The Manufacture and Production of Colouring Matters derived from Anthraquinone and Alizarin Blue.
Year: 1891

page_text: Date of Application, 21st May, 1891
Complete Specification Left, 6th Feb., 1892-Accepted, 26th Mar., 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of Colouring Matters derived from
Anthraquinone and Alizarin Blue.
1 BENJAMIN WILLCOX of 47 Lincolns 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, to be as follows:-
In the Specification accompanying the application for Letters Patent No. 14353
granted to James Yate Jolinson and dated October 5th 1888 an intermediate.
product is described which is obtained by the action of fuming sulphuric acid of
high percentage upon alizarin blue and is capable of being converted by certain
reactions into new dyes or colouring matters known as "alizarin blue-green" and
alizarin green."
My foreign correspondents have now discovered that, by the action, under
certain conditions, of sulphuric acid anhydride upon alizarin blue a substance is
obtained which is totally distinct from the intermediate product described in the
aforesaid Specification No. 1435388 and which according to its chemical properties
is an analogue of the intermediate product of alizarin bordeaux obtained according
to the process described in the Specification accompanying my application for
Letters Patent No. 8725 dated June 5th 1890. For the production of this new
product it is essential that the action of the anhydride upon the alizarin blue
should be maintained as energetic as possible.
The following is given as an example of the method of conducting the process
according to this invention the parts being by weight.
10 parts of dry alizarin blue are introducted into 200 parts or more of fuming
sulphuric acid containing 80 per cent. of anhydride and the mixture is allowed to
stand with occasional stirring at a temperature of from 30 to 50 dgrees centigrade
for some time say for 8 to 14 days. From time to time a test portion is poured out
into water filtered off, dissolved in potash or soda lye and after decomposing at
boiling heat with sulphuric or hydrochloric acid the resulting deposit is filtered off
and dissolved in concentrated sulphuric acid. The reaction is known to be
completed when this solution acquires a pure blue colour or ceases to differ from
the previous sample.
The reacting mass is then poured out direct on to ice after dilution with
concentrated sulphuric acid and the mordant dyeing intermediate product thus
obtained is treated in a similar manner to the alizarin bordeaux sulphuric acii ether
according to the Specifications accompanying my applications for Letters Patent
dated June 5th 1890 No. 8725 and August 22nd 1890 No. 13235 that is to say is
converted into colouring matter either by dissolving in alkali and decomposing the
boiling alkaline solution with acids, or directly by heating with acids.
The colouring matter thus obtained is found to differ from quinoline derivative
of alizarin bordeaux described in the Specification No. 87250. It likewise differs
from the "alizarin indigo blue" described in the Specification accompanying the
application for Letters Patent granted to James Yate Johnson dated October 20th
1888 No. 15121.
Although possessing many points of resemblance it nevertheless differs very
distinctly from the latter inasmuch as its solution in concentrated sulphuric acid
displays in the spectroscope two sharply characteristic absorption bands which are
not presented by the alizarin indigo blue obtained according to the Specifications
Nos. 14353 and 15121
By causing the anthra-diquinone (alizarin-cyanine-quinone) described in the

page_text: Specification accompanying my application for Letters Patent dated 18th March
1891 No. 4871 upon phenol or its substitution products a series of new technically
valuable mordant dyeing colouring matters is obtained. In accordance with the
quantitative results obtained with this reaction it appears that one molecular
proportion of the anthra-diquinone unites with one molecular proportion of the
phenol.
The combination of these two components takes place most advantageously in a
sulphuric acid solution and proceeds even at ordinary temperature. The production
of the anthra-diquinone and the combination thereof with the phenol employed may
be conveniently combined in one operation.
The following is given as an example of the method of conducting this process
the parts being by weight.
10 parts of dry alizarin bordeaux are dissolved in 200 parts of sulphuric acid at
66 degrees Baumé and oxidised with 10 parts of manganese in the manner described
in my aforesaid Specification No. 4871" and in accordance with the directions
therein contained.
