The Manufacture or Preparation of Paradiamidodiphenylamine- carboxylic Acid, and of Colouring Matters therefrom.
Year: 1898

page_text: Date of Application, 8th Dec., 1898
Complete Specification Left, 23rd Aug., 1899-Accepted, 23rd Sept., 1899
PROVISIONAL SPECIFICATION.
The Manufacture or Preparation of Paradiamidodiphenylamine-
carboxylic Acid, and of Colouring Matters therefrom.
1, 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) to be as follows:-
Carboxylic derivatives of diphenylamine have not hitherto found technical applica-
tion and are but slightly known in scientific literature. In the "Annals of
Chemistry "(Annalender Chemie, Vol. 279, p. 270) a nitro-p-tolylanthranilic acid and
an amido-p-tolylanthranilic acid are described, but so far these have remained
unnoticed industrially. By nitrating orthochloro benzoic acid, and condensing the
product with paraphenylenediamine my foreign correspondents have succeeded in
preparing by a very convenient method, a nitroamidodiphenylaminecarboxylic acid,
which yields, on reduction, an extremely valuable paradiamidodiphenylaminecarboxylic
acid.
The following is an example of the preparation of the new compound but I do not
Forty-five kilograms of sodium chloro-nitrobenzoate (Cl: NO, COOH = 1:46)
with 22 kilograms of paraphenylenediamine and 12 kilograms of calcined carbonate
of soda, or an equivalent quantity of a compound capable of fixing the liberated
hydrochloric acid, are dissolved in 500 litres of water, and the solution is boiled for
five hours in a reflux apparatus. On cooling, the sodium salt of nitroamidodiphenyl-
amine-carboxylic acid separates in lustrous, brown needles. On acidifying, the free
carboxylic acid is obtained as a yellow precipitate, which is somewhat soluble in hot
water.
Fifty kilograms of the free nitroamido-diphenylaminecarboxylic acid are reduced
with 50 kilograms of iron filings, 3000 liters of water and 5 kilograms of acetic acid.
When reduction is complete, sodium carbonate is added until the liquid is alkaline,
it is then filtered, and carefully acidified with hydrochloric acid, which precipitates the
free diamido-carboxylic acid. It is all redissolved on adding further quantities of
hydrochloric acid, forming the hydrochloride, which is precipitated on adding excess
of hydrochloric acid. The new diamido-diphenylamine carboxylic acid is somewhat
readily soluble in hot water, crystallizing in sinall needles, and it forms stable salts
with mineral acids, the hydrochloride is readily soluble in water and the sulphate
dissolves more sparingly. The new carboxylic acid is converted into a readily. soluble
tetrazo-compound under the influence of nitrous acid, but a monodiazo-compound
with a free-amido-group may be also obtained. In virtue of this property of yielding
a tetrazo-compound as well as a diazo compound under the influence of nitrous acid,
paradiamidodiphenylaminecarboxylic acid forms a suitable initial material for the
CD 077

page_text: preparation of mono- and disazo colouring matters. The latter, in particular, are
especially valuable, because in clearness and purity of tone, as well as in strength of
colour, they surpass the analogous colouring matters from other paradiamines
The preparation of the new dyes are illustrated by the following examples.
The preparation of the new dyes are illustrated by the following examples.
EXAMPLE 1.
31.6 kilograms of diamidodiphenylaminecarboxylic acid hydrochloride are dissolved
in 500 liters of water, cooled with ice, and treated with 30 kilograms of hydrochloric
acid and 14 kilogrames of nitrite. When the nitrite has been used up, the tetrazo
compound is run into a cooled, aqueous solution of 0 kilograms of sodium 1:4-naphthol-
sulphonate and 40 kilograms of carbonate of soda. A reddish violet intermediate 1
compound is first formed, and is converted into the blue tetrazo dye after 12 hours
agitation. The colouring matter is precipitated by salt from the warmed liquid. It
dyes unmordanted cotton blue in the brine bath. A red colouring matter is obtained
by replacing naphtholsulphonic acid with naphthionic acid, and a violet-red dye is
produced by employing metanaphthylenediaminesulphonic acid.
1
EXAMPLE 3.
The tetrazo-compound prepared according to Example 1 is run into a cold, dilute
solution of sodium carbonate, and immediately treated with 25 kilograms of sodium
1 : : 4-naphtholsulphonate and 10 kilograms sodium carbonate. The intermediate
product is formed after some time, when an alkaline solution of 36 kilograms of
amidonaphtholdisulphonic acid H is added to it. When the combination is complete,
the colouring matter is isolated in the customary way; it dyes cotton blue.
EXAMPLE 4.
31.6 kilograms of diamidodiphenylaminecarboxylic acid hydrochloride are converted
into the tetrazo-compound according to Example 1, and rendered feebly alkaline by
means of a cold, dilute solution of sodium carbonate. To this liquid is immediately
added, with agitation, a solution of 24 kilograms of amidonaphtholsulphonic acid Ġ
and 11 kilograms of sodium carbonate. The intermediate product is at once formed
and is only partly precipitated. On treating it with an alkaline solution of 35 kilo-
grams of amidonaphtholdisulphonic acid K, it gradually becomes redissolved, and,
when combination is complete, a colouring matter is obtained which dyes unmordanted
cotton blue-black. The K-acid can be replaced by other amidonaphtholsulphonic
acids, phenols, amines, or their derivatives.
The mixed dye from one molecular proportion of diamido-diphenylaminecarboxylic

