The Manufacture or Production of Anthraquinone Dyestuffs.
Year: 1899

page_text: [Communicated from abroad by THE FARBENFABRIKEN VORMALS FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Anthraquinone Dyestuffs.
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 production of diamido anthrarufinemono-
sulphonic acid, and diamidochrysazine monosulphonic acid, from diamidoanthrarufine
disulphonic acid and diamidochrysazine disulphonic acid. My foreign correspondents
have found that the said disulphonic acids (which are described in the Specification
to Letters Patent No. 12011%) can be transformed in a very profitable manner into
the above-mentioned monosulphonic acids (which are likewise described in the said
Specification), if they are subjected to the action of suitable reducing agents.
On performing the new reaction by means of alkaline sulphides, or similar reducing
agents, the monosulphonic acids are formed directly, whilst on using other reducing
agents, leuco compounds of the monosulphonic acids are produced, which, in order to
obtain the monosulphonic acids, are subjected to the action of suitable oxydizing
agents.
As is described in the above mentioned Patent No. 12011, the diamidodisulphonic
acids, which are the starting materials for the present invention, are obtained by
treating the corresponding dinitro compounds with reducing agents. Therefore, in
carrying out the present invention, it is not necessary to start from the diamidodi-
sulphonic acids themselves, but the said dinitro compounds may be the starting point;
thus, the production of the diamidodisulphonic acids, and the transformation of the
same into the monosulphonic acids, or their leuco compounds, are combined in one
operation.
In order to illustrate the first mentioned method, the following Example A is given,
the parts being by weight.
EXAMPLE A.
A mixture prepared from 10 parts of diamidoantbrarufine disulphonic acid,
1000 parts of water, and 30 parts of sodium sulphide (Na,S), is heated on a water
bath, the color of the mixture being soon transformed into a deep blue. When, on
testing diamidoanthrarufinedisulphonic acid is no longer found to be contained in the
reaction mixture, the latter is allowed to cool. Subsequently, the diamidoanthrarufine
monosulphonic acid is separated by the addition of common salt.
The process proceeds in an analogous manner, if diamido chrysazinedisulphonic
acid is to be transformed into the corresponding monosulphonic acid, or if, instead of
sodium sulphide, ammonium sulphide, or other alkaline sulphide, is employed.
מ
077

page_text: As above mentioned, the reaction proceeds in a somewhat different manner, if other
reducing agents are employed, certain leuco compounds of the monosulphonic acids
being thus produced. According to further researches of my foreign correspondents,
this reduction takes place in two phases, that is to say, at first a class of leuco
compounds is obtained, which my foreign correspondents term "leuco compounds I,"
whilst by a further reduction these "leuco compounds I" are transformed into
another class of leuco compounds, which may be termed leuco compounds II.
In order to illustrate the production of these two classes of leuco compounds, the
following Examples Band Care given,
In a mixture prepared from 20 parts of dinitroanthrarufine disulphonic acid and
200 parts of hydrochloric acid of 15 degrees Baumné, 100 parts of stannous chloride,
dissolved in 200 parts of hydrochloric acid, are added. The resulting mixture is
heated on a water-bath, until a test portion poured into water yields a pure yellow
color. Subsequently, 100 parts of water are added to the reaction mixture, and the
same is then filtered. The residue remaining on the filter represents the new "leuco
compound II." It is a yellow crystalline mass, which is soluble with great difficulty
in water. By concentrated sulphuric acid, it is dissolved with a yellow color. The
new compound is soluble in dilute caustic soda-lye with a red color, which, by the
action of the oxygen contained in the air, is slowly changed into blue.
In a inauner analogous to that described in the foregoing Examples B and C, the
"leuco compounds I." and "II." of the diamido chrysazine monosulphonic acid (which
are very similar to the corresponding anthrarufine derivatives) can be obtained.
The transformation of the leuco compounds into the diamidomonosulphonic acids
themselves, may be illustrated by the foregoing typical Example D.
EXAMPLE D.
10 parts of the "leuco compounds I" described in the above Example B, are
dissolved in 500 parts of water and 50 parts of a caustic soda lye of 30 degrees
Baumé. A current of air is then caused to pass through the resulting solution, until
the latter has assumed an intense and pure blue color. During this operation, the
most part of the diamidoanthrarufinemonosulphonic acid will be separated from the
solution in the shape of its sodium salt, which can be isolated by filtration.
Instead of the oxygen contained in the air, other oxydizing agents, such as con-
centrated sulphuric acid, potassium bichromate, ferric, chloride, or the like, can be
employed, in order to transform the hereinbefore defined leuco compounds into the
corresponding monosulphonic acids.
My foreign correspon·lents wish to point out that they do not at all intend to
confine themselves to the particulars given in the above specification, as the examples

