The Manufacture and Production of New Derivatives of Diphenyl- amino Carboxylic Acid and Colouring-matters therefrom.
Year: 1899

page_text: Date of Application, 14th Mar., 1899
Complete Specification Left, 14th Dec., 1899-Accepted, 20th Jan., 1900
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Derivatives of Diphenyl-
amino Carboxylic Acid and Colouring-matters therefrom.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention, which has been
communicated to me by Kalle & Co., of Biebrich on the Rhine, in the German
Empire, to be as follows:-
Certain hydroxydinitrodiphenyl aminocarboxylic acids yield very valuable colouring
matters when fused with sodium sulphide and sulphur. The said colouring matters
have the property of dyeing unmordanted cotton pure black, or shades of violet-
black, from brine baths containing a little soda and sodium sulphide. The colours
produced in this manner are increased in intensity and purity by subsequent treat-
ment with metallic salts, such as fluor-chrome, or copper sulphate.
The hydroxydinitrodiphenyl aminocarboxylic acids required for the production of
these colouring matters are obtained in the following manner :
1. Chlorodinitrobenzoic acid, melting at 199-200°, (obtained by nitrating ortho-
chlorobenzoic acid dissolved in sulphuric acid with 2 molecular proportions of nitric
acid, or of a nitrate), is allowed to act on the equivalent quantity of paramido phenol,
dissolved in a neutral medium, in the presence of a salt having alkaline action, or of
soda. This gives rise to a hydroxydinitrodiphenyl aminocarboxylic acid in which
the COOH group and the OH group are in the two different benzene rings united by
the NH group.
This new compound is subsequently referred to as hydroxydinitro-
diphenyl aminocarboxylic acid A.
2. 1:2:4-chloro dinitrobenzene is allowed to act on paramido salicylic acid
(OH: COOH: NH₁=1: 2: 4) under the conditions herein before described in
paragraph 1; in this way there is formed a hydroxydinitrodiphenylaminocarboxylic
acid of the constitution
hereinafter referred to as hydroxydinitrodiphenylaminocarboxylic acid B.
3. If dinitrochlorobenzene be replaced by dinitrochlorotoluene (CH: Cl: NO₂:
NO, 1: 2: 3: 5) there is formed a dinitrotolylhydroxydiphenylaminocarboxylic
acid of the constitution

page_text: HYDROXYDINITRODIPHENYLAMINOCARBOXYLIC ACID C
.
- is obtained.
The free acids of the three different hydroxydinitrodiphenylaminocarboxylic acids
. dissolve with great difficulty in cold and hot water, but are more readily soluble in
hot alcohol, from which they crystallise in yellowish-brown needles. The acids form
with the alkali metals, stable salts obtained by dissolving them in the equivalent
quantity of caustic alkali, or alkali carbonate. The sodium salts dissolve readily in
hot water but less readily in cold water, and can be readily obtained in crystalline
form.
.: The conversion of these condensation products into colouring matters by fusion
with sulphur and sodium sulphide can be effected as follows:
In a boiler placed in an oil-bath, 200 kilograms of crystallized sodium sulphide are
dissolved in a small quantity of hot water. Seventy-five kilograms of flowers of
sulphur, and 100 kilograms of the sodium salt of hydroxydinitrodiphenylaminocar-
boxylic acid A, are then added to the stirred liquid. The temperature of the oil-bath
is raised so that in from 3 to 4 hours the temperature of the melt reaches 140-1500.
This temperature is then maintained until the mass becomes quite dry and friable.
It is allowed to cool, and is then broken up, when it can be used for dyeing. It
forms a powder with pale bronzey lustre which is readily soluble in water forming a
greenish-black solution and sparingly soluble in alcohol forming a dirty, greenish
blue solution. The aqueous solution of the colouring matter becomes bluish-black
when treated with concentrated caustic soda. Hydrochloric acid precipitates the dye
in black flocks. The new substance forms a greenish-blue solution in sulphuric acid,
the addition of water causing a black precipitate. Cotton is dyed deep black in a
brine bath, the colours being very pure, and gaining in depth of tone and in purity,
by subsequent treatinent with metallic salts.
If
hydroxydinitrodiphenylaminocarboxylic acid B be treated as described in this
example, a dye is produced which colours cotton shades of bluish-black. In using
this hydroxydinitrodiphenylaminocarboxylic acid the dye is produced in the melt
at 150°, and its formation proceeds somewhat rapidly.