page_text: Instead of combining the tetrazo compound obtained according to Example 5 with
two molecular proportions of toluylene diamine to form a simple dye, it can also be
united with two molecular proportions of different substances with the production of
very valuable colouring matters. The process closely resembles those of Examples 3
and 4.
The mixed colouring matter from the further diazotised intermediate compound of
equal molecular proportions of diamido-diphenylaminecarboxylic acid and amido-
naphtholsulphonic acid G (gamina acid) with the following substances dyes cotton as
indicated:
1 molecular proportion of gamına acid, and
1
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1
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1
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دو
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1
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toluylene-diamine
"gamma acid, and
"
metanaphthylene-di-
amine sulphonic acid
"gamma acid, and
B-oxynaphthoic acid
toluylenediamine, and
B-oxynaphthoic acid
وو
2 2 2 2 2 :
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"
, toluylenediamine, and
metanaphthylene-di-
aminesulphonic acid
black.
blue-black.
blue-black.
black.
blue-black.

page_text: If the intermediate compound obtained according to Examples 5 and 6 from
diamidodiphenylamine-carboxylic acid and amidonaphtholsulphonic acid G be
replaced by the intermediate compounds from the same diamido base with a-naphthyl-
amine or its ẞ- or B-sulphonic acid, there are likewise obtained colouring-inatters
of exactly similar character with but slightly modified shade.
Dated this 8th day of December 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
Forty five kilograms of sodium chloronitrobenzoate (Cl: NO₂: COOH = 1:4: 6)
with 22 kilograms of paraphenylenediamine and 12 kilograms of calcined carbonate
of soda, or an equivalent quantity of a compound capable of fixing the liberated
hydrochloric acid (for instance sodium acetate) are dissolved in 500 liters of water,
and the solution is boiled for five hours in a reflux apparatus. On cooling, the sodium
salt of nitroamidodipdenylaminecarboxylic acid separates in lustrous, brown needles.
On acidifying, the free carboxylic acid is obtained as a brownish precipitate, which is
somewhat soluble in hot water.
Fifty kilograms of the free nitroamidodiphenylaminecarboxylic acid are reduced
with 50 kilograms of iron filings, 3000 liters of water and 5 kilograms of acetic acid.
When reduction is complete, sodium carbonate is added until the liquid is alkaline,
it is then filtered, and carefully acidified with hydrochloric acid, which precipitates
the free diamidocarboxylic acid. It is all redissolved on adding further quantities
of hydrochloric acid, forming the hydrochloride, which is precipitated on adding
excess of hydrochloric acid. The new diamidodiphenylamine carboxylic acid is some-
what readily soluble in hot water, crystallizing in small needles, and it forms stable
salts with mineral acids, the hydrochloride is readily soluble in water and the sulphate
dissolves more sparingly. The new carboxylic acid is converted into a readily soluble
tetrazo-compound under the influence of nitrous acid, but a monodiazo-compound
with a free amido group inay be also obtained. In virtue of this property of yielding

