PREPARATION OF THE PRODUCT OF REDUCTION OF DINITROBENZILE IN AN ALKALINE MEDIUM, AND OF THE POLYAZOIC DERIVATE
Year: 1887

page_text: Date of Application, 2nd July, 1887
Complete Left, 29th Mar., 1888
Complete Accepted, 4th May, 1888
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIÈRS COLORANTES ET
PRODUITS CHIMIQUES DE ST. DENIS, ALCIDE FRANÇOIS POIRRIER, Manufacturer,
and DANIEL AUGUSTE ROSENSTIEHL, Chemist, all of 105, Rue Lafayette, Paris,
France.]
I, JOHN IMRAY of No. 28 Southampton Buildings, Chancery Lane in the County of
Middlesex, Consulting Engineer and Patent Agent do hereby declare the nature of
this invention to. be as follows:-
This invention relates to the manufacture of azo colouring matters by subjecting
dinitrobenzile to reduction in an alkaline medium, and combining its polyazoic
derivate with phenols, oxyphenols, naphthols, oxynaphthols, primary, secondary or
tertiary amines, diamines, or the alkylic, sulphonic or carboxylic derivates of these
substances.
I. PREPARATION OF
THE
PRODUCT OF
REDUCTION
OF
DINITROBENZILE IN
AN
ALKALINE MEDIUM, AND OF THE POLYAZOIC DERIVATE.
Dinitrobenzile is the compound obtained by nitrating benzoine (Sagumenny
Berichte der Deutschen chemischen Gesellschaft 1872 page 1100).
5 kilogs. of this substance are mixed with 50 litres of water and 23 kilogs. of soda
ley at 36° B. The mixture is heated to ebullition and 10 kilogs. of zinc powder are
slowly introduced into it in successive small doses. The liquid becomes quite
discoloured. It is then poured into 65 kilogs. of bydrochloric acid at 20° B. and the
mixture is kept boiling for 20 or 30 minutes. The whole is neutralised with 22 kilos.
600 of carbonate of soda and filtered. The precipitated carbonate of zinc is washed
several times with boiling water. The liquors are collected together and after
concentration are available for the preparation of the polyazoic derivate. For this
purpose, a quantity of the solution of the reduction product corresponding to 12 kilogs.

page_text: 100 of the amide derivate has added to it 22 kilogs. of hydrochloric acid at 20° B.,
is cooled with ice, and has poured into it 26 kilogs: of a solution of nitrite of soda
at 33%. The mixture is agitated for a short time and then left to react for 2 or
3 hours.
II. PREPARATION OF THE COLOURING MATTERS.
The following are examples of the preparation of colouring matters obtained with
alpha-sulpho-alpha-naphthol and with metaphenylenediamine.
1° Alpha-sulpho-alpha-naphthol. The liquor containing the poly-azoic derivate has
added to it 24 kilogs. 400 of alpha-sulpho-alpha-naphthol in the condition of soda salt
and is alkalised with carbonate of soda. It is left for some time at rest, and is then
precipitated with salt. Thus is obtained a violet colouring matter very soluble in
water.
2° Metaphenylenediamine. The liquor containing the poly-azoic derivate has
added to it a solution of 10 kilos. 800 of metaphenylenediamine in 1000 litres of
water, and to this is added a quantity of carbonate of soda sufficient to render tho
solution after reaction slightly alkaline. It is then precipitated with salt, giving a
colouring matter for red brown dye.
By substituting for the alpha-sulpho-alpha-naphthol or the metaphenylenediamine
an equivalent quantity of one of the substances mentioned below, colouring matters
are obtained of analogous character, as follows:-
-
Bisulphonaphthol gives a violet colouring matter
Alpha-naphthol
Beta-naphthol
Naphthionic acid
red violet
"
red violet
"1
red
orange
"
orange
23
yellow
Alpha-naphthylamine,,
Resorcine
Salicylic acid
All the colouring matters thus prepared from dinitrobenzile among other
properties possess that of dyeing cotton without mordant, in an alkaline bath."
The proportions of the reagents and the reducing agents may be varied.
1
1 1

page_text: I. PREPARATION OF THE PRODUCT OF REDUCTION OF DINITROBENZILE IN AN ALKALINE
MEDIUM, AND OF THE POLYAZOIC DERIVATE.
Dinitrobenzile is the compound obtained by nitrating benzoine (Sagumenny
Berichte de Deutschen chemischen Gesellschaft 1872 page 1100).
5 kilogs. of this substance are mixed with 50 litres of water and 23 kilogs. of soda
lye at 36° Beaumé. The mixture is heated to ebullition and 10 kilogs. of zinc
powder are slowly introduced into it in successive small doses. The liquid becomes
quite discoloured. It is then poured into 65 kilogs. of hydrochloric acid at 20° B.
and the mixture is kept boiling for 20 or 30 minutes. The whole is neutralised with
22.6 kilogs. of carbonate of soda and filtered. The precipitated carbonate of zinc is
washed several times with boiling water. The liquors are collected together and after
concentration are available for the preparation of the polyazoic derivate. For this
purpose, a quantity of the solution of the reduction product corresponding to
12-1 kilogs. of the amide derivate has added to it 22 kilogs. of hydrochloric acid at
20° B., is cooled with ice and has poured into it 26 kilogs. of a solution of nitrite of
soda at 33%. The mixture is agitated for a short time and then left to react for 2 or
3 hours.
II. PREPARATION OF THE COLOURING MATTERS.
The following are examples of the preparation of colouring matters obtained with
alpha-sulpho-alpha-naphthol and with metaphenylenediamine.
1° Alpha-sulpho-alpha-naphthol. The liquor containing the polyazoic derivate has
added to it 244 kilogs. of alpha-sulpho-alpha-naphthol in the condition of soda salt
and is alkalised with carbonate of soda. It is left for some time at rest, and is then
precipitated with salt. Thus is obtained a violet colouring matter very soluble in
water.

page_text: 2° Metaphenylenediamine. The liquor containing the polyazoic derivate has added
to it a solution of 10-8 kilogs. of metaphenylenediamine in 1000 litres of water, and to
this is added a quantity of carbonate of soda sufficient to render the solution after
reaction slightly alkaline. It is then precipitated with salt, giving a colouring matter
for red brown dye.
By substituting for the alpha-sulpho-alpha-naphthol or the metaphenylenediamine
an equivalent quantity of one of the substances mentioned below, colouring matters
are obtained of analogous character, as follow:-
Bisulphonaphthol gives a violet colouring matter
Alpha-naphthol
Beta-naphthol
Naphthionic acid
red violet
"
"
"
red violet
"
"
"
red
"
"
""
orange
orange
"
yellow
""
37
32
"2
"
Alpha-naphthylamine,,
Resorcine
Salicylic acid
All the colouring matters thus prepared from dinitrobenzile among other properties
possess that of dyeing cotton without mordant, in an alkaline bath. They can also
serve as materials for the manufacture of other colouring matters.
The proportions of the reagents and the reducing agents may be varied.
Having now particularly described and ascertained the nature of my said Inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is:
1. The herein described process of reduction of dinitrobenzile in an alkaline
medium.
2. The herein described process for manufacturing colouring matters by combining
the polyazoic derivate obtained by reduction of dinitrobenzile in an alkaline medium,
with phenols, oxyphenols, naphthols, oxynaphthols, primary, secondary or tertiary
amines, diamines, or the alkylic, sulphonic or carboxylic derivates of these
substances.
3. As new products, the colouring matters obtained in the manner above referred
to as well as the product of reduction of dinitrobenzile in an alkaline medium, which
product serves for their manufacture.
1
3011
CM1 1000