The Manufacture and Production of New Derivatives of Alizarin and its Analogues.
Year: 1891

page_text: Date of Application, 11th Dec., 1891
Complete Specification Left, 10th Sept., 1892-Accepted, 15th Oct.. 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Derivatives of Alizarin
and its Analogues.
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
and Company of Elberfeld in the Empire of Germany) to be as follows :-
My foreign correspondents have discovered that by employing the pentahydroxy-
anthraquinone which is obtained from symmetrical dihydroxybenzoic acid and
gallic acid according to the process described in the "Berichte der Deutschen
Chemischen Gesellschaft" volume XXI. page 251, in place of the hydroxyanthra-
quinones mentioned in the Specification of Letters Patent No. 8725 of 1890, a new
alizarin compound results which differs from the original compound in that it
possesses the valuable property of being suitable for dyeing.
The process for the manufacture of this new colouring matter may be carried out
in the same manner as that described in the said Specification of the Patent
No. 8725 for the other hydroxyanthraquinones, a sulphuric ether of the dye-stuff
being formed in the first place which intermediate product is capable of dyeing
mordanted wool and can be converted into the dye-stuff itself in the well known
manner.
The following may be given as an example of the mode of producing this new
colouring matter.
10 parts, by weight, of pentahydroxyanthraquinone are introduced into 200 parts
by weight, of fuming sulphuric acid containing 80 per cent. of anhydride and this
mixture is allowed to stand at a temperature of 30 degrees centigrade for about
24 hours. The solution resulting is poured onto ice and the liquid mixture is then
heated to boiling and subsequently the precipitate is filtered off. By dissolving the
said precipitate in soda-lye and heating its alkaline solution (after heating again to
boiling) with hydrochloric or sulphuric acid the new dye-stuff is caused to separate
as a fine precipitate which is filtered off and washed. In this state it is a brown
paste soluble in sodium-carbonate solution with a red colour in ammonia with a
blueish-red colour and in soda-lye with a violet colour. It is dissolved by concen-
trated sulphuric acid with a violet colour. This new dye-stuff produces a reddish-
violet colour on wool mordanted with alumina salts and a violet colour on wool
mordanted with chromium salts.
II.
In the Provisional Specification accompanying my application for Patent
No. 13677 dated 13th August 1891 a new dye-stuff is described formed from
anthrachrysone by oxidation, belonging to the series of the alizarin cyanines and
found to be identical with the hexahydroxyanthraquinone formed by the oxidation
of alizarin bordeaux with fuming sulphuric acid. My foreign correspondents
employed sulphuric anhydride for the above conversion of anthrachrysone into the
new dye-stuff. They have now found that anthrachrysone can be converted into a
valuable dye-stuff by other oxidising agents such for example as manganese dioxide.
The reaction, however, takes place with greater difficulty than in analogous cases
such for example as the oxidation of alizarin-bordeaux to alizarin-cyanine and a
higher temperature is preferably employed.
The following is given as an example of the mode of effecting the oxidation of
anthrachrysone by means of manganese, dioxide.
10 parts, by weight, of dried anthrachrysone are introduced into 200 parts, by

page_text: The alizarin-bordeaux or tetrahydroxyanthraquinone described in the Speci-
fication of Letters Patent 8725 of 1890.
The alizarin pentacyanine or pentahydroxyanthraquinone described in the
Specification accompanying the application for Patent 4871 dated
18th March 1891.
The alizarin hexacyanine or hexahydroxyanthraquinone described in the last
named Specification.
The hexahydroxyanthraquinone which is obtained according to the process
described in the Specification of Letters Patent No. 17712 dated
4th November 1890 from alizarin bordeaux according to the Specification
of Letters Patent No. 18729 dated 19th November 1890 from anthra-
quinone, according to the Provisional Specification, accompanying the
application for Patent No. 13677 dated 13th August 1891 from anthra-
chrysone by oxidising it by the aid of strong fuming sulphuric acid,
n be converted by the action of strong nitric acid into new dyestuffs, which are
luble in water.
The reaction taking place in this case is a very complicated one. At first the

page_text: aforesaid compounds are nitrated and a hydroxyl group becomes introduced into the
molecule of several of them, instead of hydrogen, as for example, into the alizarin
bordeaux, but finally the nitric acid changes all the above mentioned compounds
into quinones, the so called anthradiquinones. Owing to this reaction these new
colouring matters have been termed by my foreign correspondents, "nitro-hydroxy-
anthradiquinones."
