The Manufacture of New Derivatives of Anthraquinone.
Year: 1890

page_text: Date of Application, 19th Nov., 1890
Complete Specification Left, 5th Aug., 1891--Accepted, 12th Sept., 1891
PROVISIONAL SPECIFICATION.
The Manufacture of New Derivatives of Anthraquinone.
I BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which has been
communicated to me from abroad by Farbenfabriken vormals Friedrich Bayer
& Co. of Elberfeld in the Empire of Germany to be as follows:-
In the Specifications accompanying my applications for Patents No. 8725
dated 5th June 1890 No. 12715 dated 13th August 1890 and No. 17712
dated 4th November 1890 different colouring matters are described under the
generic terms "Alizarine Bordeaux" and "Alizarine Cyanine) which are
obtained by the action of sulphuric acid anhydride (in the form of strong fuming
sulphuric acid) upon alizarine and its analogues.
My foreign correspondents have now discovered that new colouring matters of a
similar description can be obtained by the action of sulphuric acid anhydride
preferably in the form of strong fuming sulphuric acid upon the product of
oxidation of flavo- and anthra-purpurine namely oxyflavo-purpurine and oxy-
anthra-purpurine. These last mentioned bodies are produced by the action of
oxidising agents upon flavo- and anthra-purpurine in the presence of concentrated
sulphuric acid. For the purposes of the oxidation arsenic acid or manganese or
other oxygen yielding bodies can be employed.
In order to manufacture the product of oxidation of flavo-purpurine the process
is conducted as follows for example the parts being by weight.
About 10 parts of dry flavo-purpurine, 8 parts of dry arsenic acid and 150 parts
of sulphuric acid at 66 degrees Baumé are heated in the first place to from about
150 to 160 degrees Centigrade for about 3 hours. The melt is then poured into
1000 parts of water, boiled, filtered, and washed neutral. For the sake of
further purification the oxyflavo purpurine is extracted from the product thus
obtained by means of a boiling solution of alum or sulphate of aluminium and
again separated from this solution by boiling with sulphuric or hydrochloric
acid.
The product thus obtained differs essentially from flavo-purpurine. The latter
dissolves in ammonia with a yellowish brown colour but the solution of the new
product is orange-red. In potash or soda lye on the other hand the solution of
the new product is yellower but brighter than that of flavo-purpurine and when
exposed to the light is as little permanent as the alkaline solution of flavo-
purpurine. Flavo-purpurine dissolves in concentrated sulphuric acid with a
brownish yellow colour oxy-flavo-purpurine under like conditions gives a blueish
and redder colour. In a boiling solution of aluminium sulphate or alum oxy-
flavo-purpurine dissolves with a redder colour and amber coloured fluorescence
and can be separated from this solution by boiling with strong mineral acids.
The colours obtained with oxy-flavo-purpurine upon mordanted wool are
considerably bluer than those resulting from the employment of flavo-purpurine.
Upon mordanted cotton the purpurine character is sharply accentuated especially
with iron and weak alumina mordants.
Anthra purpurine is oxidised into oxyanthra-purpurine in a similar manner.
The product differs from the original material in the same way as oxyflavo
purpurine differs from flavo purpurine. The oxyanthra-purpurine is distinguished
by-the readiness with which it can be dissolved in a hot solution of sulphate of
alumina.
These two new dyestuffs obtained by oxidising flavo- and anthra-purpurine

page_text: with manganese or arsenic acid can be converted, as stated according to the
process described in the Specification accompanying the application for Patent
No. 8725 by treatment with sulphuric acid anhydride preferably in the form of
strong fuming sulphuric acid, likewise into a new mordant dyeing sulphuric acid ether
of the new oxyanthra quinone which being dissolved in alkali and decomposed with
acids or directly by heating with sulphuric acid can be converted into a new
dyestuff of the alizarine bordeaux group. The process for the production of this
substance is similar to that described in the Specification accompanying my
application for Patent No. 87250
The new bordeaux thus obtained display the same differences relatively to the
original material as do other known bordeaux. Their solution in concentrated
sulphuric acid as well as the colours which they produce upon metallic mordants
are considerably bluer than the colours of oxy-flavo- or oxy-anthra purpurine.
