Manufacture of Colouring Matters by Reduction of Tetra-nitro- anthrachrysone and Dinitro-anthrachrysone-disulphonic Acid.
Year: 1893

page_text: Date of Application, 10th July, 1893
Complete Specification Left, 10th Apr., 1894-Accepted, 12th May, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE vormals MEISTER. LUCIUS
AND BRUNING, of Hoechst / Main, Germany, Chemical Manufacturers.]
Manufacture of Colouring Matters by Reduction of Tetra-nitro-
anthrachrysone and Dinitro-anthrachrysone-disulphonic Acid.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows :-
By reducing tetra-nitro-anthrachrysone and dinitro-anthrachrysone-disulphonic
acid there can be produced colouring matters, which according to the conditions
under which the operation has been conducted, dye chromed wool green or blue
shades.
When the reduction is proceeded with in alkaline solution there are obtained
colouring matters which dye chromed wool green shades; when it is proceeded
with in acid solution, the colouring matters obtained dye chromed wool pure blue
shades:
The process for the production of the colouring matters is the same for both
raw materials and is described more fully in the following examples..
7
REDUCTION OF TETRA-NITRO-ANTHRACHRYSONE.
a) PRODUCTION OF THE COLOURING MATTER IN ALKALINE SOLUTION.
Tetra-nitro-anthrachrysone is introduced into about the 20-fold quantity of
water, in which has been dissolved a somewhat larger quantity of alkali (in the
form of fixed alkali or of carbonate of soda). than is according to theory,
necessary for 4 hydroxyl-groups; it is then admixed at ordinary temperature with
a solution of sulphide of sodium (the quantity demanded for by 4 nitro-groups) in
not too large a quantity of water. At the beginning of the operation the solution
assumes a red, afterwards a blue green and shortly after a green colour. In order
that the reaction may become complete, the solution is allowed to rest at ordinary
temperature for from 12 to 24 hours and is afterwards heated on a water bath for
a short time, say one hour.
.
After cooling down, the colouring matter is filtered off, purified by precipitating
it from its aqueous solution by means of common salt. or acid, and is then brought
into the form of a paste.
For the sulphide of sodium may be substituted glucose, sulphide of ammonium,
sulphate of iron and similar reducing agents.
In hot water the colouring matter dissolves with a blue colour, in diluted soda
lye with a violet and in ammonia with blue colour.
From its dissolutions in water or diluted alkalies it is precipitated very easily by
acids or salt solutions. In concentrated sulphuric acid it dissolves with a violet
colour.
Chromed wool is dyed deep green to black green shades, which are perfectly
fast to soap and fulling. The capability of dyeing uniform shades of this colouring
matter is like: that of alizarine colouring matters.

page_text: b) PROCESS FOR THE PRODUCTION
OF THE COLOURING MATTER IN ACID
SOLUTION.
The production of the colouring matter in acid solution is carried through quite
as easily as in alkaline solution; example;
Tetra-nitro-anthrachrysone is dissolved in from the 30 to 40 fold quantity of
diluted hydrochloric or sulphuric acid and admixed with a somewhat larger
quantity of zinc than is demanded by theory for the reduction of the four nitro
groups; it is left standing at ordinary temperature for from 12 to 24 hours with
frequent stirring.
As the reaction proceeds, the yellow red solution of nitro-anthrachrysone loses
in colour and the colouring matter separates in the form of dark flakes.
In order to obtain the reaction complete, the solution is heated at water bath
temperature for a short time. The colouring matter is filtered off, washed, pre-
cipitated from its diluted alkaline solution by means of common salt, and employed
for dyeing purposes in paste form.
In quite an analogous manner is effected the production of the colouring matter
by reduction by means of tin chloride in hydrochloric solution.
When the quantity of tin chloride demanded by theory is introduced into the
diluted hydrochloric solution of the nitro-anthrachrysone, it assumes an intense red
colour and shortly after, separation of the colouring matter sets in.