page_text: contained therein are merely typical, and can be varied within wide limits, without
altering thereby the nature of the present invention.
Dated this 24th day of August 1899.
NEWTON & SON,
Agents for the Applicant,
The Manufacture or Production of Anthraquinone Dyestuffs. .
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 production of diamidoanthrarufinemono-
sulphonic acid and diamidochrysazinemonosulphonic acid, from dianidoanthrarufinedi-
sulphonic acid and diamidochrysazinedisulphonic acid. My foreign correspondents
have found that the said disulphonic acids (which are described in the Specification
to Letters Patent No. 12011%) can be transformed, in a very profitable manner, into
the above-mentioned nonosulphonic acids (which are likewise described in the said
Specification), if they are subjected to the action of suitable reducing agents.
On performing the new reaction by means of alkaline sulphides or similar reducing
agents, the monosulphonic acids are formed directly, whilst on using other reducing
agents, leuco-compounds of the monosulphonic acids are produced, which, in order to
obtain the nonosulphonic acids, are subjected to the action of suitable oxydizing
agents.
As is described in the above mentioned Patent No. 120117, the diamidodisulphonie
acids which are the starting materials for the present invention, are obtained by
treating the corresponding dinitro compounds with reducing agents. Therefore, in
carrying out the present invention, it is not necessary to start from the diamidodi-
sulphonic acids themselves, but the said dinitro compounds may be the starting
point; thus, the production of the diamidodisulphonic acids, and the transformation
of the same into the monosulphonic acids or their leuco-compounds, are combined
in one operation.
In order to illustrate the first-mentioned method, the following Example A is given,
the parts being by weight
--
EXAMPLE A.
A mixture prepared from 10 parts of diamidoanthrarufinedisulphonic acid,
1000 parts of water and 30 parts of sodium sulphide (NaS) is heated on a water-
bath, the color of the mixture being soon transformed into a deep blue. When, on
testing, diamidoanthrarufinedisulphonic acid is no longer found to be contained in
the reaction mixture, the latter is allowed to cool. Subsequently, the diamidoanthraru-
finemonosulphonic acid is separated by the addition of common salt.
The process proceeds in an analogous manner, if diamidochrysazinedisulphonic acid
is to be transformed into the corresponding monosulphonic acid, or if, instead of
sodium sulphide, aminonium sulphide or other alkaline sulphide is employed.
As above mentioned the reaction proceeds in a somewhat different manner, if other
reducing agents are employed, certain leuco-compounds of the monosulphonic acids
being thus produced. According to further researches of my foreign correspondents,
this reduction takes place in two phases, that is to say, at first a class of leuco-compounds

page_text: EXAMPLE D.
10 parts of the "leuco compound I" described in the above Example B, are dissolved
in 500 parts of water and 50 parts of a caustic soda-lye of 30 degrees Baumé. A
current of air is then caused to pass through the resulting solution, until the latter
has assumed an intense and pure blue color. During this operation, the most part
of the diamidoanthrarufinemonosulphonic acid will be separated from the solution in
the shape of its sodium salt, which can be isolated by filtration.
Instead of the oxygen contained in the air, other oxydizing agents, such as concen-
trated sulphuric acid, potassium bichromate, ferric chloride, or the like, can be em-
ployed in a suitable manner, in order to transform the herein before defined leuco-
compounds into the corresponding monosulphonic acids.
My foreign correspondents wish to point out, that they do not at all intend to
confine themselves to the particulars given in the above Specification, as the
examples contained therein 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-

page_text: 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 process for the production of paradiamidoanthrarufinemonosulphonic acid
and paradiamidochrysazinemonosulphonic acid, which process consists in treating
the corresponding disulphonic acids with alkaline, reducing agents, such as alkaline
sulphides or the like, substantially as herein before described.
2. The process for the production of new leuco-compounds of paradiamidodioxy-
anthraquinone sulphonic acids, which process consists in treating, in neutral acid or
alkaline solution, paradiamido anthrarufinedisulphonic acid and paradiamidochry-
sazine disulphonic acid, with suitable reducing agents, substantially as herein before
described.
3. The process for the production of paradiamidoanthrarufinemonosulphonic acid
and paradiamidochrysazinemonosulphonic acid, which process consists in treating
the leuco compounds obtainable by the process claimed under Claim 2, with oxidizing
agents, substantially as herein before described.
4. As new articles of manufacture, the new products obtainable by the processes
herein before described and claimed.
Dated thin 15th day of V 1000
NEWTON & SON,
Agents for the Applicant.