The Manufacture or Production of Anthraquinone Derivatives.
Year: 1899

page_text: Date of Application, 24th May, 1899
Complete Specification Left, 9th Feb., 1900-Accepted, 10th Mar., 1900
[Communicated from abroad by the FARBENFABRIKEN VORMALS FRIEDRICH BAYER
& Co., of Elberfeld, Germany.]
The Manufacture or Production of Anthraquinone Derivatives.
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 found that, by treating diamido-anthraquin-
ones, or sulphonic acids thereof, with suitable oxidizing agents, diamido-oxy-
anthraquinones, or sulphonic acids thereof, can be obtained.
Thus, for instance, by subjecting 1.5 diamido-anthraquinone to the oxidizing
action of manganese dioxide (MnO2), or the like, a mixture of paradiamido-
anthrarufine and diamido-anthrachrysone is obtained. On subjecting the di-
sulphonic acid of 1.5 diamido-anthraquinone to the action of oxidizing agents,
a dye stuff sulphonic acid is obtained, which exhibits properties similar to those
of the diamidodioxy anthraquinone disulphonic acids described in the Specifi-
cation of Letters Patent No. 120117.
In order to illustrate the new process, the following examples are given (the
parts being by weight):-
EXAMPLE A.
15 parts of manganese dioxide are slowly added, with stirring, to a solution of
10 parts of 1.5 diamido-anthraquinone, in 60 parts of concentrated sulphuric
acid (of 60 degrees Bé.), care being taken that the temperature of the solution
does not exceed 40 degrees Centigrade. The resulting mixture assumes, at first,
a green, and then a dark blue color, during the reaction. When the oxidation
is finished, the mixture is poured into a solution prepared from 2000 parts of
water and 20 parts of a sodium bisulphite solution (of 30 degrees Baumé). The
mixture thus obtained is heated to boiling, and then filtered. The residue
remaining on the filter is washed with water. Subsequently, the diamido-anthra-
chrysone contained in this residue is isolated therefrom by extracting the same
with the aid of a dilute caustic soda-lye. That part of the residue which is not
dissolved by the caustic lye consists (according to the researches of my foreign
correspondents), for the most part, of diamido-anthrarufine. In order to be
purified, it is repeatedly extracted by means of boiling dilute soda-lye. Sub-
sequently, it is acidulated by means of hydrochloric acid and recrystallized from
nitro-benzene. Thus, the pure paradiamido-anthrarufine is obtained in the shape
of glittering needles.

page_text: trated sulphuric acid (66 degrees Baumé). After a short time, the mixture will
assume a blue color. It is then heated for some while at about 50 degrees Centi-
grade. Subsequently it is cooled, and poured into 2000 parts of water, which
have been mixed with 40 parts of a sodium bisulphite solution (of 30 degrees
Baumé). The resulting liquid is first heated to boiling, then it is filtered, and
finally allowed to cool. Thus, the dyestuff contained therein is caused to separate
in the shape of a dark precipitate.
The so-produced coloring matter represents, when isolated by filtration, a dark
paste, which dissolves in hot water with a violet-red color, but in a dilute caustic
soda lye, and in ammonia liquor, with a blue color. By concentrated sulphuric
acid, it is dissolved with a brownish-red color, which changes into blue on the
addition of boric acid. The blue solution thus obtained exhibits a spectrum
which consists of two lines in the orange and in the yellow parts.
The dye-stuff obtained according to the above example B dyes unmordanted
wool, in acid baths, pure and fast violet-blue shades. On chrome-mordanted
wool, it yields pure greenish-blue shades.
My foreign correspondents wish it to be understood that they do not at all
intend to confine themselves to the particulars given in the above examples, as
these are merely typical, and can be varied within wide limits. Thus, for
instance, instead of the basic materials mentioned in the examples, other di-
amido anthraquinones, or sulphonic acids thereof, can be employed, or the man-
ganese dioxide therein used may be replaced by other oxidizing agents acting
in the same or in a similar manner, such as nitric acid, persulphates, or the like.
1 1
Ou
1
1000
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Anthraquinone Derivatives.
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 have found that, by treating diamido-anthraquin-
ones, or sulphonic acids thereof, with suitable oxydizing agents, diamido-oxy-
anthraquinones, or sulphonic acids thereof, can be obtained.
Thus, for instance, by subjecting 1.5 diamido-anthraquinone to the oxydizing
action of manganese dioxide (MnO2), or the like, a mixture of paradiamido-
anthrarufine and diamido-anthrachrysone is obtained. On subjecting the di-
sulphonic acid of 1.5 diamido-anthraquinone to the action of oxydizing agents,
a dye stuff sulphonic acid is obtained which exhibits properties similar to those
of the diamido oxyanthraquinone disulphonic acids described in the Specifi-
cation of Letters Patent No. 1201107.
In order to illustrate the new process, the following examples are given (the
parts being by weight);-
EXAMPLE A.
15 parts of manganese dioxide are slowly added, with stirring, to a solution of
10 parts of 1.5 diamidoanthraquinone, in 300 parts of concentrated sulphuric
acid (of 60 degrees Bé.), care being taken that the temperature of the solution
does not exceed 40 degrees Centigrade. The resulting mixture assumes, at first,

