Manufacture of Penta- and Hexaoxy-anthraquinonedisulphonic Acids.
Year: 1898

page_text: Date of Application, 23rd May, 1898
Complete Specification Left, 3rd Feb., 1899-Accepted, 18th Mar., 1899
PROVISIONAL SPECIFICATION.
Manufacture of Penta- and Hexaoxy-anthraquinonedisulphonic
Acids.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Chartered Patent Agent, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by The Farbwerke vormals Meister Lucius and Brüning, of Hoechst
a/Main, in the Empire of Germany, Chemical Manufacturers) to be as follows:-
In the Provisional Specification No. 0533 of 1898 are described two new
isomeric tetra-oxyanthraquinonedisulphonic acids, derived from two new isomeric
tetraoxyanthraquinones, and obtained by the action of gentle oxidising agents
such as peroxide of lead, peroxide of manganese, chloride of lime, ferric salts
chromates, persulphates, nitric acid and the like upon diamidodisulpho-
anthraflavic acid and diamidodisulphoisoanthraflavic acid. Whilst the only hitherto
known tetraoxyanthraquinonedisulphonic acid, that is to say, the anthra-
chrysonedisulphonic acid is not changed in concentrated sulphuric acid solution
by oxidising agents, such, for instance, as manganese dioxide, and is easily trans-
formed by nitric acid into dinitroanthrachrysonedisulphonic acid, both the new
tetraoxyanthraquinonedisulphonic acids behave differently. If these sulphonic
acids be treated with manganese dioxide or nitric acid, then they are oxidised, as
my foreign correspondents have found, into new pentaoxyanthraquinonedi-
sulphonic acids. The pentaoxyanthraquinones which serve as bases to the new
sulphonic acids are also new and are not identical with the pentaoxyanthra-
quinones hitherto known.“
These two new pentaoxyanthraquinone disulphonic acids can be further
oxidised in a concentrated sulphuric acid solution by oxidising agents usually
employed in this case, such, for instance, as manganese dioxide peroxide of lead,
arsenic acid, etc., into two isomeric hexaoxyanthraquinone-disulphonic acids, of
which one is identical with the hexaoxyanthraquinonedisuplhonic acid described
in the Specification No. 17543 of 1893. For the manufacture of these two
hexaoxyanthraquinonedisulphonic acids an isolation of the two pentaoxyanthra-
quinone disulphonic acids is not absolutely necessary. It is best to start from
the two tetraoxyanthraquinonedisulphonic acids described in the Specification
No. 6533 of 1898 and to treat them with an abundant excess of oxidising agents.
The new penta- and hexaoxyanthraquinone disulphonic acids are valuable blue
mordant dyestuffs. The following examples illustrate the process.
EXAMPLE I.
Tetraoxyanthraquinonedisulphonic acid from anthraflavic acid is dissolved in
form of its acid potassium salt in 10 to 20 times its quantity in weight of
sulphuric acid of 66° Bé. and to the well cooled solution is slowly run in with
active stirring somewhat more than the quantity corresponding to 1 molecule of
finely ground manganese dioxide

page_text: After a short time the reaction begins, the mixture becoming a clear intense
blue. To complete the reaction, the mass is stirred for some hours and cooled at
the same time; then further stirred for from 12 to 24 hours at ordinary tempera-
ture, poured into a sufficient quantity of water and boiled after having added,
if required, some solution of a bisulphite. From the filtered pure red solution
the acid potassium salt of pentaoxyanthraquinonedisulphonic acid is separated
by potassium chloride and may again be purified by recrystallisation.
With the same result nitric acid may be used as oxidising agent, by adding to
the concentrated sulphuric acid solution of tetraoxyanthraquinonedisulphonic
acid 1 molecule of nitric acid either as the acid itself or as a suitable nitrate
under the conditions above set forth. The course of the reaction is the same.
The product is soluble with some difficulty in cold water, more easily in hot
water with a red colour, which on addition of ammonia and soda becomes a more
intense red, and red-violet on addition of fixed alkalies. An excess of alkali
precipitates the sulphonic acid in red flakes. In concentrated sulphuric acid
the sulphonic acid is soluble with a red-violet colour. The solution exhibits a
red fluorescence.
The pentaoxyanthraquinonedisulphonic acid dyes wool red in an acid bath.
The acid dye, subsequently treated with chromium fluoride produces a pure blue
fast to milling.
EXAMPLE II.
Under exactly the same conditions the tetraoxyanthraquinonedisulphonic acid
from isoanthraflavic acid may be transformed by the same oxidising agents into
one of the above described isomeric pentaoxyanthraquinone disulphonic acids.
Its manufacture is carried out under the conditions set forth in Example I.
In order to isolate the new compound the violet mixture is in this case also
poured into water, boiled, salted out with potassium chloride and the product
to be purified is precipitated from its aqueous solution by an excess of fixed
alkali and re-transformed into the acid of potassium salt.
The pure product is a red crystalline powder, easily soluble in hot water with
a red solution becoming violet on addition of alkali. An excess of alkali pre-
cipitates the alkali salt from the aqueous solution in violet blue crystalline
flakes.
Concentrated sulphuric acid dissolves the sulphonic acid with a red colour.
The concentrated solution exhibits a red fluorescence.
The red dye of the new pentaoxyanthraquinone-disulphonic acid upon wool in
an acid bath produces on subsequent treatment with chromium fluoride a blue
fast to milling and light, but its tint is of a somewhat redder hue than that
obtained from pentaoxyanthraquinone disulphonic acid derived from anthraflavic
acid.
EXAMPLE III.
Pentaoxyanthraquinonedisulphonic acid obtained according to Example I is
stirred into 10 to 12 times its weight of concentrated sulphuric acid to which is
added, while cooling, somewhat more than the quantity corresponding to 1 mole-
cule of finely ground manganese dioxide. The reaction takes place at ordinary
temperature and is completed within 1 to 2 days.
The violet blue mixture is poured into water boiled filtered, and the dyestuff
is isolated by salting out with potassium chloride and may be purified by re-
crystallisation from water.
The product obtained is identical with the hexaoxyanthraquinonedisulphonic
acid described in the Specification No. 17543 of 1893 the acid alizarine blue.
EXAMPLE IV.
Tetraoxyanthraquinonedisulphonic acid obtained from diamidodisulphoiso--
anthraflavic acid, is dissolved in about 20 times the quantity of sulphuric acid of

