensing agent, that is to say, an agent capable of causing or facilitating the
action, but merely by applying a somewhat higher temperature. Under these
conditions, the action in general proceeds with less ease, and requires a higher
temperature, than when using suitable agents. The process consists in heating the
hydroxyanthraquinones, or the like, together with the aromatic amido compounds,
at a temperature which will suffice to cause the action. The following example is
given in order to illustrate this process.
FIFTH EXAMPLE.
A mixture containing 10 parts of purpurin and 100 parts of paratoluidine is
heated to boiling in a vessel provided with a reflux condenser, until purpurin is no
longer distinguishable. The product thus formed is isolated in the known manner.
My foreign correspondents have described in the foregoing examples, distinct
methods of producing some of the products and dye-stuffs herein before defined.
Naturally, my foreign correspondents do not limit themselves to the particulars
given in these examples, as the mode of working can be varied without departing
from the natur
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Derivatives of Hydroxyanthra-
quinones.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement:
-
My foreign correspondents some time ago discovered a process for producing

page_text: new products or dye-stuffs derived from hydroxyanthraquinone, which process
consists in allowing hydroxy derivatives of anthraquinone to act in a suitable
manner on organic amido compounds, especially on primary monamines or diamines
of the aromatic series. This process is very readily carried out by heating the
said hydroxy derivatives of anthraquinone with amido compounds in the presence of
certain agents capable of causing or facilitating the action, for instance, boric acid,
hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulphuric acid, phosphoric
acid, acetic acid, benzoic acid, or zinc chloride. Other agents acting in the same
or a similar manner can also be used. The action proceeds with surprising
readiness, on using such or the like agents, and in some cases takes place even on
heating on the water bath, whilst in other cases a somewhat higher temperature:
(from about 130 to 200 degrees Centigrade) is necessary.
Amongst the hydroxy derivatives of anthraquinone used by my foreign
correspondents, may be mentioned quinizarin, purpurin, hydroxyanthra purpurin,.
hydroxyflavopurpurin, anthrachryson, alizarin bordeaux, alizarinpentacyanine,.
alizarin hexacyanine, and hexahydroxyanthraquinone, but other hydroxyanthra-
quinones, and derivatives of hydroxyanthraquinones, can also be used, for instance,
nitropurpurin, amidopurpurin, alphanitro alizarin, alphanitroflavopurpurin, alpha-
nitroanthra purpurin, paradinitroanthrarufin, dinitroanthrachryson, and betanitro-
alizarin hordeaux, or the like.
Of 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., auiline, ortho and paratoluidine, xylidine, alpha and betanaphthaline, meta
and paraphenylene diamine, metatoluylene diamine, benzidine, and paradiamido.
diphenylmethane, but the process is not restricted to the use of these amines.
The researches of my foreign correspondents have shewn that the condensation.
herein before defined, of di-, tri-, or polyhydroxyanthraquinones, or the like, with
aromatic amido compounds, proceeds in such a manner that at first only one
hydroxy group of the hydroxyanthraquinones is displaced by the residue of the
aromatic amido compound used, but that subsequently other hydroxy groups are
similarly affected. Consequently, my foreign correspondents have found that,
instead of using simply di-, tri-, or polyhydroxyanthraquinones, or the like, the
products can also be used which are formed from a molecular proportion of a
di, tri, or polyhydroxyanthraquinone, or the like, and a molecular proportion of an
aromatic amine or diamine. Such condensation products are allowed to act, at
suitable temperatures, on aromatic amines or diamines, in the presence of suitable:
condensing agents, or agents capable of causing or facilitating the action.
Thus, for instance, in producing purpurin dianilide, purpurin monanilide can be
used in place of purpurin. Purpurin dianilide, for example, is obtained by heating
purpurin anilide with aniline in the presence of boric acid, aniline hydrochloride, or
other agents capable of causing or facilitating the action.
According to the researches of my foreign correspondents, the monosubstituted
hydroxyanthraquinones, or the like (such as purpurin-monanilide), cau also be
condensed with an aromatic amido compound other than that used in preparing
the monosubstituted product, disubstituted hydroxyanthraquinones being thus
formed which contain the radicles of two different amido compounds. In those
cases in which a symmetrical hydroxyanthraquinone is used (for instance,
quinizarin), it does not matter in what order the radicles of the two different
amido compounds are introduced, as in either case the same disubstituted hydroxy-
anthraquinone is formed. Isomeric disubstituted hydroxyanthraquinones, or the
like, are produced, however, on using unsymmetrical hydroxyanthraquinones, and
introducing the radicles of the two different aromatic amido compounds in one or
other order.
Products are thus obtained which can be directly used as dye-stuffs or colors, or
which may be converted into valuable dye-stuffs by the introduction of acid groups,
such as the sulphonic group.