My foreign correspondents have further discovered that anthra-rufin which does
not possess colouring properties can be converted, by the action of sulphuric acid
anhydride according to the process described in the Specification accompanying
my application for a Patent No. 8725 into a new and colouring oxy-anthra
quinone.
In this case also a mordant dyeing intermediate product, a sulphuric acid ether,
of the new oxyanthraquinone. is formed in the first instance which by treatment
with alkali and subsequent boiling with acids or directly by heating with acids can
be converted into the new bordeaux. In other respects the process is similar to
that described in the Specification accompanying my application No. 872500.
The new product dissolves in soda lye with a reddish-violet colour or with a
violet colour and amber coloured fluorescence in concentrated sulphuric acid. It
dyes a beautiful blueish red on alumina mordants and a violet on chromium
mordants.
It has further been ascertained by my foreign correspondents in the course of
their researches in connection with the oxidation of alizarine and its analogues by
means of sulphuric acid anhydride that anthra-quinone itself under certain
conditions can be directly converted by the action of sulphuric acid anhydride into
dyestuff's of the alizarine bordeaux and alizarine cyanine series. For this purpose
it is essential that the anhydride be employed in a highly concentrated form and
preferably in an absolutely pure condition.
lu this case the formation of the colouring matter takes place at ordinary
temperature. In the same way as the alizarine bordeaux formed in the first
instance is converted as stated in the Specification accompanying the application
No. 177120 by the highly energetic action of sulphuric acid anhydride preferably
in the form of strong fuming acid upon alizarine, into an alizarine cyanine like
body so there is obtained in like manner from anthra-quinone different products
according to the duration of the period of action of the anhydride and to the
quantity employed. In this case also the sulphuric acid ether of the colouring
matter formed is obtained in the first instance from which the dyestuff is isolated
by dissolving in alkali and boiling with diluted acids or in a direct way by heating
with acids. The following is given as an example of the method of conducting
the process the parts being by weight.
About 10 parts of anthra-quinone are mixed with about 100 parts of sulphuric
acid anhydride and maintained at a temperature not over about 50 degrees Centi-
grade in a closed vessel until all the anthra-quinone has disappeared. The mass is
then mixed with twice the quantity of sulphuric acid mono-hydrate, poured out
onto ice, heated to boiling and filtered. The precipitate is dissolved in soda-lye
boiled and decomposed with hydrochloric or sulphuric acid. The dyestuff separated
is filtered off and washed. It dissolves in soda-lye with a blueish-violet colour and
in concentrated sulphuric acid with a violet colour and intense red fluorescence.
When the action of sulphuric acid anhydride upon anthra-quinone at a high
temperature and in a closed vessel is allowed to go on the sulpho acids of the new
dyestuff are formed. These sulpho acids may be directly employed as water-soluble

page_text: wool dyes or by separating or splitting off the sulpho group in the known manner
the fundamental dyestuff's may be obtained.
The following is given as an example of the method of conducting the operation.
About 10 parts by weighs of anthra-quinone and 100 parts of sulphuric acid
anhydride are heated in a closed vessel for about 10 hours to from 100 to 120
degrees Centigrade.
The materials are then poured out onto about 1000 parts of ice heated to boiling
for about one hour to decompose the sulphuric acid ester of the sulpho acid
the sulpho acid being separated after cooling by the addition of chloride of
potassium.
In order to convert this sulpho acid into the corresponding unsulphurised dye-
stuff about 10 parts by weight of the sulpho acid obtained as herein before described
are heated to from about 180 to 190 degrees Centigrade for atont 6 hours with
about 100 parts of sulphuric acid at 66 degrees Baumé. The materials are then
poured out into water, the dyestuff separated by filtration and purified by repeated
dissolving.
Dated this 19th day of November 1890
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture of New Derivatives of Anthraquinone.
