Manufacture of Azoamines by the Reduction of Azo Colouring Matters Derived from Nitramines.
Year: 1890

page_text: Date of Application, 29th Jan., 1890
Complete Specification Left, 28th Oct., 1890-Accepted, 29th Nov., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIÈRES COLORANDES
ET PRODUITS CHIMIQUES DE ST. DENIS, ALCIDE FRANÇOIS POIRRIER, Manu-
facturer, and DANIEL AUGUSTE ROSENSTIEHL, Chemist, all of 105, Rue Lafayette,
Paris, France.]
Manufacture of Azoamines by the Reduction of Azo Colouring
Matters Derived from Nitramines.
I, JOHN IMRAY of No. 28 Southampton Buildings, Chancery Lane, in the County
of London, Consulting Engineer and Patent Agent, do hereby declare the nature of
this invention to be as follows:-
This invention relates to a manufacture of azoamines by the reduction of the azo
coloring matters derived from nitramines.
The process for this purpose is based on the following facts.
The azo coloring matters, when submitted to the action of the reducing agents in
an alkaline medium, are destroyed, as is well known. When operating upon azo bodies
which are derivates of nitramines, there may be seized in this reaction, before it has
arrived at its extreme limit, several well defined phases.
1. The first product of the reaction is a coloring matter derived from azoxyamine;
two molecules of nitrated azo matter combine into one in losing three atoms of
oxygen out of the four that are united with the nitrogen in the compound.
2. The reducing agent continuing to act, the last atom of oxygen is removed in its
turn and there are formed azo matters derived from azoamines.
3. In a third phase, the last named substances are converted into free azo-
amines and into an amido derivative, the nature of which need not be considered
here.
4. Lastly, the ultimate products of the reduction result from the destruction
of the azo-amines themselves, the molecule of which divides itself into two molecules
of diamines; this last reaction is only mentioned as a record.
The first phase above mentioned already forms the subject matter of a prior
patent.
The process which forms the subject of the present invention is based on the
reactions mentioned under the second and third heads.
Example. Paranitraniline is diazotised and coupled in the well known manner with
bisulphonaphthol.
100 kilos. of the azo coloring matter thus obtained are dissolved in 1000 litres of
water rendered alkaline by the addition of 100 litres of caustic soda of 40° Bé. The
temperature is raised to 50° C. for facilitating the solution, and 80 kilos. of glucose
of 75 p.c. are introduced.
When the whole is well mixed the mass is heated to boiling point.
The violet coloration of the liquor is gradually converted into a brown coloration.
By cooling, the paraazoaniline is separated in the form of crystalline needles, it is
collected and washed with water. For purifying the same, it is redissolved in hydro-
chloric acid, filtered and neutralized by soda.
The azoaniline is precipitated and collected, washed and dried.
In place of paranitraniline may be used metanitraniline, and equivalent quantities
of their homologue derivates of toluidine, xylidine &c.
The reducing agents are glucose, zinc, tin in powder, oxide of tin, and generally
those reducing agents that act in an alkaline medium.
In diazotising the nitrated amine, it may be combined with the various phenoles and
mines, either sulphonised or carboxylised, or not.

page_text: It is however preferred to take the combinations that are soluble in water, in the
presence of alkalis. The proportions and the temperatures indicatod may be varied
between wide limits.
2011 1
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Azoamines by the Reduction of Azo Colouring
Matters Derived from Nitramines.
I, JOHN IMRAY of No. 28 Southampton Buildings, Chancery Lane, in the County
of London, Consulting Engineer, and 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 :-
-
This invention relates to a manufacture of azoamines by the reduction of the azo-
coloring matters derived from nitramines.
The process for this purpose is based on the following facts.
The azo coloring matters, when submitted to the action of reducing agents in an
alkaline medium, are destroyed, as is well known. In operating upon azo-bodies which
are derivates of nitramines before this reaction has reached its extreme limit several
well defined phases may be noted.
1. The first product of the reaction is a coloring matter derived from azo-xyamine.
Two molecules of nitrated azo matter combine into one, losing three atoms of oxygen
out of the four that are united with the nitrogen in the compound.
2. As the reducing agent continues to act, the last atom of oxygen is removed in its
turn and there are formed azo matters derived from azoamines.
3. In a third phase, the last named substances are converted into free azo-
amines and into an amido derivative, the nature of which need not be considered
here.
4. Lastly, the ultimate products of the reduction result from the destruction of the
azo-amines themselves, the molecule of which divides itself into two molecules of
diamines this last reaction is only mentioned as a record.
i
The first phase above mentioned already forms the subject matter of a prior
patent.
The process which forms the subject of the present invention is based on the reactions
mentioned under the second and third heads, which reactions have been discovered by
the communicators of this invention.
Example. Paranitraniline is diazotised and coupled in the well known manner with
bisulphonaphthol.
100 kilos. of the azo coloring matter thus obtained are dissolved in 1,000 litres of
water rendered alkaline by the addition of 100 litres of caustic soda solution of 40° Bé.
The temperature is raised to 50° (). to facilitate solution, and then 80 kilos. of glucose
of 75 per cent. are introduced.
When the whole is well mixed, it is heated to ebullition.
The violet color of the liquor gradually changes to a brown. By cooling, the para-
azoaniline is separated in the form of crystalline needles, it is collected and washed
with water. It is purified by being redissolved in hydrochloric acid, filtered and
neutralised by soda.
The azoaniline is precipitated, collected, washed and dried.
Instead of paranitraniline may be used metanitraniline, and equivalent quantities of
their homologue derivates of toluidine, xylidine &c.
The reducing agents are glucose, powdered zinc and tin, oxide of tin, and generally
those reducing agents that act in an alkaline medium.
In diazotising the nitrated amine, it may be combined with the various phenols and
amines, either sulphonised or carboxylised, or not

page_text: It is however preferred to take the combinations that are soluble in wator, in the
presence of alkalies. The proportions and the temperatures may be varied within
considerable limits.
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
The manufacture of azoamines by the reduction, of the azo colouring matters obtained
from nitramines, substantially as herein described.
Dated this 28th day of October 1890.
ABEL & IMRAY,
Agents for the Applicant.