page_text: dioxide about the quantity corresponding to 4 molecules, oxidation requires about
one day at ordinary temperature, the violet tinted product of reaction is poured
into water and the dyestuff is isolated and purified as described in Example III.
The new hexaoxyanthraquinonedisulphonic acid is a brown red crystalline
powder, soluble in hot water with a red colour. The aqueous solution turns
violet-blue, on addition of soda, blue on addition of ammonia and caustic soda-
lye. An excess of caustic soda-lye precipitates it in blue flakes. In concentrated
sulphuric acid the disulphonic acid is soluble with a blue red colour.
From a tinctorial point of view it is the analogue of the acid alizarine blue.
Its red dye in an acid bath upon wool produces when subsequently treated with
chromium fluoride a blue which is somewhat redder than the acid alizarine blue,
but quite as good in respect of fastness.
00
1000
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Penta- and Hexaoxy-anthraquinonedisulphonic
Acids.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Chartered Patent Agent, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by The Farbwerke vormals: Meister Lucius and Brüning, of Hoechst
a/Main, in the Empire of Germany, Chemical Manufacturers,) and in what manner
the same is to be performed, to be particularly described and ascertained in and
by the following statement:-
-
In the Provisional Specification No. 6533 of 1898 are described two new
isomeric tetra-oxyanthraquinonedisulphonic acids, derived from two new isomeric
tetraoxyanthraquinones, and obtained by the action of gentle oxidising agents
such as peroxide of lead, peroxide of manganese, chloride of lime, ferric salts,
chromates, persulphates, nitric acid and the like upon diamidodisulpho-
anthraflavic acid. Whilst the only hitherto known tetraoxyanthraquinone-
disulphonic acid, that is to say, the anthrachrysonedisulphonic acid is not changed
in concentrated sulphuric acid solution by oxidising agents, such, for instance,
as manganese dioxide, and is easily transformed by nitric acid into dinitroanthra-
chrysonedisulphonic acid, both the new tetraoxyanthraquinonedisulphonic acids
behave differently. If these sulphonic acids be treated with manganese dioxide
or nitric acid, then they are oxidised, as my foreign correspondents have found,
into new pentaoxyanthraquinonedisulphonic acids. The pentaoxyanthraquinones
which serve as bases to the new sulphonic acids are also new and are not identical
with the pentaoxyanthraquinones hitherto known.
These two new pentaoxyanthraquinone disulphonic acids can be further
oxidised in a concentrated sulphuric acid solution by oxidising agents usually
employed in this case, such, for instance, as manganese dioxide peroxide of lead,
arsenic acid, etc., into two isomeric hexaoxyanthraquinone-disulphonic acids, of
which one is identical with the hexaoxyanthraquinonedisulphonic acid described
in the Specification No. 17543 of 1893. For the manufacture of these two
hexaoxyanthraquinonedisulphonic acids an isolation of the two pentaoxyanthra-
quinone-disulphonic acids is not absolutely necessary. It is best to start from
the two tetraoxyanthraquinonedisulphonic acids described in the Specification
No. 6533 of 1898 and to treat them with an abundant excess of oxidising agents.