It is now heated on a water bath for a short time; the reaction mass is poured
into diluted hydrochloric acid (1 part of concentrated hydrochloric acid to 1 part
of water) filtered and the product washed with water.
The purification is proceeded with in the same manner as described above.
It is to be understood that instead of zinc and hydrochloric acid or tin chloride
and hydrochloric acid there may be employed any other usual reducing agents in
acid solution.
The colouring matter which is obtained in this process in the form of its sodium
salt, is in the form of a grey blue coloured paste. In a dry state it presents itself
in form of a black powder with metallic lustre, dissolving in concentrated sulphuric
acid with brown red colour. The alkali salts of the colouring matter are of difficult
solubility in water.
Chromed wool is dyed uniform shades ranging from blue grey to blue, according
to the strength of the dyeing bath. These shades are perfectly fast in fulling, to
soap and light.
REDUCTION OF THE DINITRO-ANTHRACHRYSONE DISULPHONIC ACID.
a) REDUCTION of the colourING MATTER IN ALKALINE SOLUTION...
Dinitro-anthrachrysone-disulphonic acid is introduced in about the 25 fold quantity
of water, in which has been dissolved the quantity of alkali necessary for converting
it into the alkali salt of the sulphonic acid, and is then admixed at ordinary
temperature with a solution of sulphide of sodium (the quantity demanded by
theory for the 4 nitro groups) in a not too copious quantity of water. Immediately
there sets. in intense red violet colouration and separation of a crystalline
precipitate.
The whole is allowed to rest at ordinary temperature for a few hours and
afterwards heated at water bath temperature for a short time in order to complete
the reaction. After cooling, the colouring matter is filtered off, washed and for
further purification is precipitated from its diluted aqueous solution by means of
acid or common salt.
"
It is self evident that for the sulphide of sodium may be substituted other usual
reducing agents in alkaline solution.
The colouring matter is in form of a red brown powder, of indifferent solubility

page_text: in cold water, dissolving in hot water with a pure blue colour, in diluted alkali with
a violet and in concentrated sulphuric acid also with a violet colour. The solution
in concentrated sulphuric acid possesses a strong red fluorescence.
The colouring matter dyes non-mordanted wool blue in acid bath, chromed wool
green, and alummed wool blue green shades. The tints produced in the acid bath
can subsequently be shaded by means of metallic salts.
b) PRODUCTION OF THE COLOURING MATTER IN ACID SOLUTION.
In acid solution the reduction of the dinitro-anthrachrysone-disulphonic acid
also proceeds quite smoothly.
It is completed in the shortest time when tin chloride is employed as reducing
agent, but also the other usual reducing agents give very good results.
The operation is conducted for example as hereinafter described.
Dinitro anthrachrysone-disulphonic acid is dissolved in about the 20 fold
quantity, by weight, of diluted hydrochloric acid (1 part of HCl for 3 parts
of H₂O) and admixed with the solution of the quantity of tin-chloride demanded
by theory.
The solution immediately assumes an intense red coloration and shortly after-
wards the reaction product begins to separate. The solution is allowed to rest at
ordinary temperature for a few hours and is finally heated at water bath
temperature for a short time.
The reaction liquid is poured into diluted hydrochloric acid (1 part HCl to
1 part H,O) and the colouring matter is filtered and washed with water.
For effecting its purification it is recrystallised from water or precipitated from
a diluted aqueous acid solution by means of common salt.
The colouring matter presents itself in the form of a dark blue crystalline
powder with metallic lustre, dissolving indifferently well in cold water with a
violet colour in hot water with a beautiful red violet colour, in diluted alkali
with a red blue colour, in concentrated sulphuric acid with a yellow red colour.
The alkaline solutions show red fluorescence.
The colouring matter dyes as well on mordants as in acid bath; wool is dyed
in acid bath pure violet shades, alummed wool violet blue shades and chromed
wool pure blue shades. The tints produced in acid bath can subsequently be
shaded at will by means of metallic mordants.
The shades produced on mordanted wool are perfectly fast to fulling.