The property of being soluble in water may be ascribed to the quinone group
which these anthradiquinones contain beside the quinone group of anthraquinone,
although the anthradiquinones which have not been subjected to the action of nitric
acid are more or less soluble in water.
In order to carry out this process either the strongest nitric acid is allowed to act
upon the said hydroxyanthraquinones, mixed with an indifferent solvent, or the
perfectly dried hydroxy anthraquinones are exposed to the vapours of fuming
nitric acid.
In the first case the process may be conducted as follows:-
10 parts by weight of dried and finely powdered alizarin bordeaux are mixed
with 100 parts, by weight, of glacial acetic acid and thereupon 30 parts by weight
of nitric acid of the specific gravity of 15 are allowed to flow into the mixture.
After standing for say about 12 to 18 hours, the reaction is complete and the new
colouring matter soluble in water having separated in solid form may be isolated
by filtration.
When penta- or hexa-hydroxyanthraquinone is subjected to this process, the
reaction proceeds in less time, thus if 10 parts by weight of either of the two
diquinones and from 7.5 to 15 parts by weight of nitric acid be employed, the con-
version is complete in about 6 to 10 hours.
Instead of glacial acetic acid, other solvents for example, ligroin or chloroform
may be used with the same result.
In the second case the process can be carried out as follows:-
The dried finely powdered hydroxyanthra quinones are placed in thin layers in
closed chambers in which flat vessels are placed containing fuming nitric acid.
The reaction is complete when a portion of the dye-stuff dissolves readily and
clearly in cold water. The whole material is converted within from about 12 to
20 hours.
The colouring matters thus obtained easily dissolve in cold water forming a dark
red coloured liquid. When these solutions are allowed to stand for some time, or
when they are heated to boiling or mixed with sulphurous acid, insoluble substances
are separated which crystallise from a mixture of acetone and alcohol in beautiful
red crystals with a metallic lustre. These possess the composition of nitro-hydroxy-
anthraquinones.
A dinitrohexahydroxyanthraquinone is obtained from the hexahydroxyanthra-
quinone by treating with nitric acid and by reducing in the aforesaid manner.
Alizarin bordeaux or tetra hydroxyanthraquinone and alizarin cyanine R or penta-
hydroxyanthraquinone yield the same mononitropentahydroxyanthraquinone.
The dyestuff soluble in water obtained from the hexahydroxyanthraquinone of
the Specifications of Patents Nos. 177120 and 18729 and of application for Patent
No. 13677 is distinguished by the readiness with which it crystallises. Its solution
in liquid ammonia is greenish blue, in sodium carbonate solution or soda lye blueish
green, and on adding an excess of the latter reagent a greenish precipitate is
separated. It is dissolved by concentrated sulphuric acid with a blue colour, and
this sulphuric acid solution, (unlike the original hexahydroxyanthraquinone) does
not show a distinct absorption spectrum.
These new soluble colouring matters, yield greenish chrome lakes and owing to
their solubility in water are especially suitable for use in printing.
Dated this with 3
D
1001
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of New Derivatives of Alizarin
and its Analogues.
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) 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 have discovered that by employing the penta-hydroxy
anthraquinone which is obtained from symmetrical dihydroxybenzoic acid and
gallic acid according to the process described in the "Berichte der Deutschen
Chemischen Gesellschaft" volume XXI page 751 in place of the hydroxy-
anthraquinones mentioned in the Specification of Letters Patent No. 8725 of 1890 a
new alizarin compound results which differs from the original compound in that it
produces violet shades on wool mordanted with chromium salts whilst those
produced by the pentahydroxy anthraquinone are brown.
The process for the manufacture of this new colouring matter may be carried
out in the same manner as that described in the said Specification of the Patent
No. 8725 for the other hydroxy-anthraquinones a sulphuric ether of the dye-stuff
being formed in the first place which intermediate product is capable of dyeing
mordanted wool and can be converted into the dye-stuff itself in the well known
manner.
The following is given as an example of the mode of producing this new colouring
matter the parts being by weight.