page_text: a green, and then a dark blue color, during the reaction. When the oxydation
is finished, the mixture is poured into a solution prepared from 2000 parts of
water and 20 parts of a sodium bisulphite solution (of 30 degrees Baumé). The
mixture thus obtained is heated to boiling, and then filtered. The residue
remaining on the filter is washed with water. Subsequently, the diamido-anthra-
chrysone contained in this residue is isolated by extracting the same
with the aid of a dilute caustic soda-lye. That part of the residue which is not
dissolved by the caustic lye consists (according to the researches of my foreign
correspondents) for the most part of diamido-anthrarufine. In order to purify
Sub-
it, it is repeatedly extracted by means of boiling dilute soda-lye.
sequently it is acidulated by means of hydrochloric acid, and recrystallized from
nitro-benzene. Thus, the pure paradiamido-anthrarufine is obtained in the shape
of glittering needles.
EXAMPLE B.
20 parts of manganese dioxide are slowly introduced, with continuous stirring,
at about from 40 to 45 degrees Centigrade, into a solution prepared from 20 parts
of the disulphonic acid of 1.5 diamido-anthraquinone and 400 parts of concen-
trated sulphuric acid (66 degrees Baumé). After a short time, the mixture will
assume a blue color. It is then heated for some while at about 50 degrees Centi-
grade. Subsequently it is cooled and poured into 2000 parts of water which
have been mixed with 40 parts of a sodium bisulphite solution (of 30 degrees
Baumé). The resulting liquid is first heated to boiling, then it is filtered, and
finally allowed to cool. Thus, the dyestuff contained therein is caused to separate
in the shape of a dark precipitate.
The so produced coloring matter represents, when isolated by filtration, a dark
paste which dissolves in hot water with a violet-red color, but in a dilute caustic
soda lye, and in ammonia liquor, with a blue color. By concentrated sulphuric
acid, it is dissolved with a brownish-red color, which changes into blue on the
addition of boric acid. The blue solution thus obtained exhibits a spectrum
which consists of two lines in the orange and in the yellow parts.
The dye-stuff obtained according to the above example B, dyes unmordanted
wool, in acid baths, pure and fast violet-blue shades. On chrome-mordanted
wool, it yields pure greenish-blue shades.
My foreign correspondents wish it to be understood that they do not at all
intend to confine themselves to the particulars given in the above examples, as
these are merely typical, and can be varied within wide limits. Thus, for
instance, instead of the starting materials mentioned in the examples, other di-
amido anthraquinones, or sulphonic acids thereof, can be employed, or the man-
ganese dioxide therein used may be replaced by other oxydizing agents acting
in the same or in a similar manner, such as nitric acid, persulphates, or the like.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, as communicated to
me from abroad, I declare that what I claim is:
The process for the production of diamidooxyanthraquinones, or sulphonic
acids thereof, by treating diamidoanthraquinones, or their sulphonic acids, with
suitable ozydizing agents, substantially as herein before described.
Dated thin 0th day of Wahmu 1900
NEWTON & SON,
Agents for the Applicant.