Dated this 10th day of May 1893.
ABEL & IMRAY,
Agents for the Applicant.
. COMPLETE SPECIFICATION.
Manufacture of Colouring Matters by Reduction of Tetra-nitro-
anthrachrysone and Dinitro-anthrachrysone-disulphonic Acid.
1, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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 :-
By reducing tetra-nitro-anthrachrysone and dinitro-anthrachrysone-disulphonic
acid there can be produced colouring matters, which according to the conditions
under which the operation has been conducted, dye chromed wool green or blue
shades.
When the reduction is proceeded with in alkaline solution there are obtained
colouring matters which dye chromed wool green shades; when it is proceeded with
in acid solution, the colouring matters obtained dye chromed wool pure blue shades.

page_text: The process for the production of the colouring matters is the same for both raw
materials and is described more fully in the following examples.
REDUCTION OF TETRA-NITRO-ANTHRACHRYSONE.
a) PRODUCTION OF THE COLOURING MATTER IN ALKALINE SOLUTION.
Tetra-nitro-anthrachrysone is introduced into about the 20 fold quantity of
water, in which has been dissolved a somewhat larger quantity of alkali (in the
form of fixed alkali or of carbonate of soda) than is according to theory necessary
for 4 hydroxyl-groups; it is then admixed at ordinary temperature with a solution
of sulphide of sodium (the quantity demanded for by 4 nitro-groups) in not too
large a quantity of water. At the beginning of the operation the solution assumes
a red, afterwards a blue green and shortly after a green colour. In order that the
reaction may become complete, the solution is allowed to rest at ordinary
temperature for from 12 to 24 hours and is afterwards heated on a water bath for
a short time, say one hour.
After cooling down, the colouring matter is filtered off, purified by precipitating
it from its aqueous solution by means of common salt or acid, and is then brought
into the form of a paste.
For the sulphide of sodium may be substituted glucose, sulphide of ammonium,
sulphate of iron and similar reducing agents.
In hot water the colouring matter dissolves with a blue colour, in diluted soda lye
with a violet and in ammonia with blue colour.
From its dissolutions in water or diluted alkalies it is precipitated very easily by
acids or salt solutions. In concentrated sulphuric acid it dissolves with a violet
colour.
Chromed wool is dyed deep green to black green shades, which are perfectly fast
to soap and fulling. The capability of dyeing uniform shades of this colouring
matter is like that of alizarine colouring matters.
b) PROCESS FOR THE PRODUCTION OF THE COLOURING MATTER IN ACID
SOLUTION.
The production of the colouring matter in acid solution is carried through quite
as easily as in alkaline solution; example;
Tetra-nitro-anthrachrysone is dissolved in from the 30 to 40 fold quantity of
diluted hydrochloric or sulphuric acid, and admixed with a somewhat larger
quantity of zinc than is demanded by theory for the reduction of the four nitro
groups; it is left standing at ordinary temperature for from 12 to 24 hours with
frequent stirring.
As the reaction proceeds, the yellow red solution of nitro-anthrachrysone loses in
colour, and the colouring matter separates in the form of dark flakes.
In order to obtain the reaction complete, the solution is heated at water bath
temperature for a short time. The colouring matter is filtered off, washed,
precipitated from its diluted alkaline solution by means of common salt, and
employed for dyeing purposes in paste form.
In quite an analogous manner is effected the production of the colouring matter,
by reduction by means of tin chloride in hydrochloric solution.
When the quantity of tin chloride demanded by theory is introduced into the
diluted hydrochloric solution of the nitro-anthrachrysone, it assumes an intense red
colour and shortly after, separation of the colouring matter sets in.
It is now heated on a water bath for a short time; the reaction mass is poured
into diluted hydrochloric acid (1 part of concentrated hydrochloric acid to 1 part of
water) filtered and the product washed with water.
The purification is proceeded with in the same manner as described above

page_text: It is to be understood that instead of zinc and hydrochloric acid or tin chloride-
and hydrochloric acid, there may be employed any other usual reducing agents in.
acid solution.
