Manufacture of New Derivatives of Oxydiphenylamine.
Year: 1899

page_text: Date of Application, 11th Mar., 1899
Complete Specification Left, 17th Nov., 1899-Accepted, 23rd Dec., 1899
TROVISIONAL DILUITTUATION.
Manufacture of New Derivatives of Oxydiphenylamine.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, in the County of London, Consulting Engineer and Chartered Patent Agent,
do hereby declare the nature of this invention (as communicated to me from
abroad by Actien-Gesellschaft für Anilin-Fabrikation, of Berlin, in the Empire of
Germany, Chemical Manufacturers) to be as follows:-
My foreign correspondents have found that nitro-derivatives of oxydiphenyl-
aminesulphonic acids are obtained by allowing dinitrochlorobenzene (1:3: 4) or
sulphonic acids of ortho- or para-chloronitrobenzene to act upon para-amidophenol or
upon its sulphonic acids.
The products thus obtained can be used as wool-dyestuffs and may also be
transformed into valuable cotton-dyestuffs by treating them with sulphur and
sulphides of alkali metals.
The process for the production of the new derivatives of oxydiphenylamine is
illustrated by the following examples:
1.) Manufacture of dinitro-oxydiphenylamine-sulphonic acid from dinitrochloro-
benzene (13: 4) and para-amidophenol-ortho-sulphonic acid.
On
20.2 kilos. of dinitrochlorobenzene (1:3:4) are dissolved in 200 litres of alcohol.
Assolution of 80.9 kilos. of para-amidophenol-ortho-sulphonic acid, 5.5 kilos. of sodium
carbonate and 15 kilos. of sodium acetate in 100 litres of water is then added and the
mixture is boiled for several hours in a vessel connected with a reflux condenser.
cooling, the sodium salt of the new acid crystallizes from the solution. It forms in
air-dry state orange coloured leaflets, which at higher temperature are transformed
into brown-red crystals, having a darkish-green lustre. The new acid dissolves in
water with yellow colour, in concentrated sulphuric acid with brown-yellow colour
which becomes darker on heating.
Dinitro-oxydiphenylaminesulphonic acid obtained in the manner described dyes
wool in acid bath lemon-colour tints and yields yellowish-brown shades on
chromium-mordanted wool.
2.) Manufacture of nitro-oxydiphenylaninemonosulphonic acid from ortho-nitro-
chlorobenzene-para-sulphonic acid and para-amidophenol. 27, 6 kilos.of the potassium.
salt of ortho-nitrochlorobenzene-para-sulphonic acid and 10.9 kilos. of para-ainido-
phenol are heated in a closed vessel with 150 litres of water and 15 kilos. of calcium
carbonate for two and a half hours at 140° C. After cooling, the product of the
reaction separates in crystalline forin. It is again dissolved by heating- the mixture,
and is finally completely precipitated by means of potassium chloride, the calcium
carbonate having been previously removed by filtration.
The potassium salt of the new acid is thus obtained in the form of reddish-brown
crystals, which dissolve in water with brown-yellow colour and in concentrated sul-
phuric acid with blueish-violet colour. Nitro-oxydiphenylaminesulphonic acid dyes
wool in acid bath brownish-yellow tints, while on chromium-mordanted wool more
brown shades are obtained.

page_text: 3. MANUFACTURE OF NITRO-OXYDIPHENYLAMINESULPHONIC
ACID FROM PARA-NITRO-
CHLOROBENZENE-ORTHO-SULPHONIC ACID AND PARA AMIDOPHENOL.
By substituting in the preceding example for the potassium salt of ortho-nitro-
chlorobenzene-para-sulphonic acid the equivalent quantity of the potassium salt of
para-nitrochlorobenzene-ortho-sulphonic acid, the isomeric nitro-oxydiphenylamine-
sulphonic acid is obtained, which likewise separates in the form of reddish-brown
crystals of the potassium salt. It dyes wool in acid bath greenish-yellow tints and
yields brown shades on chromium-mordanted wool.