I BENJAMIN WILLOOX of 47 Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention, which has been
communicated
to me from abroad by the Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of Germany, and in what manner the
same is to be performed to be particularly described and ascertained in and by
the following statement:-.
In the Specifications accompanying my applications for Patents No. 8725
dated 5th June 1890, No. 12715 dated 13th August 1890 and No. 17712 dated
4th November 1890 different colouring matters are described under the joint terms
"Alizarin Bordeaux" and "Alizarin Cyanin" which are obtained by the action of
sulphuric acid anhydride (in the form of strong fuming sulphuric acid) upon
alizarin and its analogues.
My foreign correspondents have now discovered that new colouring matters of
similar properties can be obtained by the action of sulphuric anhydride, preferably
employed in the form of strong fuming sulphuric acid, on the products of oxidation
of flavo- and anthra-purpurin namely oxyflavo-purpurin and oxyanthra-purpurin.
These last mentioned bodies are produced by the action of oxidising agents on
flavo- and anthra-purpurin in the presence of concentrated sulphuric acid. As
oxidising agents; arsenic acid, manganese dioxide or other compounds yielding
oxygen may be employed.
In order to manufacture these products of oxidation the process is conducted as
follows for example the parts being by weight.
FIRST EXAMPLE.
MANUFACTURE OF OXYFLAVO-PURPURIN.
About 10 parts of dry flavo-purpurin 8 parts of dry arsenic acid and 150 parts
of sulphuric acid at 66 degrees Baumé are heated in the first place to from
about 150 to 160 degrees Centigrade for about 3 hours. The melt is then poured
into 1000 parts of water, boiled, filtered and washed until neutral. The oxyflavo-
purpurin formed is extracted from the raw product thus obtained by means of a
boiling solution of aluminium sulphate and separated again from this solution by
builing with sulphuric or hydrochloric acid.

page_text: The product thus obtained differs essentially from flavo-purpurin. The latter
dissolves in ammonia with a yellowish-brown colour, whilst the solution of the new
product is orange-red. In potash- or soda-lye on the other hand the new product
dissolves with a colour yellower and brighter than flavo-purpurin. On exposure
to the light its alkaline solutions are decomposed as easily as those of flavo-
purpurin. The latter dissolves in concentrated sulphuric acid with a brownish-
yellow colour; oxyflavo-purpurin however so dissolves with a blueish red colour.
By a boiling solution of aluminium sulphate or of alum oxyflavo-purpurin is
dissolved with a red colour and an amber like fluorescence. From this solution it
may be separated again by boiling with strong mineral acids.
The shades obtained with oxyflavo-purpurin upon mordanted wool are much
bluer than those resulting when flavo-purpurin is employed. On mordanted cotton
the purpurin character becomes prominent especially when iron or weak alumina
mordants are employed.
Anthra-purpurin is oxidised to oxyanthra-purpurin in the same manner. The
differences between this oxy-derivative and the original material are similar to
the differences between oxy-flavo-purpurin and flavo-purpurin. Oxy-anthra-
purpurin is distinguished by its easy solubility in hot solutions of sulphate of
alumina.
These two new dyestuff's obtained by oxidising flavo- and anthra-purpurin with
manganese dioxide or arsenic acid in concentrated sulphuric acid solution can be
converted according to the process described in the Specification of the application
for Patent No. 8725 by treatment with sulphuric anhydride, the latter preferably
being employed in the form of strong fuming sulphuric acid; they can likewise be
converted into new colouring matters which are the sulphuric ethers of new
oxyanthra-quinones and have the property of dyeing fibre with the aid of mordants.
When dissolved in alkali and decomposed with acids or directly when heated with
sulphuric acid these said others can be changed into new dyestuffs of the alizarin-
bordeaux series. The process for the production of these substances is analogous
to that described in the Specification of my application for Patent No. 8725º.
The new bordeaux thus obtained shew the same characteristic properties as the
other known bordeaux. Their solutions in concentrated sulphuric acid, and the
colours produced by them with the aid of metallic mordants, are considerably
bluer than are those of oxyflavo- or oxyanthra-purpurin.