Into the sulphuric acid solution thus obtained, being a solution of the quinone of
the colouring matter described in the aforesaid Specification No. 48711 as
cyanine (penta oxy anthra quinone), 10 parts of salicylic acid are gradually
introduced the temperature not being allowed to rise above 25 degrees centigrade.
The change in the colour of the sulphuric acid solution from blue to blue-green
indicates that the reaction is taking place.
The reaction is accelerated by stirring and after about 18 hours the mass is
poured out into 2000 parts of water. The materials being boiled the separated
colouring matter is filtered and washed neutral. The product is further purified
by dissolving in soda lye filtering the alkaline solution and precipitating with
an acid.
This product differs essentially from the alizarin cyanine I (pentacyanine)
described in the Specification No. 4871. It is especially distinguishable by its
pure blue-green colour and by the absorption spectrum of its solution in concentrated
sulphuric acid. It dyes mordants in bluer or greener colours than the aforesaid
penta-cyanine. By the action of ammonia upon the new product a new and very
beautiful blue-green colouring matter is obtained.
The quinones of the alizarin cyanine II (hexa-oxy-anthra-quinone) described in
the aforesaid Specification No. 4871" also act in a similar manner to the penta-
cyanine-quinone as does also the isomeric hexa-oxy-anthra-quinone obtained by
the oxidation of alizarin bordeaux with sulphuric acid or of anthra-quinone with
sulphuric acid anhydride.
The salicylic acid employed according to the foregoing example may be replaced
by phenol di- and tri-hydroxy-benzene and their homologues alpha- and beta-
naphthol dihydroxy-naphthaline or by the sulpho- or carboxy-acids or the sulpho-
carboxy acids of any of these substances and other substitution products.
In place of preparing the quinone in the first place and afterwards combining
it with the phenols these separate operations may be combined in one taking for
example a solution of alizarine bordeaux in sulphuric acid and introducing into it
a mixture of manganese and salicylic acid or dissolving alizarin bordeaux and
salicylic acid in sulphuric acid and adding the manganese. In all these cases the
reaction is the same and consists in the action of an anthra-diquinone upon
a phenol.
My foreign correspondents have discovered that the alizarin bordeaux described
in the Specification No. 8725 and its analogues, also the poly-oxy-anthra-quinones
obtained therefrom by further oxidation and other compounds belonging to this
new class of colouring matters (such as the quinoline derivative of alizarin
bordeaux or the alizarin blue-green, alizarin green or alizarin indigo-blue described
in the Specifications No. 1435358 and 151218 and the products obtained according
to the processes hereinbefore described) can by the action of ammonia be converted
very easily into new and valuable colouring matters.

page_text: the water bath until a sample precipitated with acid dissolves with a yellow colour
in concentrated sulphuric acid and the process is completed in other respects as in
the preceding example. The product dyes a pure green on chromium mordants.
By employing in place of the alizarin green the products obtained according to the
process hereinbefore described by the action of anthra-di-quinones (quinones of the
penta- and hexa-oxy-anthra-quinones etc.) upon phenols and their substitution
products colouring matters are obtained which dissolve in concentrated sulphuric
acid with a red-violet colour and produce extremely beautiful bluish-green tones
upon chromium mordants.
Dated this 21st day of M 1901
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents:
COMPLETE SPECIFICATION.
The Manufacture and Production of Colouring Matters, derived from
Anthraquinone and Alizarin Blue.
I, BENJAMIN WILLCOX of 47 Lincolns 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 :-
I.
In the Specification of my application for Letters Patent No. 4871 dated
18th March 1891 so called anthradiquinones (alizarin cyanine quinones) are
described. My foreign correspondents have found that these anthradiquinones can
be converted into new and technically valuable dye-stuff's capable of dyeing with
the aid of mordants by allowing them to act on phenols, or substitution products
thereof, one molecular proportion of the anthradiquinone uniting apparently with
one molecular proportion of the phenol or substitution product thereof. The com-
bination of these two components is effected most advantageously in a sulphuric
acid solution and proceeds even at ordinary temperatures.
