Improvements in the Manufacture and Production of Derivatives of Diphenylamine Carboxylic Acid and Colouring Matters therefrom.
Year: 1899

page_text: Date of Application, 22nd Mar., 1899
Complete Specification Left 19th Dec 1200. Accoutod
4000
Improvements in the Manufacture and Production of Derivatives of
Diphenylamine 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) to be as follows:-
-
In the Specification of my application for Letters Patent of 14th March 1899
No. 5581 I have described various carboxylated derivatives of. oxydinitrodiphenyl-
amine, and the transformation of these compounds into black dyestuffs by treat-
ment with sodium sulphide and sulphur at a high temperature. My foreign
correspondents have now discovered that instead of the oxydinitrodiphenylamine
carbonic acids described in the Specification of the aforesaid application other
homologues may be employed.
Such homologues are obtained for instance by acting with chlordinitrobenzene
(:CI.NO,.NO, 1.2.4) upon the amidocresotinic acids of the following constitutions,

page_text: I designate these new compounds oxydinitrodiphenylamine carbonic acids D
and E.
They are prepared in the manner described for the preparation of the oxydini-
trodiphenylamine carbonic acid B in, the Specification of the aforesaid former
application.
EXAMPLE.
50 kilos of amido-ortho-cresotinic acid (:NH,. OH. COOH. CH, : 1.4.3.5 :) are
dissolved together with 36 kilos of sodium carbonate in 500 liters of hot water
and 60 kilos of chlordinitrobenzene are then added. The reaction commences
almost immediately and is completed by heating the mass to 95-100 degrees
Centigrade, whilst energetically agitated for two, or three hours. Towards the
end of the reaction the sodium salt of the new condensations-product begins to
separate out in brown crystals. After all the chlordinitrobenzene is absorbed,
the condensation product is filtered and pressed. The formation of the colouring
matter can be effected for example in the following manner: 100 kilos of crystal-
lised sodium sulphide are dissolved, with a small quantity of hot water, in a
pan, fitted with an agitator. 30 kilos of finely ground sulphur and 30 kilos of
sodium salt of the oxydinitrodiphenylamine carbonic acid D, are then added
and the temperature of the mass is afterwards (say within about 3 hours) raised
to about 150 degrees Centigrade. The melt is then kept at this temperature
until it is perfectly dry. It may then be ground and be directly used for dyeing.
It is a black powder readily soluble in water, the solution being greenish-black
and soluble in alcohol the solution being bluish-green. The colour of the
aqueous solution changes to blue-black on the addition of caustic soda. In
concentrated sulphuric acid the new dyestuff is soluble, the solution being dirty
blue. On the addition, of water it is precipitated. It dyes cotton from a salt
bath deep bluish-black of great fastness.
If the oxydinitrodiphenylamine carbonic acids be treated in the same manner
a dyestuff of very similar properties is obtained.
Dated this 22nd dor of Vorab 1800
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture and Production of Derivatives of
Diphenylamine 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-Rhine,
in the German Empire) and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement:-
In the Specification of my application for Letters Patent of 14th March 1899
No. 5581 I have described various carboxylated derivatives of oxydinitrodiphenyl-
amine, and the transformation of these compounds into black dyestuffs by treat-
ment with sodium sulphide and sulphur at a high temperature. My foreign
correspondents have now, discovered that instead. of the oxydinitrodiphenylamine
carboxylic acids described in the. Specification of the aforesaid application other
homologues may be employed. Such homologues are obtained for instance by

page_text: acting with chlordinitrobenzene (:CI. NO. NO,; 1.2.4:) upon the amidocre-
sotinic acids of the following constitutions:-
EXAMPLE.
50 kilos of amido-ortho-cresotinic acid (NH. OH. COOH. CH: 1. 4. 3. 5) are
dissolved together with 36 kilos of sodium carbonate in 500 liters of hot water
and 60 kilos of chlordinitrobenzene are then added. The reaction commences
almost immediately and is completed by heating the mass to 95-100 degrees
Centigrade, whilst energetically agitated for two, or three hours. Towards the
end of the reaction the sodium salt of the new condensations-product begins to
separate out in brown crystals. After all the chlordinitrobenzene is absorbed,
the condensation product is filtered and pressed. The formation of the colouring
matter can be effected for example in the following manner; 100 kilos of crystal-
lised sodium sulphide are dissolved, with a small quantity of hot water, in a
pan, fitted with an agitator. 30 kilos of finely ground sulphur and 30 kilos of
sodium salt of the oxydinitrodiphenylamine carboxylic acid I are then added,.
and the temperature of the mass is afterwards (say within about 3 hours) raised
to about 150 degrees Centigrade. The melt is then kept at this temperature
until it is perfectly dry. It may then be ground and be directly used for dyeing.
It is a black powder readily soluble in water, the solution being greenish-black
and soluble in alcohol the solution being bluish-green. The colour of the
aqueous solution changes to blue-black on the addition of caustic soda. In
concentrated sulphuric acid the new dyestuff is soluble, the solution being dirty

page_text: blue. On the addition of water it is precipitated. It dyes cotton from a salt
bath deep bluish-black of great fastness.
If the oxydinitrodiphenylamine carboxylic acid E be treated in the same
manner, a dyestuff of very similar properties is obtained.
Having now particularly described and ascertained the nature of the said 5
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The manufacture of the two new dinitrophenyloxytolylamine carboxylic
2. The manufacture of black substantive cotton dyes containing sulphur by
treating the dinitrophenyloxytolylamine carboxylic acids specified in the preced-
ing claiming clause with sodium sulphide and sulphur at a high temperature.
3. The products obtained by the processes claimed in the preceding claiming 20
clauses.
I'
. 1
1011
1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.