10 parts of pentahydroxy anthraquinone are introduced into 200 parts of fuming
sulphuric acid containing 80 per cent. of anhydride and this mixture is allowed to
stand at a temperature of 30 degrees centigrade for about 24 hours. The resulting
solution is poured on to ice and the liquid mixture is then heated to boiling and
subsequently the precipitate is filtered off. By dissolving the said precipitate in
soda-lye and treating its alkaline solution (after heating again to boiling) with
hydrochloric or sulphuric acid in excess the new dye-stuff separates as a fine
precipitate which is filtered off and washed. It is then in the state of a brown paste
soluble in sodium-carbonate solution with a red colour, in ammonia with a bluish-red
colour and in soda-lye with a violet colour. It is dissolved by concentrated sulphuric
acid with a violet colour. This new dye-stuff produces a reddish violet colour on
wool mordanted with alumina salts and a violet colour on wool mordanted with
chromium salts.
In the Specification of Letters Patent No. 13677 dated 13th August 1891 a new
dye-stuff is described formed from anthrachrysone by oxidation and belonging to
the series of the alizarin cyanines and identical with the hexa-hydroxy-anthra-
quinone formed by the oxidation of alizarin bordeaux with fuming sulphuric acid.
My foreign correspondents employed sulphuric anhydride for the above conversion
of anthrachrysone into the new dye-stuff. They have now found that anthrachrysone
can be converted into a valuable dye-stuff by other oxidising agents such for
example as manganese dioxide, and the like. The action however takes place with
greater difficulty than in analogous cases such for example as the oxidation of
alizarin bordeaux to alizarin cyanine and a higher temperature is preferably
employed.
The following is given as an example of the mode of effecting the oxidation of
anthrachrysone by means of manganese dioxide, the parts being by weight.
10 parts of dried anthrachrysone are introduced into 200 parts of sulphuric acid
(66 degrees Baumé) aud after the addition of 15 parts of powdered manganese
dioxide the mixture is heated to a temperature of about 150 degrees to 180 degrees

page_text: centigrade until a portion poured into sulphuric acid shews the colour, the fluorescence,
and the absorption spectrum, of hexahydroxyanthraquinone. When the conversion
is complete the mixture is poured into water and the dye-stuff is filtered off washed
and purified by redissolving it in alkalies and again separating with acids.
In order to oxidise the anthrachrysone at ordinary or moderately elevated
temperature a greater quantity of the oxidising agent is to be employed and it
must be allowed to act for a longer time. It is likewise preferable to employ a
greater quantity of concentrated sulphuric acid. In operating at a moderate teniper-
ature an intermediate product (a so called anthradiquinone) is formed in the first place
which my foreign correspondents have found to be identical with the diquinone of
hexa-hydroxy-anthraquinone described in the Specification of Letters Patent
No. 4871 of 1891. The said diquinone is converted into the hydroquinone viz.
hexa-hydroxy-anthraquinone, by heating it with water or more practically by
treating it with reducing agents. My foreign correspondents have found that this
reaction also partially takes place on heating the said diquinone with sulphuric
acid and at elevated temperatures and in consequence thereof the aforesaid
sulphuric liquid obtained in the foregoing example contains the hexa-hydroxy-
anthraquinone in considerable amount.
In order to illustrate the method of oxidising anthra-chrysone at ordinary or
moderately elevated temperature the following example is given the parts being by
weight.
10 parts of anthrachrysone are dissolved in 300 parts of sulphuric acid
(66 degrees Baumé) and 22 parts of powdered manganese dioxide are added whilst
the mixture is well stirred, taking care that the temperature does not rise above
35 degrees centigrade. The completion of the reaction is ascertained by taking
out samples of the mixture separating therefrom the hexa-hydroxy-anthraquinone
and examining the sulphuric solution of the latter with the spectroscope. If only
the absorption spectrum typical of hexa-hydroxy-anthraquinone appears the
sulphuric solution is poured onto ice and the anthradiquinone thus separated is
filtered off and this is subsequently converted into hexa-hydroxy-anthraquinone by
heating it in the well known manner with reducing agents, such as for example,
sulphurous acid.