:
4. MANUFACTURE OF NITRO-OXYDIPHENYLAMINEDISULPHONIC ACID FROM ORTHO-NITRO-
CHLOROBENZENE-PARA-SULPHONIC ACID AND PARA-AMIDOPHENOL-ORTHO-SULPHONIC
ACID.
By substituting in the Example (2) for para-amidophenol the equivalent quantity
(21.1 kilos.) of the sodium salt of para-amidophenol-ortho-sulphonic acid, the corre-
sponding disulphonic acid of nitro-oxydiphenylamine is obtained, which separates in
the forin of yellow-brown crystals. These crystals dissolve in water with dark yellow
colour and in concentrated sulphuric acid with brown colour. Nitro-oxydiphenyl-
aminedisulphonic acid thus obtained dyes wool in acid bath orange-yellow tints on
chromium-mordanted wool more brownish shades are obtained.
PROM PARA-NITRO-
5. MANUFACTURE OF NITRO-OXYDIPHENYLAMINEDISULPHONIC ACID
CHLOROBENZENE-ORTHO-SULPHONIC ACID AND PARA-AMIDOPHENOL-ORTHO-SULPHONIC
ACID.
By substituting in Example (4) for ortho-nitrochlorobenzene-para-sulphonic acid
para-nitrochlorobenzene-ortho-sulphonic acid, the corresponding isomeric nitro-
oxydiphenylaminedisulphonic acid is obtained. It forms yellowish-brown crystals,
dissolving in water with yellow colour, in concentrated sulphuric acid with red-violet
colour. It dyes wool in acid bath lemon-colour tints; on chromium-mordanted wool
somewhat greener shades are obtained.
Dated this 11th day of March 1899.
COMPLETE SPECIFICATION.
Manufacture of New Derivatives of Oxydiphenylamine.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings, in
the County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (as communicated to me from abroad by
Actien-Gesellschaft für Anilin-Fabrikation, of Berlin in the Empire of Germany,
Chemical Manufacturers) and in what manner the same is to be performed to
be particularly described and ascertained in and by the following statement:-
My foreign correspondents have found that nitro-derivatives of oxydiphenyl-
aminesulphonic acids are obtained by allowing dinitrochlorobenzene (1:34) or
sulphonic acids of ortho- or para-chloronitrobenzene to act upon para-amidophenol
or upon its sulphonic acids.
The products thus obtained, can be used as wool-dyestuffs and may also be
transformed into valuable cotton-dyestuffs by treating them with sulphur and sulphides
of alkali metals.

page_text: The process for the production of the new derivatives of oxydiphenylamine. is
illustrated by the following examples:
of
1) Manufacture of dinitro-oxydiphenylaminesulphonic acid from dinitrochloro-
benzene (134) and para-amidophenol-ortho-sulphonic acid. 20.2 kilos. of dinitro-
chlorobenzene (1:3: 4) are dissolved in 200 litres of alcohol. A solution of 80.9 kilos.
para-amidophenol-ortho-sulphonic acid, 5.5 kilos. of sodium carbonate and 15 kilos.
of sodium acetate in 100 litres of water is then added and the mixture is boiled for
several hours in a vessel connected with a reflux condenser. On cooling, the sodium
salt of the new acid crystallizes from the solution. It forms in air-dry state orange
coloured leaflets, which at higher temperature are transformed into brown-red
crystals, having a darkish-green lustre. The new acid dissolves in water with yellow
colour, in concentrated sulphuric acid with brown-yellow colour which becomes darker
on heating.
Dinitro-oxydiphenylaminesulphonic acid obtained in the manner described dyes
wool in acid bath lemon-colour tints and yields yellowish-brown shades on chromium-
mordanted wool.