page_text: EXAMPLE A.
A mixture of 10 parts of purpurinmonanilide, 100 parts of betanaphthylamine,
and 10 parts of crystallized boric acid, is heated at 150 degrees Centigrade, unti!
no further change in the color of the heated mass is distinguishable. When cold,
the mass is powdered, and then boiled with diluted hydrochloric acid, in order to
remove the betanaphthylamine used in excess and the boric acid. The product
thus obtained is purified by crystallization from pyridin. It forms dark-brown
lustrous scales.
EXAMPLE B.
A mixture containing 10 parts of the condensation product from molecular
proportions of purpurin and betanaphthylamine, 100 parts of aniline, and 10 parts
of boric acid, is heated, at 150 degrees Centigrade, until the blue color of the
heated mass no longer increases in intensity. The aniline used in excess, and
the boric acid, are then removed in any suitable manner, and the product is
crystallized from pyridine. The pure product forms crystals exhibiting a metallic
lustre.
The isomeric products obtained by means of the processes described in the
foregoing two examples, differ, in that the former dissolves in aniline, affording a
bluish colored solution, and in concentrated sulphuric acid, with a blue color, which
becomes violet after some time, whereas the latter dissolves in aniline, yielding a
violet-blue colored solution, and in concentrated sulphuric acid, affording a greenish-
blue colored solution.
Unlike the original monosubstituted products, viz., purpurin monanilide, and
purpurin monobetanaphthalide, the color of the sulphuric solutions of the said two
disubstituted products is but slightly altered by the addition of boric acid. The
sulphonic derivatives obtained from these disubstituted purpurines produce intense
dark-blue shades.
A product which crystallises from aniline in light brown crystals, and dissolves
in aniline with a yellowish-red color, and in concentrated sulphuric acid with a
blue color, is formed on using metatoluylene diamine in place of the betanaphthyl-
amine prescribed in the preceding example A.
The product which is obtained on using alphanaphthylamine in place of the
aniline used in the foregoing example B, and which contains the radicles of both
alpha and betanaphthylamine, crystallises from pyridine in needles which dissolve
in aniline with a pure greenish-blue color, and in concentrated sulphuric acid with
a bluish-green color. The sulphonic acid of this product dyes clear blue shades on
wool mordanted with chromium salts.
A great number of other mixed disubstituted hydroxyanthraquinones, or
derivatives thereof, is obtained by means of the process illustrated by the foregoing
two examples. Products or dye-stuffs are thus formed which can be converted into
more valuable products, or dye-stuffs, by subsequently introducing acid groups,
such as the sulphonic group.
The researches of my foreign correspondents have also shown, that not only
hydroxyanthraquinones, but also hydroxyanthraquinoline quinones (such as alizarin
blue and its analogues), can be easily condensed with aromatic amido compounds,
dye-stuffs being thus obtained which in general produce greener shades.
This process is illustrated by the following example. The parts are by weight.

page_text: 10 parts of quinizarinsulphonic acid are mixed with 100 parts of paratoluidine
and 10 parts of boric acid. The mixture is heated at 130 degrees Centigrade,
until the green color of the heated mass no longer increases in intensity. After
removing the excess of paratoluidine, for instance, by distillation with steam, the
remaining dye-stuff, which is a sulphonic acid, is crystallized from diluted hydro-
chloric acid. This sulphonic acid readily dissolves in pure water, affording a green-
colored solution. It is soluble with difficulty in dilute acids.
It produces green shades on unmordanted and chromated wool.
Analogous products are obtained in a similar manner, on using either other
hydroxyanthraquinone sulphonic acids, or hydroxyanthraquinoline quinone
sulphonic acids, or other aromatic amido compounds.
The products containing sulphonic groups are in some cases valuable dye-stuffs,
and the insoluble products obtained from hydroxyanthraquinone sulphonic acids, or
hydroxyanthraquinoline quinone sulphonic acids, and aromatic amido compounds,
can be converted by sulphonation into coloring matters, some of which are also of
great value.
My foreign correspondents have, moreover, observed that the condensation
hereinbefore defined, of hydroxyanthraquinones, or derivatives thereof, hydroxy-
anthraquinoline quinones, bydroxyanthraquinone sulphonic acids, and hydroxy-
anthraquinoline quinore sulphonic acids, with aromatic amido compounds, can
also be carried out without adding condensing agents, or agents capable of causing
or facilitating the action, merely by applying a somewhat higher temperature.
Under these conditions, the action, as a rule, proceeds with less ease, and require3.
a higher temperature than when using suitable condensing agents. The process