page_text: The new penta- and hexaoxyanthraquinone disulphonic acids are valuable blue
mordant dyestuffs. The following examples illustrate the process.
EXAMPLE I.
Tetraoxyanthraquinonedisulphonic acid from anthraflavic acid is dissolved in
form of its acid potassium salt in 10 to 20 times its quantity in weight of
sulphuric acid of, 66° Bé. and to the well cooled solution is slowly run in with
active stirring somewhat more than the quantity corresponding with 1 molecular
proportion of finely ground manganese dioxide.
After a short time the reaction begins, the mixture becoming a clear intense
blue. To complete the reaction, the mass is stirred for some hours and cooled at
the same time; then further stirred for from 12 to 24 hours at ordinary tempera-
ture, poured into a sufficient quantity of water and boiled after having added,
if required, some solution of a bisulphite. From the filtered pure red solution
the acid potassium salt of pentaoxyanthraquinonedisulphonic acid is separated
by potassium chloride and may again be purified by recrystallisation.
With the same result nitric acid may be used as oxidising agent, by adding to
the concentrated sulphuric acid solution of tetraoxyanthraquinonedisulphonic
acid 1 molecular proportion of nitric acid either as the acid itself or as a suitable
nitrate under the conditions above set forth. The course of the reaction is the
game.
The product is soluble with some difficulty in cold water, more easily in hot
water with a red colour, which on addition of ammonia and soda becomes a more
intense red, and red-violet on addition of fixed alkalies. An excess of alkali
precipitates the sulphonic acid in red flakes. In concentrated sulphuric acid
the sulphonic acid is soluble with a red-violet colour. The solution exhibits a
red fluorescence.
The pentaoxyanthraquinone disulphonic acid dyes wool red in an acid bath.
The acid dye, subsequently treated with chromium fluoride produces a pure blue
fast to milling.
EXAMPLE II.
Under exactly the same conditions the tetraoxyanthraquinonedisulphonic acid
from isoanthraflavic acid may be transformed by the same oxidising agents into
one of the above described isomeric pentaoxyanthraquinone disulphonic acids.
Its manufacture is carried out under the conditions set forth in Example I.
In order to isolate the new compound the violet mixture is in this case also
poured into water, boiled, salted out with potassium chloride and the product
to be purified is precipitated from its aqueous solution by an excess of fixed
alkali and re-transformed into the acid potassium salt.
The pure product is a red crystalline powder, easily soluble in hot water to
a red solution becoming violet on addition of alkali. An excess of alkali pre-
cipitates the alkali salt from the aqueous solution in violet blue crystalline
flakes.
Concentrated sulphuric acid dissolves the sulphonic acid with a red colour.
The concentrated solution exhibits a red fluorescence.
The red dye of the new pentaoxyanthraquinone-disulphonic acid upon wool in
an acid bath produces on subsequent treatment with chromium fluoride a blue
fast to milling and light, but its tint is of a somewhat redder huc than, that
obtained from pentaoxyanthraquinonedisulphonic acid derived from anthraflavic
acid..
EXAMPLE III.
Pentaoxyanthraquinonedisulphonic acid obtained according to Example I is
stirred into 10 to 12 times its weight of concentrated sulphuric acid to which is
added, while cooling, somewhat more than the quantity corresponding with 1
molecular proportion of finely ground manganese dioxide. The reaction takes
place at ordinary temperature and is completed within 1 to 2 days.

page_text: The violet blue mixture is poured into water boiled filtered, and the dyestuff
is isolated by salting out with potassium chloride and may be purified by re-
crystallisation from water.
The product obtained is identical with the hexaoxyanthraquinonedisulphonic
acid described in the Specification No. 17543 of 1893 the acid alizarine blue.
EXAMPLE IV.
Tetraoxyanthraquinonedisulphonic acid obtained from diamidodisulphoiso-
anthraflavic acid, is dissolved in about 20 times the quantity of sulphuric acid of
66° Bé. in which is stirred, while cooling, an excess of finely ground manganese
dioxide about the quantity corresponding to 4 molecular proportions oxidation
requires about one day at ordinary temperature, the violet tinted product of
reaction is poured into water and the dyestuff is isolated and purified as described
in Example III.
The new hexaoxyanthraquinonedisulphonic acid is a brown red crystalline
powder, soluble in hot water with a red colour. The aqueous solution turns
violet-blue, on addition of soda, blue on addition of ammonia and caustic soda-
lye. An excess of caustic soda lye precipitates it in blue flakes. In concentrated
sulphuric acid the disulphonic acid is soluble with a blue red colour.
From a tinctorial point of view it is the analogue of the acid alizarine blue.
Its red dye in an acid bath upon wool produces when subsequently treated with
chromium fluoride a blue which is somewhat redder than the acid alizarine blue,
but quite as good in respect of fastness.
Having now particularly described and ascertained the nature of this inven-.
tion and in what manner the same is to be performed, I declare that what I
claim is;
1. The herein described manufacture of two new pentaoxyanthraquinone-
disulphonic acids by treating the two isomeric tetraoxyanthraquinonedisulphonic
acids, dissolved in concentrated sulphuric acid, with the calculated quantity of an
oxidising agent, such as manganese dioxide or nitric acid, for the introduction
of a hydroxyl-group.
2. The herein described manufacture of two isomeric hexaoxyanthraquinone-
disulphonic acids by further oxidising the pentaoxyanthraquinonedisulphonic
acids as above set forth in concentrated sulphuric acid with oxidising agents,
such as manganese dioxide peroxide of lead or the like.
3. The products manufactured as set forth in Claims 1 and 2.
1000
Dated this 3rd day of February
1000
1890.
ABEL & IMRAY,
Agents for the Applicant.