The Manufacture or Production of Hydroxyanthraquinone- quinolines.
Year: 1894

page_text: Date of Application, 2nd Feb., 1894
Complete Specification Left, 2nd Nov., 1894-Accepted, 8th Dec., 1894
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Hydroxyanthraquinone-
quinolines.
I HENRY EDWARD NEWTON of The Office for Patents 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent do hereby declare the
nature of this invention to be as follows:-
:―
My foreign correspondents have discovered some time ago that anthrachryson
is, when heated with sulphuric acid, in the presence of boric acid or agents acting
in a similar manner, converted into hexahydroxyanthraquinone, and that technically
valuable products are also obtained, if other dihydroxy-, trihydroxy-, or tetra-
hydroxyanthraquinone derivatives, or anthraquinone itself, are used in place of
anthrachryson. The boric acid, or the equivalent, added to the reaction mixture,
exerts a favourable influence upon the continuance of the said process.
My foreign correspondents have now found, that anthraquinone quinoline, and
hydroxyanthraquinone quinolines, can also be further hydroxylated, viz., converted
into products containing a greater number of hydroxylic groups, by treating them
with concentrated sulphuric acid in the presence of boric acid or other agents
acting in a similar manner. The researches of my foreign correspondents have
shown that, for instance, alizarin blue (which is a dihydroxyanthraquinone-
quinoline) can thus be transformed with great ease into dihydroxy- and trihydroxy-
alizarin blue, which process is carried out in a considerably shorter time, and more
simply and cheaply, than the process described in the Specifications of the English
Letters Patent No. 1435388 and 1512188, according to which the production of
compounds containing a greater number of hydroxylic groups than the original
materials, is effected by using a large excess of strong fuming sulphuric acid.
In order to illustrate one method of practically carrying out the new process
above referred to, the following example is given. The parts are by weight.
EXAMPLE.
CONVERSION OF
ALIZARIN
BLUE
INTO
DIHYDROXY-
AND
TRIHYDROXY-
ALIZARIN BLUE.
10 parts of dry alizarin blue are mixed with 10 parts of crystallized boric acid
and 200 parts of sulphuric acid (66 degrees Baumé), and the resulting mixture is
heated at from 260 to 270 degrees Centigrade. The reaction proceeds rapidly;
the heated mass assumes a blue colour, and sulphur dioxide is set free copiously.
The end of the re-action may be ascertained by the fact that the blue colour of the
heated mass does not increase, and the violence of disengagement of sulphur
dioxide has slackened. When this stage is arrived at, the mass, after cooling, is
poured into water, and the dye stuff separated is filtered off. The colouring
matter thus produced is a mixture of the known dihydroxy and trihydroxyalizarin
blue, and yields greenish blue shades, when dyed with the aid of chromium
mordants.
The alizarin blue used in the above example can be replaced by the beta
quinoline derivatives of flavopurpurin, anthrapurpurin, cr similar hydroxyanthra-
quinone, or by the alpha quinoline derivatives of alizarin, flavopurpurin, anthra-
purpurin or other hydroxyanthraquinones, or by anthraquinone quinoline itself.
27

page_text: The researches of my foreign correspondents have also shown that the sulphonic
acids and other derivatives of the said quinoline compounds can be used in the
process above referred to.
In order to produce these hydroxyanthraquinone quinolines, my foreign corre-
spondents do not limit themselves to the directions given in the above example, as
these can be varied. For instance, the reaction can be effected at considerably
lower temperatures; for example, at 210 degrees Centigrade, in which case the
heating is to be continued for a somewhat longer period. The sulphuric acid
(66 degrees Baumé) can be replaced by stronger acids, such as monohydrated
sulphuric acid, or moderately fuming sulphuric acid, and in place of boric acid,
such compounds can be used which yield boric acid in the presence of sulphuric
acid, using, for instance, boron trichloride or the like.
Dated this 2nd of February 1894.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Hydroxyanthraquinone-
quinolines.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, 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 :-
My foreign correspondents some time ago discovered that when heated with
sulphuric acid in the presence of boric acid, or agents acting in a similar manner,
anthrachryson is converted into hexahydroxyanthraquinone, and that technically
valuable products are also obtained, if other dihydroxy-, trihydroxy, or tetra-
hydroxy-anthraquinone derivatives, or anthraquinone itself, are used in place of
anthrachryson. The boric acid, or equivalent substance, added to the mixture,
exerts a favourable influence on the continuance of the said process.
My foreign correspondents have now found, that hydroxyanthraquinone-
quinolines can also be further hydroxylated, viz., converted into products containing
a greater number of hydroxyl groups, by heating them with concentrated sulphuric
acid in the presence of boric acid, or other boron compounds yielding boric acid
when used together with sulphuric acid. The researches of my foreign corre-
spondents have shewn, that, for instance, alizarin blue (which is a dihydroxy-
anthraquinonequinoline) can thus be transformed with great ease into dihydroxy
and trihydroxy alizarin blue, which process is carried out in a considerably shorter
time, and more simply and cheaply than the process described in the Specifications
of the English Letters Patent No. 14353 and 15121, according to which, the
production of compounds containing a greater number of hydroxyl groups than
the original materials, is effected merely by using a large excess of strong fuming
sulphuric acid.
In order to illustrate one method of practically carrying out the new process
above referred to, the following example is given. The parts are by weight.

page_text: from 260 to 270 degrees Centigrade. The action proceeds rapidly, the heated
inass assuming a blue color, and sulphur dioxide being copiously liberated; it is
terminated when the blue colour of the heated mass does not increase in intensity,
and the disengagement of sulphur dioxide falls off. When this stage is arrived at,
the mass is allowed to cool, and is then poured into water, and the separated dye-
stuff is filtered off. The colouring matter thus produced is a mixture of the known.
dibydroxy and trihydroxy alizarin blue, and yields greenish-blue shades when dyed
with the aid of chromium mordants.
Instead of the alizarin blue used in the above example, the beta quinoline
derivatives of flavopurpurin, anthrapurpurin, or similar hydroxyanthraquinones,
can be used.
The researches of my foreign correspondents have also shewn, that the sulphonic
acids and other derivatives of the said quinoline compounds, can be used in the
process above referred to.
In order to produce these hydroxyanthraquinonequinolines, my foreign corre-
spondents do not limit themselves to the directions given in the above example,
as these can be varied. For instance, the process can be carried out at considerably
lower temperatures, for example, at 210 degrees Centigrade, in which case the
heating is to be continued for a somewhat longer period. The sulphuric acid
(66 degrees Baumé) can be replaced by stronger acids, such as monohydrated
sulphuric acid or moderately fuming sulphuric acid, and in place of boric acid,
compounds can be used which yield boric acid in the presence of sulphuric acid, for
instance, boron trichloride, salts of boric acid, or the like.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed (as communicated to me
from abroad), I declare that what I claim is :-
1. The conversion of hydroxyanthraquinonequinolines, or sulphonic acids thereof,
into products containing a greater number of hydroxylic groups than the original
materials, which process consists in heating, at elevated temperatures, mono-
hydroxy-, dihydroxy, or trihydroxy-anthraquinonequinolines, or sulphonic acids
thereof, with concentrated or monohydrated, or moderately fuming sulphuric acid,
in the presence of boric acid, or other boron compounds yielding boric acid when
used together with sulphuric acid.
2. The use, in the process claimed by the foregoing first claim, of beta quinoline
derivatives of alizarin, flavopurpurin, or anthra purpurin, or other hydroxyanthra-
quinonequinolines, or sulphonic acids thereof.
Dated this 2nd day of November 1894.
NEWTON & SON,
Agents for the Applicant.