page_text: a tetrazo compound as well as a diazo compound under the influence of nitrous acid,
paradiamidodiphenylamine carboxylic acid forins a suitable initial material for the
preparation of mono- and disazo-colouring matters. The latter, in particular, are
especially valuable, because in clearness and purity of tone, as well as in strength of
colour, they surpass the analogous colouring matters from other paradiamines.
The preparation of the new dyes are illustrated by the following examples.
316 kilograms of diamidodiphenylaminecarboxylic acid hydrochloride are dissolved
in 500 liters of water, cooled with ice, and treated with 30 kilograms of hydro-
chloric acid and 14 kilograms of nitrite. When the nitrite has been used up, the
tetrazo compound is run into a cooled, aqueous solution of 50 kilograms of sodium
14-naphtholsulphonate and 40 kilograms of carbonate of soda. A reddish violet
intermediate compound is first formed, and is converted into the blue tetrazo dye
after 12 hours agitation. The colouring matter is precipitated by salt from the
warmed liquid. It dyes unmordanted cotton blue in the brine bath. A red colouring
matter is obtained by replacing naphtholsulphonic acid with naphthionic acid, and a
violet-red dye is produced by employing metanaphthylenediaminesulphonic acid.
to
The solution of tetrazodiphenylaminecarboxylic acid prepared according
Example is run into a cooled solution of 70 kilograins of amidonaphthol-
disulphonic acid K and 45 kilograms of carbonate of soda. The coupling is complete
after 12-20 hours agitation. The dye is isolated in the usual way, and colours
unmordanted cotton pure blue.
"
AIR
aidwexa
SILLO
Sun

page_text: EXAMPLE 6.
Instead of combining the tetrazo compound obtained according to Example 5 with
two molecular proportions of toluylenediamine to form a simple dye, it can also be
united with two molecular proportions of different substances with the production of
very valuable colouring matters. The process closely resembles those of Examples 3
and 4.
The inixed colouring matter from the further diazotised intermediate compound of
equal molecular proportions of diamidodiphenylaminecarboxylic acid and amido-
naphtholsulphonic acid G (gamma-acid) with the following substances dyes cotton as
indicated:
1 molecular proportion of gamma acid, and
1 molecular proportion of toluylenediamine
1 molecular proportion of gamma acid, and
1
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"
1
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1
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1
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1
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,,netanaphthylene-di-
aminesulphonic acid
"gamma acid, and
beta-oxynaphthoic acid
"
,, toluylenediamine, and
,, metanaphthylene-di-
aminesulphonic acid
» toluylenediamine and
"
"
"
"
"
beta-oxynaphthoic acid}
-
black.
blue black.
blue black.
blue black.
black.

page_text: If the intermediate compound obtained according to Examples 5 and 6 from
diamidodiphenylamine carboxylic acid and amidonaphtholsulphonic acid G be
replaced by the intermediate compounds from the same diamido-base with a-naphthyl-
amine or its 8 or ẞ-sulphonic acid, there are likewise obtained colouring-matters
of exactly similar character with but slightly modified shade.
Having now described this invention and in what manner the same is to be
carried out I declare that what I claim is :-
1. The manufacture of para-diamidodiphenylamineortho-carboxylic acid by heating
chloronitrobenzoic acid (Cl.NO,COOH 1, 4, 6) in solution together with para-
phenylenediamine and in the presence of a compound capable of fixing the hydro-
chloric acid liberated during the reaction.
2. The manufacture of substantive cotton dyes by combining the tetrazo compound
derived from para-diamidodiphenylamine-ortho-carboxylic acid with two molecular
proportions of an amine, phenol, amidophenol, or of a sulphonic-, or carboxylic, acid
of the same, or with one molecular proportion of each of two different compounds
belonging to the before named classes of chemical bodies.
3. The manufacture of substantive cotton dyes by combining the tetrazo com-
pound derived from para-diamidodiphenylamine-ortho-carboxylic acid with one
molecular proportion of an amine suitable for further diazotation (alpha-naphthyl-
amine, alpha-naphthylamine-ẞ- or B-sulphonic acid, or gamma-amidonaphthol-
sulphonic acid), rediazotizing the intermediate body obtained, and combining with
two molecular proportions of an amine, phenol, amidophenol, or of a sulphonic, or
carboxylic, acid of the same, or with one molecular proportion of each of two different
compounds belonging to the before named classes of chemical bodies.
Dated this 23rd day of August 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.