2) Manufacture of nitro-oxydiphenylaminemonosulphonic acid from ortho-nitro-
chlorobenzene-para-sulphonic acid and para-amidophenol. 27.6 kilos of the potassium
salt of ortho-nitrochlorobenzene-para-sulphonic acid and 10.9 kilos. of para-amido-
phenol are heated in a closed vessel with 150 litres of water and 15 kilos. of calcium
carbonate for two and a half hours at 140° C. After cooling, the product of the re-
action partly separates in crystalline form. It is again dissolved by heating the mix-
ture, and is finally completely precipitated by means of potassium chloride, the
calcium carbonate having been previously removed by filtration.
The potassium salt of the new acid is thus obtained in the form of reddish-brown
crystals, which dissolve in water to a brown-yellow solution and in concentrated
sulphuric acid to a blueish-violet solution. Nitro-oxydiphenylaminesulphonic acid
dyes wool in acid bath brownish-yellow tints, while on chromium-mordanted wool
more brown shades are obtained.
3. MANUFACTURE OF NITRO-OXYDIPHENYLAMINESULPHONIC
ACID FROM PARA-NITRO-
CHLOROBENZENE-ORTHO-SULPHONIC ACID AND PARA-AMIDOPHENOL.
By substituting in the preceding example for the potassium salt of ortho-nitro-
chlorobenzene-para-sulphonic acid the equivalent quantity of the potassium salt of
para-nitro-chlorobenzene-ortho-sulphonic acid, the isomeric nitro-oxydiphenylamine-
sulphonic acid is obtained, which likewise separates in the form of reddish-brown
crystals of the potassium salt. It dyes wool in acid bath greenish-yellow tints and
yields brown shades on chromium-mordanted wool.
4. MANUFACTURE OF NITRO-OXYDIPHENYLAMINEDISULPHONIC ACID FROM ORTHO-NITRO-
CHLOROBENZENE-PARA-SULPHONIC ACID AND PARA AMIDOPHENOL-ORTHO-SULPHONIC
ACID.
By substituting in the Example (2) for para-amidophenol the equivalent quantity
(21.1 kilos.) of the sodium salt of para-amidophenol-ortho-sulphonic acid, the-corre-
sponding disulphonic acid of nitro-oxydiphenylamine is obtained, which separates in
the form of yellow-brown crystals. These crystals dissolve in water with dark yellow
colour and in concentrated sulphuric acid with brown colour. Nitro-oxydiphenyl-
aminedisulphonic acid thus obtained dyes wool in acid bath orange-yellow tints on
chromium-mordanted wool more brownish shades are obtained.
5. MANUFACTURE OF NITRO-OXYDIPHENYLAMINEDISULPHONIC ACID
FROM PARA-NITRO-
CHLOROBENZENE-ORTHO-SULPHONIC ACID AND PARA-AMIDOPHENOL-ORTHO-SULPHONIC
ACID.
By substituting in Example (4) for ortho-nitrochlorobenzene-para-sulphonic acid
nara-nitrochlorobenzene-ortho-sulphonic acid the corresponding isomeric nitro-xx-

page_text: diphenylamine-disulphonic acid is obtained. It forms yellowish-brown crystals, dis-
solving in water with yellow colour, in concentrated sulphuric acid with red-violet
colour. It dyes wool in acid bath lemon-colour tints; on chromium-mordanted wool
somewhat greener shades are obtained.
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 manufacture of nitro-derivatives of oxydiphenylamine-
sulphonic acids
a) by allowing dinitrochlorobenzene (1:3:4) to act upon para-amidophenol
sulphonic acids or
b) by allowing sulphonic acids of ortho- or para-chloronitrobenzene to act
upon para-amidophenol or its sulphonic acids.
2. The nitro-derivatives of oxydiphenylaminesulphonic acids manufactured as
herein described.
Dated this 17th day of November 1899
ABEL & IMRAY,
Agents for the Applicant.