The Manufacture or Production of Blue Dye-stuffs of the Anthraquinone Series.
Year: 1898

page_text: [Communicated from abroad by THE FARBENFABRIKEN VORMALS FRIEDRICH BAYER &
Co., of Elberfeld, Germany.]
The Manufacture or Production of Blue Dye-stuffs of the
Anthraquinone Series.
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:-
The present invention relates to the isolation of certain intermediate products
derived from anthraquinone, which were unknown up to the present time and to the
transformation of these intermediate products into blue dye-stuffs.
It is known that a blue liquid is obtained by heating 1-5 dinitroanthraquinone
with fuming sulphuric acid (containing about 40 per cent. of SO₁) in the presence of
sulphur, until a test portion of the reaction mixture is soluble in water. From this
blue liquid, hexa-oxyanthraquinone disulphonic acid can be obtained, if it is poured
into a large quantity of water, and if common salt is added to the blueish-red solution
thus produced.
Up to the present time, it has been supposed that the finished hexaoxyanthra-
quinone disulphonic acid, or a sulphuric acid ether thereof, was contained in the
blue liquid above mentioned, and that the other operations above mentioned were
only necessary in order to separate the finished hexaoxyanthraquinone disulphonic
acid from the blue liquid.
My foreign correspondents have now discovered, that this hypothesis is not correct,
and that the hexaoxyanthraquinone disulphonic acid itself is not contained in the
said blue liquid, but that an intermediate product, unknown up to the present time,
occurs therein, which intermediate product is transformed into the hexaoxyanthra-
quinone disulphonic acid, on pouring the blue liquid into water.
According to the researches of my foreign correspondents, the said new inter-
mediate product is most probably a diquinone diimide of the diamidoanthrachryson
disulphonic acid, and has the formula.

page_text: My foreign correspondents remark that the new product may also be a sulphuric
acid ether of a body having the above formula.
The researches have further shown that this intermediate product can be isolated,
if the blue liquid herein before mentioned is poured into a very cold watery solution
of a suitable salt, such as potassium chloride, sodium chloride, or the like, instead of
into pure water.
In order to illustrate this process, the following example A is given (the parts
being by weight).
EXAMPLE A.
10 parts of 1.5 dinitroanthraquinone are heated with 200 parts of fuming
sulphuric acid (containing 30 per cent. of SO), and 2 parts of sulphur, for about from
one hour and a half to two hours and a half, at from 120 to 130 degrees Centigrade.
Subsequently, the mixture is cooled to zero, and is slowly poured, while being well
stirred, into a 20 per cent. potassium chloride solution which has been cooled
10 degrees Centigrade. The precipitate thus obtained is filtered as quickly as
possible, washed with a cold watery solution of common salt, and dried at a low
temperature. The intermediate product thus obtained dissolves in concentrated
sulphuric acid with a greenish blue color, and in water with a violet-blue colour,
which changes into greenish blue by the addition of caustic soda lye.
to
-
•
In a cold sodium bisulphite solution, the body dissolves with a yellow color.
When an acidiluted watery solution of the new body is allowed to stand for some
time, the product changes into an anthradiquinone, ammonia being split off.
process proceeds probably according to the following equation :-
:-
This
The particulars given in the foregoing Example A can be varied within wide limits.
Instead of the 15 dinitroanthraquinone, its isomers can be employed. Thus, for 30
instance, from 1.8 dinitroanthraquinone, an intermediate product is obtained, which
exhibits properties analogous to those of the body described in the example.
place of the fuming sulphuric acid containing 30 per cent. of SO, acids can be used
In

page_text: 10 parts of 15 dinitro anthraquinone are heated with 200 parts of fuming sulphuric
acid (containing 30 per cent. of SO,) and two parts of sulphur, during from one hour
and a half to two hours and a half, at from 120 to 130 degrees Centigrade. The blue
liquid thus obtained is cooled to 50 degrees Centigrade, and mixed with 20 parts of
granulated zine. The mixture is then kept at the said temperature, and stirred,
until a test portion poured into concentrated sulphuric acid, dissolves no longer with
a blue, but with a yellow colour. The liquid is then decanted from the zinc into
water. From the resulting watery solution, the dyestuff is separated by the