page_text: aromatic amido compounds, at a temperature which will suffice to cause the action
to take place. The following example is given in order to illustrate this process.
EXAMPLE E.
A mixture of 10 parts of purpurin and 100 parts of paratoluidine is heated to
boiling in a vessel provided with a reflux condenser, until purpurin is no longer
distinguishable. The product is isolated in the known manner.
My foreign correspondents have described, in the foregoing examples, distinct
methods of producing some of the products and dye-stuffs hereinbefore defined, but
naturally they do not limit themselves to the particulars given in these examples,
as the mode of working can be varied without departing from the nature of this
invention.
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 production of products or dye-stuffs of the anthracene series, containing
nitrogen, by first condensing, in the presence of suitable condensing agents, or
agents capable of causing or facilitating the action, a molecular proportion of a
hydroxyanthraquinone, or derivative thereof, with a molecular proportion of a
primary aromatic amido compound, or diamido compound, and subsequently
condensing the so formed mono-substituted products, likewise in the presence
of suitable condensing agents, or agents capable of causing or facilitating the
action, with a molecular proportion of a primary aromatic amido compound, or
diamido compound, using either oue or different amido compounds.
2. In the process defined by the foregoing claim one, the use of the following
hydroxyanthraquinones, or derivatives thereof, viz., quinizarin, purpurin, hydroxy-
anthra purpurin, hydroxy flavopurpurin, anthrachryson, alizarin bordeaux, alizarin
pentacyanine, alizarin hexacyanine, hexahydroxyanthraquinone, nitropurpurin,
amido purpurin, alphanitro alizarin, alpha nitro flavopurpurin, alphanitro anthra-
purpurin, paradinitroanthrarufin, dinitroanthrachryson, betanitroalizarin bordeaux,
or the like.
3. In the process defined by the preceding claim one, the use of the following
primary aromatic amido, or diamido compounds, viz., aniline, orthotoluidine,
paratoluidine, xylidine, alphanaphthylamine, betanaphthylamine, metaphenylene
diamine, paraphenylene diamine, metatoluylene-diamine, benzidine, or the like.
- 4. For the production of the products or dye-stuffs of the anthracene series,
containing nitrogen, by means of the process defined by the foregoing claim one,
the use of the following condensing agents, viz., hydrochloric, hydrobromic, or
hydrofluoric acid, sulphuric acid, phosphoric acid, boric acid, zinc chloride, acetic
acid, benzoic acid, or the like agents acting in the same or a similar manner.
5. The process for producing dye-stuffs of the anthracene series containing
nitrogen, which process consists in treating with sulphonating agents, the products
or dye-stuffs containing two different aromatic amido radicles, which can be
produced by means of the methods defined in the preceding claims one, two, and
three, or which are produced in any other manner.
6. The production of products or dye-stuff's from hydroxyanthraquinoline
quinones, hydroxyanthraquinoline quinone sulphonic acids, or hydroxyanthra-
quinone sulphonic acids, and primary aromatic amido compounds or diamido
compounds, in the presence of suitable condensing agents, capable of causing or
facilitating the action.
7. The process for producing products or dye-stuffs of the anthracene series,
containing nitrogen, which process consists in allowing hydroxyanthraquinoline
quinones, hydroxyanthraquinoline quinone sulphonic acids, or hydroxyanthra-
quinone sulphonic acids, to act in the presence of suitable condensing agents, as

page_text: defined by the preceding claim four, on the aromatic amido or diamido compounds.
defined by the foregoing claim three.
8. The production of products or dye-stuffs of the anthracene series, containing
nitrogen, by first condensing, by means of the condensing agents hereinbefore
defined, a molecular proportion of a hydroxyanthraquinone sulphonic acid, with a
molecular proportion of one of the aromatic amido or diamido compounds above
referred to, and in subsequently again condensing, also by means of one of the
above defined condensing agents, the mono-substituted products so formed, with a
molecular proportion of an aromatic amido or diamido compound, using either one
or different amido compounds in the two operations.
9. The process for producing dye-stuffs of the anthracene series containing
nitrogen, which process consists in sulphonating the products or dye-stuffs which
can be produced by means of the methods defined by the foregoing claims six, seven,
and eight, or which are produced in any other manner.
10. The production of products or dyestuffs of the anthracene series, containing
nitrogen, which process consists in heating, at elevated temperatures, the hydroxy-
anthraquinones, or derivatives thereof, or the hydroxyanthraquinone sulphonic
acids hereinbefore defined, with the aromatic amido or diamido compounds above
referred to, without an addition of condensing agents.
11. As new products of manufacture, (a) the new products, (b) the new dye-
stuffs, produced by the processes hereinbefore defined, or in any other manner
affording the same result."
Dated this 6th day of Donamber 1805
NEWTON & SON,
Agents for the Applicant.