and Reduction of Certain Nitro Compounds for that Purpose.
Year: 1887

page_text: Date of Application, 30th June, 1887
Complete Left, 29th Mar., 1888
Complete Accepted, 18th May, 1888
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIERES COLORANTES ET
PRODUITS CHIMIQUES DE ST. DENIS, ALCIDE FRANÇOIS POIRRIER, Manufacturer,
and DANIEL AUGUSTE ROSENSTIEHL, Chemist, all of 105, Rue Lafayette,
Paris, France.]
and Reduction of Certain Nitro Compounds for that Purpose.
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 azoic yellow, orange and red colouring
matters derived either from metanitraniline, or from nitrotoluidine fusible at 107°.
Whichever of those substances be employed, the process always consists in reducing
it in an alkaline medium, in subjecting it to the action of nitrous acid and combining
the polyazoic derivate thus obtained with certain substances such as phenols,
oxyphenols, primary amines or secondary or tertiary amines, diamines or the
alkylic sulphonic or carboxylic derivates of these substances.
The following is a description in the two cases of the process of preparing the
product of reduction and the polyazoic derivate, and the mode of preparing
colouring matters with this derivate.
Preparation of the colouring matters derived from metanitraniline.
Preparation of the product of reduction of metanitraniline and preparation of the
Dolvazoic derivate.

page_text: 13.8 Kilo of metanitraniline are dissolved in 1100 litres of boiling water. Into
this solution are poured 144 Kilo. of caustic soda ley at 36° B. The mixture is
heated to boiling and has added to it carefully in small doses 19 Kilo. of zinc
powder. A yellow precipitate is formed which is the product of reduction almost
pure. Purification is completed by simple crystallisation in water mixed with 5
hydrochloric acid 106 Kilo. of this reduction product are dissolved in 25 Kilo.
of hydrochloric acid at 20° B. and 600 litres of water. The solution is cooled
and has added to it in small doses a solution of 6.9 Kilo. of nitrite of soda in
three times the quantity of water.
Preparation of the colouring matters.
As examples, are given preparations of the colouring matters obtained with
alphasulphoalphanaphthol, and with metaphenylenediamine.
Alphasulphoalphanaphthol. The liquor containing the polyazoic derivate has
added to it 225 Kilo. of alphasulphoalphanaphthol in the state of soda salt, and
10 Kilo. of carbonate of soda dissolved in 2000 litres of water. After quiescence
precipitation is effected with salt. The red colouring matter obtained as well as
all those to which this Specification relates, has, among other dyeing properties,
that of dyeing cotton without mordant, in an alkaline bath.
By substituting for the alphasulphoalpbanaphthol an equivalent quantity of the
following substances, colouring matters are obtained having like dyeing properties,
giving the following tints.
Alphanaphthol -
Bisusulphobotanaphthol or Alphanaphthylamine -
Betanaphthol, Alphasulphobetanaplithol, Naphthionic acid,
Betanaphthylamine sulphonic acid
Salicylic or Anthranilic acid, Phenol, Resorcine -
red
red
orange
yellow.
Metaphenylenediamine. The liquor containing the polyazoic derivate has added
to it a solution of 10-8 Kilo. of metaphenylenediamine in 1000 litres of water,
and enough carbonate of soda to render the solution slightly alkaline after reaction.
The colouring matter, precipitated by salt dyes cotton yellow.
Preparation of the colouring matters derived from nitrotoluidine.
a) Preparation of the product of reduction, of nitrotoluidine and preparation of the
polyazoic derivate.
The operation is like that for metanitraniline. To a boiling solution of 15-2 Kilo.
of nitrotoluidine in about 1200 litres of water and 144 Kilo. of caustic soda ley at
36° B. are added in small doses 19 Kilo. of zinc powder. A yellow precipitate is
formed which is purified by crystallisation in water mixed with hydrochloric acid.
8 Kilo. of this reduction product are dissolved in 25 Kilo. of hydrochloric acid, and
the solution is diluted with water to 600 litres volume. As this solution cools it has
added to it in small doses 4.7 Kilo of nitrite of soda dissolved in 15 litres of water.
b) Preparation of colouring matters.
Into the solution of the polyazoie derivate are poured 16.3 Kilo of alphasulpho-
alphanaphthol in a state of soda salt dissolved in 2000 litres of water and 100 Kilo.
of carbonate of soda are added. After reaction the colouring matter is readily
precipitated with salt; it dyes cotton red.
Operating in the same way with equivalent quantities of the following substances,
analogous colouring matters are obtained, as follows
Alpha and Betanaphthols give
Bisulphobetanaphthol
gives
Alphasulphobetanaphthol „
Naphthionic acid
Phenol and Resorcine
"
"
"
11
-
brown colour
red
"
orange "
orange
"
yellow
"