The production of the anthradiquinones and the combination thereof with the
phenol or substitution product thereof may be conveniently effected in one
operation. The following is given as an example of the method of conducting this
process the parts being by weight.
10 parts of dry alizarin bordeaux are dissolved in 200 parts of sulphuric acid
(66 degrees Baumé) and oxidised with 10 parts of manganese dioxide in the manner
described in my aforesaid Specification of the application for Letters Patent
'No. 4871º¹ Into the sulphuric acid solution thus obtained, being a solution of the
quinone of the colouring matter described in the aforesaid Specification No. 4871"1
as alizarin pentacyanine (pentaoxyanthraquinone), 10 parts of salicylic acid are
gradually introduced the temperature not being allowed to rise above 25 degrees
centigrade. The change in the colour of the sulphuric acid solution. from blue to
bluish-green indicates that interaction is taking place. The action is accelerated
by stirring and after about 18 hours the mass is poured into 2000 parts of water.
After heating the liquid to the boiling point the colouring matter which has
separated out is filtered off and washed in order to remove the adherent acid. The
product is further purified by dissolving it in soda-lyc, filtering the alkaline solution
and precipitating with an acid.
The product is distinguished from the alizarin pentacyanine (pentoxyanthra-
quinone) described in the Specification of the application for Letters Patent
No. 4871 by its pure bluish green colour and by the absorption spectrum of its
solution in concentrated sulphuric acid. It produces, on mordanted wool, bluer or

page_text: greener colours than those produced by the aforesaid alizarine pentacyanine. By
the action of ammonia on this new product another new and very beautiful bluish-
green colouring-matter is obtained.
The quinones of alizarin hexacyanine (hexa oxyanthraquinone) and the isomeric
hexaoxyanthraquinone obtained either by the oxidation of alizarin bordeaux with
sulphuric acid or of anthraquinone with sulphuric anhydride act in the same manner
as does the quinone of the said alizarin pentacyanine.
Instead of the salicylic acid prescribed in the foregoing example, phenol,
dihydroxy-benzenes and their homologues, alpha and beta naphthol or the
carboxylic acids or any other substitution product thereof may be employed.
11.
My foreign correspondents have discovered that the alizarin bordeaux described
in the Specification of Letters Patent No. 8725 90 and its analogues and also the
polyoxyanthraquinones obtained therefrom by further oxidation as well as other
compounds belonging to this class of colouring-matters (such as alizarin blue-green,
alizarin green, alizarin indigo-blue described in the Specifications of Letters Patent
Nos. 14353 and 15121 can very easily be converted into new and valuable
colouring-matters by the action of ammonia.
The action taking place in this process appears to consist simply in the substitu-
tion of an amido-group for a hydroxyl group.
In the case of many of the substances herein before specified the action may be
completed at ordinary temperature, but if not then heating with an excess of a
solution of ammonia on a water bath is generally sufficient.
All the new colouring-matters thus obtained differ from the original materials by
the much redder or yellower colours of their solutions in concentrated sulphuric
acid, by the bluer tone of their solutions in indifferent or other solvents such as
alcohol or glacial acetic acid, by the considerably bluer or greener shades produced
by them and also by the bluer or greener colour of their alkaline solutions. Many
of the colouring-matters thus obtained are to a certain extent soluble in baryta.
water. They are remarkable for their
great fastness.
The process for their production consists in general either in allowing the above
mentioned substances to remain in contact with or to heat them with diluted liquor
ammoniæ until the solution in sulphuric acid of a test portion precipitated with acid
ceases to shew any further change in colour either towards red or yellow. When
this stage has been reached the liquid is simply diluted with water and the colouring.
matter is precipitated with hydrochloric or sulphuric acid.
The following are given as examples of the method of conducting the process the
parts being by weight.
ALIZARIN BORDEAUX AND AMMONIA.