In the Specification of Letters Patent No. 12715 dated 13th August 1890 new
alizarin dye-stuffs are described which are obtained by the action of ammonia on
the sulphuric ethers of alizarin-bordeaux and its analogues. These colouring
matters containing nitrogen are superior to the original bordeaux products as much
bluer shades are produced by them. By treating with ammonia the sulphuric ethers
of the bordeaux of alizarin, of purpurin, of anthragallol, of flavopurpurin, of
anthrapurpurin, or of rufigallic acid my foreign correspondents have converted
them into the new dye-stuffs which are described in the last named Specification
and they have found that a new valuable dye-stuff of this series results from the
action of ammonia on the sulphuric ether of the colouring matter which is produced
by oxidising with strong fuming sulphuric acid, alizarin bordeaux, anthraquinone
and anthrachrysone which colouring matter possesses the composition of a hexa-
hydroxy-anthraquinone as described in the Specification of Letters Patent No 13677
of 1890.
In order to produce the new dye-stuff either the sulphuric ether obtained by
treating alizarin-bordeaux, anthraquinone or anthrachrysone, with sulphuric
anhydride, or the sulphuric ether, which results from the action of sulphuric
anhydride employed as strong fuming sulphuric acid on hexa-hydroxy-anthraquinone,
is separated with the precaution mentioned in the aforesaid Specification and
thereupon dissolved in concentrated liquid ammonia. After some hours this solution
is mixed with water and the new dye-stuff is separated by the addition of acid.
It is a dark precipitate which dissolves in sodium carbonate and ammonia solutions
In alcohol it.
with a violet colour and in soda-lye with a violet-blue colour.
dissolves with a bluish-red colour and in concentrated sulphuric acid with a

page_text: violet-red colour. Its solution in concentrated sulphuric acid (unlike the sulphuric
acid solution of the hexa-hydroxy-anthraquinone) does not shew a distinct absorption
spectrum.
The new dye-stuff produces a violet colour cn wool mordanted with alumina salts
and a pure blue colour on wool mordanted with chromium salts.
My foreign correspondents have further found that by the action of strong nitric
acid the following poly-hydroxy-anthraquinones can be converted into new dye
stuffs which are soluble in water viz. :-the alizarin bordeaux or tetrahydroxyanthra-
quinone described in the Specification of Letters Patent No. 8725 dated 5th June
1890 the alizarin pentacyanine or pentahydroxy-anthraquinone described in the
Specification of Letters Patent No. 4871 dated 18th March 1891; the alizarin
hexacyanine or hexahydroxyanthraquinone described in the last named Specification;
or the hexahydroxyanthraquinone which is obtained according to the process
described in the Specification of Letters Patent No. 17712 dated 4th November
1890 from alizarin bordeaux according to the Specification of Letters Patent
No. 18729 dated 19th November 1890, from anthraquinone, according to the
Specification of Letters Patent No. 13677 dated 13th August 1891 from
anthrachrysone by oxidising it with the aid of strong fuming sulphuric acid or by
other processes.
The action taking place in this case is a complicated one. At first the aforesaid
compounds are nitrated, and a hydroxyl group is introduced into the molecule of
several of them in place of hydrogen, as for example into the alizarin bordeaux,
and finally the nitric acid changes all the above mentioned compounds into quinones
viz. dye-stuffs of the series of the so called anthradiquinones. Owing to this
reaction, these new colouring matters soluble in water have been termed by my
foreign correspondents "nitro-hydroxy-anthradiquinones."
"
The property of solubility in water may be ascribed to the quinone group,
which these anthradiquinones contain beside the ketone group of anthraquinone,
as the anthradiquinones which have been formerly described by my foreign
correspondents are likewise more or less soluble in water.
In order to carry out this process either strong nitric acid is allowed to act upon
the said hydroxy-anthraquinones mixed with an indifferent solvent, or the perfectly
dried hydroxy-anthraquinones are exposed to the vapours of nitric acid.
In the first case the process may be conducted as follows: the parts being by
weight.
10 parts of dried and finely powdered alizarin bordeaux are mixed with 160 parts
of glacial acetic acid and thereupon 30 parts, of nitric acid of the specific gravity
of 15 are allowed to flow into the cooled mixture. After standing say about
12 to 18 hours the action is complete and the new colouring matter soluble in water
having separated in a solid form may be isolated by filtration.