page_text: addition of common salt. It is identical with that obtained according to the above
Example B.
Instead of zinc, other suitable reducing agents, such as tin, phenylhydrazine,
phenylhydrazinesulphonic acids, can be employed.
My foreign correspondents wish it to be understood that they do not intend to limit
themselves to the particulars given in the examples, as these are merely typical, & can
be varied within wide limits, without altering thereby the nature of the present
invention.
Dated thie ftb dow of Santambor 1000
The Manufacture or Production of Blue Dye-stuffs of the
Anthraquinone Series.
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 :-
The present invention relates to the isolation of certain intermediate products
derived from anthraquinone, hitherto unknown, and to the transformation of these
intermediate products into blue dye-stuffs.
It is known that a blue liquid is obtained by heating 15-dinitroanthraquinone with
fuming sulphuric acid (containing about 40 per cent. of SO3) in the presence of
sulphur, until a test portion of the reaction mixture is soluble in water. From this
blue liquid, hexaoxyanthraquinone disulphonic acid can be obtained, if it is poured
into a large quantity of water, and if common salt is added to the bluish-red solution
thus produced.
It has heretofore been supposed that the finished hexaoxyanthraquinone disulphonic
acid, or a sulphuric acid ether thereof, was contained in the blue liquid above
mentioned, and that the other operations above mentioned were only necessary in
order to separate the finished hexaoxyanthraquinone disulphonic acid from the blue
liquid.
My foreign correspondents have now discovered that this hypothesis is not correct,
and that the hexaoxyanthraquinone disulphonic acid itself is not contained in the said
blue liquid; but that an unknown intermediate product is to be found therein, which
intermediate product is transformed into the hexaoxyanthraquinone disulphonic
acid, on pouring the blue liquid into water.
According to the researches of my foreign correspondents, the said new
intermediate product is most probably a diquinone diimide of the diamido anthra-
chrysone disulphonic acid, and has the formula-

page_text: My foreign correspondents remark that the new product may also be a sulphuric
acid ether of a body having the above formula.
The researches have further shown that this intermediate product can be isolated,
if the blue liquid hereinbefore mentioned is poured into a very cold watery solution
of a suitable salt, such as potassium chloride, sodium chloride, or the like, instead of
into, pure water.
In order to illustrate this process, the following examnie A is given (the warts beinơ

page_text: compound with the sulphuric acid can also be performed in the presence of boric
acid.
If boric acid is present during the reaction, it is in general preferable to use a
fuming sulphuric acid which contains a larger percentage of SO, or higher
temperatures than those which are employed if the reaction is performed without
the addition of boric acid. It may be remarked that the reaction can also be
performed, though less satisfactorily, without the addition of sulphur.
My foreign correspondents have further found, that, by treating the new inter-
mediate products hereinbefore defined with reducing agents, diamido-tetraoxyanthra-
auinone disulphonic acids are produced, ea according to the following equation :—

page_text: stirred until a test portion poured into concentrated sulphuric acid, dissolves no longer
with a blue, but with a yellow color. The liquid is then decanted from the zine into
water. From the resulting watery solution, the dye-stuff is separted by the
addition of common salt. It is identical with that obtained according to the above
Example B.
Instead of zinc, other suitable reducing agents, such as tin, phenylhydrazine,
phenylhydrazinesulphonic acids can be employed.
My foreign correspondents wish it to be understood that they do not intend to
limit themselves to the particulars given in the examples, as these are merely typical,
and can be varied within wide limits, without altering thereby the nature of the
present invention.
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), declare that what I claim is :-
1. The isolation of new intermediate products exhibiting the properties of
quinoneimides, which process consists in pouring the reaction mixtures which are
obtained by heating dinitroanthraquinones with fuming sulphuric acid, with or
without the addition of sulphur or boric acid, into cold solutions of suitable salts, and
isolating the resulting precipitates in a suitable manner, substantially as herein before
described.
2. The production of coloring matters by treating with reducing agents the
herein before defined intermediate products (using the same either in an isolated
state, or without previous isolation from the reaction mixtures defined in the foregoing
Claim 1), substantially as herein before described.
3. As new articles of manufacture, the new immediate products obtainable
according to the process hereinbefore described and claimed.
Dated this 24th day of May 1899.
NEWTON & SON,
Agents to the Applicant.