100 parts of alizarin bordeaux paste (containing 20 per cent. of solid alizarin
bordeaux), 1000 parts of water and 500 parts of liquor ammonia containing
20 per cent. of ammonia are slowly heated to 80 degrees centigrade on a water bath,
in a vessel provided with an apparatus for recovering the escaping ammonia until.
a test portion precipitated by means of an acid dissolves in concentrated
sulphuric acid with a red colour and no further change in this. colour is observed in
a subsequent test portion. The liquid is then diluted to 4000 parts with water and
whilst boiling mixed with sulphuric acid. By these means the colouring-matter is
obtained in the form of a dark violet crystalline precipitate with a green reflex.
dissolves in concentrated sulphuric acid forming a red coloured liquid which
exhibits a yellowish red fluorescence. This solution even when diluted shews
distinct absorption bands in the spectroscope.
It
A. solution in soda lye is of a bright blue colour. On wool mordanted with
chromate of potash, the colouring matter produces a blue similar to that of alizarin
blue

page_text: ALIZARIN CYANINE R AND AMMONIA.
Alizarin cyanine R, which is the mixture of alizarin penta and hexacyanines
obtained by the oxidation of alizarine bordeaux, and ammonia interact very readily.
The product thus formed and the colouring matters resulting from the employment
of alizarin penta- or hexa-cyanine dye much more beautifully and strongly than
do the colouring-matters obtained by the action of ammonia on the anthradiquinones
(cyanine quinones) which are formed as intermediate products in the manufacture
of the cyanines.
For example 100 parts of an alizarin pentacyanine paste (containing 10 per cent.
of solid alizarin pentacyanine) 400 parts of water and 75 parts of liquor ammonia
(20 per cent.) are heated to about 50 degrees centigrade until a sample of the
liquid on treatment with acid yields a precipitate which when dissolved is concen-
trated sulphuric acid affords a red coloured solution. The dilution is then increased
to 2000 parts by adding the necessary quantity of water and the colouring-matter
is precipitated by sulphuric acid. The dye-stuff thus produced dissolves in soda-
Ive with a blue colour; it dyes an intense greenish-blue with the aid of chromium
mordants.
ALIZARIN GREEN AND AMMONIA.
100 parts of an alizarin green paste containing 10 per cent. of solid alizarin green,
500 parts, of water and 200 parts of liquor ammonia are heated at the temperature
of the water bath until a sample treated with acid yields a precipitate which
dissolves with a yellow colour in concentrated sulphuric acid. The process is
completed in the same manner as that described in the preceding examples.
The product thus obtained dyes a pure green with the aid of chromium
mordants.
By employing, in place of alizarin green, the products obtained by the action of
anthradiquinones such as the quinones of alizarinpenta- and hexa-cyanine and of
hexa-oxanthraquinone on phenols or their substitution products as before described,
colouring matters are produced which dissolve in concentrated sulphuric acid with
a reddish-violet colour and dye an extremely beautiful bluish green with the aid of
chromium mordants.
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 new alizarin dye stuffs from the quinones of alizarin
pentacyanine and alizarin hexacyanine and phenol orthocresol paracresol, resorcinol
hydroquinone, alpha or beta naphthol, salicylic acid, para hydroxy benzoic acid,
ortho cresotinic acid, meta cresotinic acid or alpha naphthol carboxylic acid.
2. The manufacture of new alizarin colouring-matters from the quinone of hexa
oxyanthraquinone isomeric with alizarin hexacyanine described in the Specifications
of Letters Patents Nos. 18729 and 17712 and resorcinol, salicylic acid, para-
hydroxy benzoic acid or ortho-cresotinic acid.
3. The production of new dye-stuffs by treating the bordeaux prepared from
alizarin, purpurin, flavo purpurin, or anthrapurpurin, also alizarin pentacyanine and
alizarin hexacyanine, hexaoxyanthraquinone the cyanines of flavo purpurin and
anthrapurpurin alizarin blue green, alizarin green alizarin indigo blue or the
products described in the preceding first and second claims with ammonia.
4. As new articles of manufacture the new products of the foregoing first, second
and third claiming clauses.
Dated this 6th day of February 1892.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.