The colouring matter which is obtained in this process in the form of its sodium
salt, is in the form of a grey blue coloured paste. In a dry state it presents itself.
in form of a black powder with metallic lustre, dissolving in concentrated sulphuric-
acid with brown red colour. The alkali salts of the colouring matter are of difficult
solubility in water.
Chromed wool is dyed uniform shades ranging from blue grey to blue, according
to the strength of the dyeing bath. These shades are perfectly fast in fulling, to-
a) REDUCTION OF THE COLOURING MATTER IN ALKALINE SOLUTION.
Dinitro-anthrachrysone-disulphonic acid is introduced in about the 25 fold:
quantity of water, in which has been dissolved the quantity of alkali necessary for
converting it into the alkali salt of the sulphonic acid, and is then admixed at
ordinary temperature with a solution of sulphide of sodium (the quantity demanded
by theory for the 4 nitro groups) in a not too copious quantity of water. Immediately
there sets in intense red violet colouration and separation of a crystalline
precipitate.
The whole is allowed to rest at ordinary temperature for a few hours and after-
wards heated at water bath temperature for a short time in order to complete the
reaction. After cooling, the colouring matter is filtered off, washed and for further
purification is precipitated from its diluted aqueous solution by means of acid or
common salt.
It is self evident that for the sulphide of sodium may be substituted other usual
reducing agents in alkaline solution.
The colouring matter is in form of a red brown powder, of indifferent solubility
in cold water, dissolving in hot water with a pure blue colour, in diluted alkali
with a violet and in concentrated sulphuric acid also with a violet colour. The
solution in concentrated sulphuric acid possesses a strong red fluorescence.
The colouring matter dyes non mordanted wool blue in acid bath, chromed wool
green, and alummed wool blue green shades. The tints produced in the acid bath.
can subsequently be shaded by means of metallic salts.
6) PRODUCTION OF THE COLOURING MATTER IN ACID SOLUTION.
In acid solution the reduction of the dinitro-anthrachrysone-disulphonic acid also.
proceeds quite smoothly.
•
It is completed in the shortest time when tin chloride is employed as reducing
agent, but also the other usual reducing agents give very good results.
The operation is conducted for example as hereinafter described.
Dinitro-anthrachrysone-disulphonic acid is dissolved in about the 20 fold
quantity, by weight, of diluted hydrochloric acid (1 part of HCl for 3 parts.
of H2O) and admixed with the solution of the quantity of tin chloride demanded
by theory.
The solution immediately assumes an intense red coloration and shortly afterwards
the reaction product begins to separate. The solution is allowed to rest at ordinary
temperature for a few hours and is finally heated at water bath temperature for a
short time. The reaction liquid is poured into diluted hydrochloric acid (1 part HCI
to 1 part H₂O) and the colouring matter is filtered and washed with water.
For effecting its purification it is recrystallised from water or precipitated from
a diluted aqueous acid solution by means of common salt.

page_text: The colouring matter presents itself in the form of a dark blue crystalline powder
with metallic lustre, dissolving indifferently well in cold water with a violet colour,
in hot water with a beautiful red violet colour, in diluted alkali with a red blue
colour, in concentrated sulphuric acid with a yellow red colour. The alkaline
solutions shew red fluorescence.
The colouring matter dyes as well on mordants as in acid bath; wool is dyed in
acid bath pure violet shades, alummed wool violet blue shades and chromed wool
pure blue shades. The tints produced in acid bath can subsequently be shaded at
will by means of metallic mordants.
The shades produced on mordanted wool are perfectly fast to fulling.
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 production of colouring matters by treating tetra-nitro-anthrachrysone-
or dinitro-anthrachrysone-disulphonic acid in alkaline or in acid solution with
reducing agents, substantially as described.
2. Colouring matters produced by the process referred to in the preceding claim.
Dated this 10th day of April 1894.
ABEL & IMRAY,
Agents for the Applicant.