Year: 1887

page_text: Date of Application, 3rd Sept., 1887
Complete Left, 31st May, 1888
Complete Accepted, 6th July, 1888
[Communicated from abroad by LA SOCIÉTÉ ANONYME DES MATIÈRES COLORANTES ET
PRODUITS CHIMIQUES DE ST. DENIS, ALOIDE FRANÇOIS POIRRIER, Manufacturer,
and DANIEL AUGuste Rosenstiehlɩ, 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 preparation of azoic colouring matters from nitro-
toluidine which, when pure, melts at 78° C. and from nitroxylidine which, when pure,
melts at 123° C. (Dictionnaire de Chimie de Würtz, Supplement, pages 1576 and
1665).
To these substances is applied the treatment described in the Provisional Specification
No. 9315 dated 30th June 1887, that is to say, whichever of the substances be treated,
the process consists in reducing the nitro-amine in an alkaline medium, subjecting tho
product of reduction to the action of nitrous acid, and combining the polyazoic
derivate thus obtained with certain substances such as the phenols, the oxyphenols,
the naphthols, the oxynaphthols, the primary, secondary or tertiary aromatic amines,
the diamines as well as the alkylic, sulphonic and carboxylic derivates of all these
substances.
The following are the processes in each case for preparing the reduction product
and the polyazoic derivate, and the modes of preparing the colouring matters from the
polyazoic derivate.

page_text: In 300 litres of water are introduced 2 kilos of nitrotoluidine. The mixture is
boiled and has added to it 15 kilos of zinc powder at 88% and 100 kilos. of caustic
soda ley of density 1.36. The zinc and soda are added in two doses with an hour's
interval. The whole is heated for 8 or 10 hours; it is then allowed to cool and is
filtered. The precipitate which is the product of reduction is purified by crystallisation
in alcohol. 12 kilos. of this are dissolved in 25 kilos of hydrochloric acid at 20° B.
and 600 litres of water; and to the solution, while it is kept cool, is added in small
doses a solution of 6.9 kilos. of nitrite of soda in 20 litres of water.
(b) Preparation of the colouring matters.
As an example, the following is the process for preparing the colouring matter
obtained with a-sulpho-a-naphthol.
The liquor containing the polyazoic derivate obtained from 12 kilos of the reduction
product has added to it 22.5 kilos of a-sulpho-a-naphthol in the state of soda salt and
10 kilos of carbonate of soda dissolved in 2000 litres of water. After quiescence for
several hours the material is precipitated by salt. There is thus obtained a red
colouring matter. By substituting for the a-sulpho-a-naphthol, equivalent quantities
of the following substances, analogous colouring matters are obtained with colours as
follows:-
-
B-sulpho--naphthol
a-sulpho-B-naphthol
Bisulphonaphthol (salt R)
Resorcine
Metaphenylenediamine ..
Naphthionic acid
B-naphthylamine sulphonic acid
a-naphthylamine
a
oxynaphthoic acid
Orange red
Orange red
-
Red
-
Red
-
Brown
-
Orange
-
Yellow
-
Red Brown
-
Brown.
II. PREPARATION OF COLOURING MATTERS DERIVED FROM NITROXYLIDINE
FUSIBLE AT 123°.
(a) Preparation of the reduction product.
To a boiling solution of 16.6 kilos of nitroxylidine in about 1300 litres of water
and 144 kilos 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 alcohol.
13.5 kilos of this reduction product are dissolved in 25 kilos of hydrochloric acid and
600 litres of water. The whole is cooled and has added to it in small doses 6.9 kilos of
nitrite of soda dissolved in 20 litres of water.
(b) Preparation of the colouring matters.
As an example, the following is the preparation of the colouring matter derived
from a-sulpho-a-naphthol.
The liquor containing the polyazoic derivate is poured into a solution of 22.5 kilos
of a-sulpho-a-naphthol and 10 kilos of carbonate of soda in 200 litres of water. After
several hours of quiescence the colouring matter is formed; it is easily precipitated by
salt; it dyes red.
By substituting for the a-sulpho-a-naphthol equivalent quantities of the following
substances, colouring matters of other tints are produced.
a-salpho-ẞ-naphthol
B-sulpho-B-naphthol
Bisulphonaphthol
Resorcine
Metaphenylenediamine
Naphthionic acid
B-naphthylamine sulphonic acid
a-naphthylamine
Orange
Orange
-
Bright red
Yellow
Brown
-
Orange Yellow
Orange
-
Brown,

page_text: The colouring matters obtained as above described possess among other properties
that of dyeing cotton in an alkaline bath, wool and silk in a bath acid, alkaline or
neutral, taking on to the various mordants or salts usually employed in dyeing.
The proportions of the reagents used may be varied.
Dated thin and date of Contember 1887
ABEL & IMRAY,
Agents for the Applicant.
1, 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 preparation of azoic colouring matters from nitro-
toluidine which, when pure, melts at 78° C., and from nitroxylidine which when
pure, melts at 123° C., (Dictionnaire de Chimie de Würtz Supplement, pages 1576
and 1665).
To these substances is applied the treatment described in the Provisional Specifi-
cation No. 9315 dated 30th June 1887, that is to say, whichever of the substances be
treated, the process consists in reducing the nitro-amine in an alkaline medium,
subjecting the product of reduction to the action of nitrous acid, and combining the
polyazoic derivate thus obtained with certain substances such as the phenols, the
oxyphenols, the naphthols, the oxynaphthols, the primary, secondary or tertiary
aromatic amines, the diamines as well as the alkylic, sulphonic and carboxylic derivates
of all these substances..
The following are the processes in each case for preparing the reduction product
and the polyazoio derivate, and the modes of preparing the colouring matters from
the polyazoic derivate..

page_text: The proportions of the reagents used may be varied.
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 :-
1. The herein described process for reducing in an alkaline medium nitrotoluidine
fusible at 78° C. and nitroxylidine fusible at 123° C.
2. The production and use of azoic colouring matters obtained by combining the
polyazoic derivate of the product of reduction of the nitrotoluidine or of the
nitroxylidine with phenols, oxyphenols, naphthols, oxynaphthols, primary, secondary
or tertiary amines, and diamines as well as with the alkylic, sulphonic and carboxylic
derivates of any of these bodies.
ABEL & IMRAY,
Agents for the Applicant.