page_text: All the colours referred to herein, except those from alpha and betanaphthol, are
soluble in water. But by treating those in the known manner with sulphuric acid,
they can be obtained as sulphonic combinations which are soluble and have dyeing
properties similar to those above described.
The proportions of the reagents, and the nature of the reducing agent may be
.varied.
D. B011 1
0
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Yellow, Orange, and Red Azoic Coloring Matters,
and Reduction of Certain Nitro Compounds for that Purpose.
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 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 the manufacture of azoic yellow, orange and red coloring
matters derived either from meta-nitraniline, or from nitrotoluidine fusible at 107°.
Whichever of those substances be employed, the process always consists in reducing
it in an alkaline medium, in subjecting it to the action of nitrous acid and combining
the polyazoic derivate thus obtained with certain substances, such as phenols,
oxyphenols, primary amines or secondary or tertiary amines, diamines, or the alkylic,
sulphonic or carboxylic derivates of these substances.
The following is a description in the two cases in the process of preparing the product
of reduction and the polyazoic derivate, and the mode of preparing coloring matters
with this derivate.
Preparation of the coloring matters derived from metanitraniline.
(a) Preparation of the product of reduction of metanitraniline and preparation of
the polyazoic derivate.
138 kilos. of metanitraniline are dissolved in 1100 litres of boiling water. Into
this solution are poured 144 kilos. of caustic soda ley at 36° B. The mixture is heated
to boiling and has added to it carefully in small doses 19 kilos. of zinc powder. A
yellow precipitate is formed which is the product of reduction almost pure. Puri-
fication is completed by simple crystallisation in water mixed with hydrochloric acid.
10.6 kilos. of this reduction product are dissolved in 25 kilos. of hydrochloric acid

page_text: at 20° B. and 600 litres of water. The solution is cooled and has added to it in
small doses a solution of 6-9 kilos of nitrite of soda in three times the quantity of
water.
(b) Preparation of the coloring matters.
As examples, are given preparations of the coloring matters obtained with alpha-
sulphoalphanaphthol, and with metaphenylenediamine. Alphasulphoalphanaphthol.
The liquor containing the polyazoic derivate has added to it 22.5 kilos. of alpha-
sulphoalphanaphthol in the state of soda salt, and 10 kilos. of carbonate of
soda dissolved in 2000 litres of water. After quiescence, precipitation is effected
with salt.
The red coloring matter obtained, as well as all those to which this specification
relates, bas, among other dyeing properties, that of dyeing cotton without mordant,
in an alkaline bath.
By substituting for the alphasulphoalphanaphthol an equivalent quantity of the
following substances, coloring matters are obtained having like dyeing properties,
giving the following tints:
Alphanaphthol -
Bisulphobetanaphthol or alphanaphthylamine
Betanaphthol, alphasulphobetanaphthol, naphthionic acid,
betanaphthylaminesulphonic acid
Salicylic or anthranilic acid phenol, resorcine
red
rod
-}
orange
yellow.
Metaphenylaminediamine. The liquor containing the polyazoic derivate has added
to it a solution of 108 kilos. of metaphenylenediamine in 1000 litres of water, and
enough carbonate of soda to render the solution slightly alkaline after reaction.
The coloring matter, precipitated by salt, dyes cotton yellow.
Preparation of the coloring matters derived from nitrotoluidine.
(a) Preparation of the product of reduction of nitrotoluidine and preparation of
the polyazoic derivato.
The operation is like that for metanitraniline. To a boiling solution of 15.2 kilos.
of nitrotoluidine in about 1200 litres of water and 144 litres of caustic soda ley
at 36° B. are added in small doses 19 kilos. of zinc powder. A yellow precipitate is
formed which is purified by crystallisation in water mixed with hydrochloric acid.
8 kilos. of this reduction product are dissolved in 25 kilos. of hydrochloric acid, and
the solution is diluted with water to 600 litres volume. As this solution cools
it has added to it in small doses 4-7 kilos. of nitrite of soda dissolved in 15 litres of
water.
(b) Preparation of coloring matters.
Into the solution of the polyazoic derivate, are poured 16-3 kilos. of alphasulpho-
alphauaphthol in a state of soda salt dissolved in 2000 litres of water and 100 kilos. of
carbonate of soda are added. After reaction the coloring matter is readily precipitated
with salt; it dyes cotton red.
Operating in the same way with equivalent quantities of the following substances,
analogous coloring matters are obtained as follow :-
Alpha and betanaphthols give
Bisulphohetanaphthol
Alphasulphobetanaphthol
Naphthionic acid
Phenol and resorcine
gives-
"
"
""
brown color
red color
orange "
yellow
3
"
These colors, as well as those obtained from nitraniline, possess, among other dyeing
properties, that of dyeing cotton without mordant, in an alkaline bath.
All the colors referred to herein, except those from alpha and betanaphthol, are
soluble in water. But by treating those in the known manner with sulphuric acid,
they can be obtained as sulphonic combinations which are soluble and have dyeing
properties similar to those above described.

page_text: The proportions of the reagents and the nature of the reducing agent 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, I declare that what I
claim is
1. The herein described process of reducing metanitraniline and nitrotoluidine in
an alkaline medium.
2. The application of the products of the reduction referred to in the preceding
claim to the manufacture of azoic coloring matters by combining the polyazoic
derivate of the product of reduction of metanitraniline or of nitrotoluidine with
phenols, oxyphenols, naphthols, oxynaphthols, primary, secondary or tertiary aminés,
diamines or the alkylic, sulphonic or carboxylic derivates of any of these substances,
substantially as herein described.
3. As new products, the coloring matters obtained as above described as well as the
new products which serve for their manufacture, namely the reduction products of
metanitraniline and nitrotoluidine and their polyazoic derivates.
ABEL & IMRAY,
Agents for the Applicant.