page_text: Application of hydroxydinitrodiphenylaminocarboxylic acid C gives rise to a
brownish-violet dye in the form of a dark brown powder, which dissolves readily in
water, but with difficulty in alcohol. The solution in concentrated sulphuric acid is
dirty violet, and on treatment with water yields a dark violet precipitate.
In conducting the fusion it is not necessary to observe the above weights or
temperatures, which are mentioned merely as an example of the way in which the
process can be made technologically successful.
A
1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Derivatives of Diphenyl-
amino Carboxylic Acid and Colouring matters therefrom.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of
London, Patent Agent, do hereby declare the nature of this invention (which has
been communicated to me from abroad by Kalle & Co., of Biebrich-on-the-Rhine, in
the German Empire), and in what inanuer the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
Certain hydroxydinitrophenylamine-carboxylic acids yield very valuable colouring
matters when fused with sodium sulphide and sulphur. The said colouring matters
have the property of dyeing unmordanted cotton pure black, or shades of violet-black,
from brine baths containing a little soda and sodium sulphide. The colours produced
in this manner are increased in intensity and purity by subsequent treatment with
metallic salts, such as fluor-chrome, or copper sulphate.
The hydroxydinitrodiphenylaminocarboxylic acids required for the production of
these colouring matters are obtained in the following manner.
1. Chlorodinitrobenzoic acid, melting at 199-200° (obtained by nitrating ortho-
chlorobenzoic acid dissolved in sulphuric acid with 2 molecular proportions of nitric
acid, or of a nitrate), is allowed to act on the equivalent quantity of paramidophenol,
dissolved in a neutral medium, in the presence of a salt having alkaline action, or of
soda. This gives rise to a hydroxydinitro-diphenylaminocarboxylic acid in which the
COOH. group and the OH group are in the two different benzene rings united by
the NH group. This new compound is subsequently referred to as hydroxydinitro-
diphenylaminocarboxylic acid A.
2.
12:4-chloro-dinitrobenzene is allowed to act on paramidosalicylic acid
(OH: COOH NH₂ = 1: 2: 4) under the conditions hereinbefore described in
paragraph 1, in this way there is formed a hydroxydinitro-diphenylaminocarboxylic
acid of the constitution

page_text: The following is a detailed description of the method of preparing the hydroxy-
dinitrodiphenylaminocarboxylic acids but I do not limit myself to the precise details
HYDROXYDINITRO-DIPHENYLAMINOCARBOXYLIC ACID C

page_text: Application of bydroxydinitrodiphenylamino-carboxylic acid C gives rise to a
brownish-violet dye in the form of a dark brown powder, which dissolves readily in
water, but with difficulty in alcohol. The solution in concentrated sulphuric acid
is dirty violet, and on treatment with water yields a dark violet precipitate.
In conducting the fusion it is not necessary to observe the above weights or tem-
peratures, which are mentioned merely as an example of the way in which the pro-
cess can be made technologically successful.
Having now particularly described and ascertained the nature of this
invention and in what manner the same is to be performed I declare that what I
claim is:-
་
1. The manufacture of a new oxydinitro-diphenylamine carboxylic acid by acting
with the chlorodinitrobenzoic acid fusing at 199-200 degrees Centigrade (cf. German
Patent No. 106510) on para-amidophenol in presence of a salt having an alkaline
action, substantially as hereinbefore described.
2. The manufacture of violet-black to blue-black substantive cotton dyes containing-
sulphur by fusing the following oxydinitrodiphenylamine carboxylic acids:
with sodium sulphide and sulphur substantially as hereinbefore described.
3. The products obtained by the processes claimed in the preceding claiming
clauses.
Tatad this 11th dow of Desambar 1800
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.