When the alizarin pentacyanine or the alizarine hexacyanine or the isomeric
hexa-hydroxy anthraquinone are subjected to this process the action proceeds in less
time thus if 10 parts of either of the said substances and from 7.5 to 15 parts of
nitric acid be employed the conversion is complete in or about 6 to 10 hours.
Instead of glacial acetic acid, other solvents) (for example ligroin or chloroform
may be used with the same result.
In the second case the process can be carried out as follows:-
The dried finely powdered hydroxyanthraquinones are placed in thin layers in
closed chambers in which flat vessels are placed containing fuming nitric acid. The
action is complete when a portion of the dye-stuff readily and clearly dissolves in
cold water. The whole material is converted in from about 12 to 20 hours.
The colouring matters thus obtained from the poly-hydroxy-anthraquinones
easily dissolve in cold water forming a dark red coloured liquid. When these
solutions are allowed to stand for some time, or when they are heated to boiling or
mixed with sulphurous acid, the quinone group contained therein is reduced and
insoluble, or difficultly soluble, substances are separated which crystallise from a

page_text: mixture of acetone and alcohol in beautiful red needles with a metallic lustre.
These possess the composition of nitro-hydroxy-anthraquinones.
A dinitro-hexa-hydroxy anthraquinone is obtained from the hexa-hydroxy-
anthraquinone by treating with nitric acid and by reducing in the aforesaid manner.
Alizarin bordeaux or tetra hydroxy-anthraquinone and alizarin-pentacyanine
yield the same mono-intro-penta-hydroxy anthraquinone.
The dye-stuff soluble in water obtained from the hexa-hydroxy-anthraquinone
of the Specifications of Letters Patent Nos. 17712 and 1872900 and No. 13677" is
distinguished by the readiness with which it crystallises. The solution in liquid
ammonia is greenish-blue, in sodium-carbonate solution, blue; in soda-lye, blueish ;
and on adding an excess of the latter two reagents a greenish precipitate is
separated. It is dissolved by concentrated sulphuric acid with a blue colour and
this sulphuric acid solution (unlike the original hexa-hydroxy-anthraquinone) does
not shew a distinct absorption spectrum. It dyes wool, mordanted with chromium
salts, a greenish-blue or blueish-black, whilst the shades produced on wool
mordanted with alumina salts are of a heliotrope-like colour.
The other new soluble colouring-matters yield blueish red, greenish-blue, blueish-
black or greenish-black, chrome lakes and, owing to their solubility in water, all
these dye stuffs are especially suitable for use in printing.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what
I claim is :-
1) The process for producing a new sulphuric ether by treating penta-hydroxy-
anthraquinone (described in the "Berichte der Deutschen chemischen Gesellschaft"
volume 21 page 751) with an excess of sulphuric anhydride or strong fuming
sulphuric acid.
2) The process for converting the sulphuric ether of the foregoing first claim
into the corresponding alizarin dye-stuff by heating it, or its alkaline solution, with
acids.
3) The manufacture for a new dye-stuff by treating penta-hydroxy-anthraquinone
described as aforesaid in the "Berichte der Deutschen chemischen Gesellschaft
with an excess of sulphuric anhydride, or strong sulphuric acid, pouring the resulting
liquid on to ice, heating to boiling the mixture so formed, filtering off the
precipitate and dissolving it in soda lye and heating this solution with hydrochloric,
or sulphuric acid, in excess.
4) The process for producing the diquinone of hexa-hydroxy-anthraquinone by
treating anthra-chrysone, in sulphuric solution, with oxidising agents at low or
moderately elevated temperatures.
5) The conversion of the diquinone of the aforegoing fourth claim into the
corresponding hydroquinone (hexa-hydroxy-anthraquinone) by treating with water
or acids or by treating with reducing agents.
6) The manufacture of hexa-hydroxy-anthraquinone by heating anthrachrysone
in sulphuric solution with oxidising agents at elevated temperatures.
7) The process for producing a new alizarin dye-stuff by treating with ammonia
the sulphuric ether of hexa-hydroxy-anthraquinone.
8) The manufacture of new alizarin dye-stuffs by the action of nitric acid on
alizarin bordeaux, alizarin pentacyanine, alizarin hexacyanine or hexa-hydroxy-
anthraquinone.
9) As new manufactures the new products hereinbefore defined.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.