My foreign correspondents have further discovered that anthra-rufin, which does
not in itself possess colouring properties, can be converted into a new oxy-anthra-
quinone suitable for dyeing by the action of sulphuric anhydride according to the
process described in the Specification of my application for a Patent No. 87250.
In this casc also an intermediate product, (a sulphuric ether of the new oxy-
anthra-quinone) capable of dyeing fibre with the aid of mordants is formed in the
first instance which by further treatment with alkali and subsequent boiling with
acids, or directly by heating with acids, can easily be converted into the new
bordeaux product. The process for its formation is analogous to that described in
the Specification of my application No. 872390.
.It
The new product dissolves in soda lye with a reddish-violet colour and in
concentrated sulphuric acid with a violet colour and amber like fluorescence.
yields a beautiful blueish-red with alumina mordants and a violet with chromium
mordants.
It has further been ascertained by my foreign correspondents in the course of
their researches on the oxidation of alizarin and its analogues by means of sulphuric
anhydride that anthra-quinone can also be directly converted by the action of
sulphuric anhydride into a dyestuff of the alizarin bordeaux and alizarin cyanin
series that is to say into hexa-oxyanthraquinone. For this purpose it is necessary
that the anhydride be employed in a highly concentrated form, preferably in an
absolute or pure form In this case the conversion takes place at ordinary
temperature, and there is obtained from anthra-quinone the sulphuric ether of
hexa-oxyanthraquinone described in the Specification of the application for

page_text: Patent No. 17712⁰⁰. From this ether the dyestuff may be isolated either by
dissolving in alkali and by boiling the resulting alkaline solution with diluted acids
or directly by heating the aforesaid ether with acids.
The following is given as an example for the production of hexaoxyanthra-
quinone.
SECOND EXAMPLE.
CONVERSION OF ANTHRAQUINONE INTO HEXAOXYANTHRAQUINONE.
A mixture of 10 parts of anthraquinone and 100 parts of sulphuric anhydride is
allowed to stand in a closed vessel at a temperature not over about 50 degrees
Centigrade until the quinone has almost been dissolved. After the liquid has been
mixed with twice the quantity of mono-hydrated sulphuric acid it is poured onto
ice; the solution is heated to boiling and the resulting precipitate is filtered off.
The solution of the latter in soda-lye is boiled and after having been filtered is
decomposed with hydrochloric or sulphuric acid; the dyestuff which separates is
then filtered off and washed. The hexaoxyanthraquinone so formed dissolves in
soda lye with a blueish-violet colour and in concentrated sulphuric acid with a
violet colour and intensely red fluorescence.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is :-
:-
First. The manufacture of oxyflavopurpurin and oxyanthrapurpurin by the
action of oxidizing agents on flavopurpurin and anthrapurpurin in the presence of
sulphuric acid.
Second. The conversion of oxyflavopurpurin and oxyanthrapurpurin into new
colouring matters which are sulphuric ethers of new polyoxyanthraquinones by
treating them with sulphuric anhydride.
Third. The production of new bordeaux-like polyoxyanthraquinones by decom-
posing the alkaline solutions of the sulphuric ethers mentioned under Claim 2
with acids or by heating the aforesaid sulphuric ethers with acids.
Fourth. The manufacture of an intermediate product (sulphuric ether) from
anthrarufin by the action of sulphuric anhydride thereon.
Fifth. The conversion of the sulphuric ether which is obtained by the treatment.
of anthrarufin with sulphuric anhydride into the bordeaux of anthrarufin by boiling
the alkaline solution of the said ether with acids or by heating the ether with
acids.
Sixth. The production of the sulphuric ether of hexaoxyanthraquinone by
acting with sulphuric anhydride on anthraquinone.
Seventh. The transformation of the sulphuric ether of hexaoxyanthraquinone
first resulting by the action of sulphuric anhydride on anthraquinone into hexaoxy-
anthraquinone by boiling the alkaline solution of the aforesaid ether with acids or
by heating the ether with acids.
Eighth. As articles of manufacture the new products herein before described.
Dated thin 5th 1901
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London.