New Carboxylated Derivatives of Amido or Hydroxy-tri-phenyl- methanes.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
New Carboxylated Derivatives of Amido or Hydroxy-tri-phenyl-
methanes.
I, HENRI RAYMOND VIDAL, of 95, Boulevard Beaumarchais, Paris, in the Republic
of France, do hereby declare the nature of this invention to be as follows:-
This invention relates to the production of new carboxylated derivatives of amido-
or hydroxy-tri-phenyl-methanes.
I obtain these products in the following manner: I heat for twenty four hours in
an oil bath, in a cauldron of enamelled cast iron-
Salicylic acid
-
-
Phenol
Oxalic acid
Sulphuric acid
-
-
-
13 kilogrammes
20
25
"
-
15
ور
The product thus obtained is poured into ten times its weight of water and treated
by a current of steam which carries off the excess of phenol. The water is poured off
and the product is purified by a dissolution in its weight of meta-bisulphite of soda
diluted with ten times its weight of water.
The colouring matter is precipitated from its solution in the meta-bisulphite by the
sulphuric acid. The sulphurous acid is driven off by ebullition.
The colouring matter is separated by filtration and desiccated.
This product constitutes the mono-carboxylated derivative of aurin.
The di- and tri-carboxylated products are obtained in the same manner by merely
changing the proportions of the salicylic acid and phenol.
For the di- carboxylated acid I employ:

page_text: obtain products in which the phenolic functions are replaced either wholly or in part
by amido functions.
The acids oxy- and amido-cinnamic react in the same conditions.
In all the preceding reactions, I may substitute for sulphuric acid and oxalic acid
as condensing agents, chloride of zinc and formic acid.
The mono- and di-carboxylated products constitute, in the acid state, products of a
bright yellow, and in the state of salts, products of a very bright scarlet red.
The colouration of tri-carboxylated products tends towards a dark red.
Dated this 2nd day of March 1907
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
COMPLETE SPECIFICATION.
New Carboxylated Derivatives of Amido or Hydroxy-tri-phenyl-
methanes.
I, HENRI RAYMOND VIDAL, of 95, Boulevard Beaumarchais, Paris, in the Republic of
France, 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 production of new carboxylated products derived from
amido or phenolic compounds and amides and phenolics of tri-phenyl-methane.
I obtain these products in the following manner:
I heat for twenty four hours in an oil bath, in a cauldron of enamelled cast iron-
Salicylic acid
Phenol
-
Oxalic acid
Sulphuric acid
-
13 kilogrammes
20
"
25
15
"
The product thus obtained is poured into ten times its weight of water and heated
by a current of steam which carries off the excess of phenol. The water is poured
off and the product is purified by a dissolution in its weight of meta-bisulphite of
soda diluted with ten times its weight of water.
The colouring matter is precipitated from its solution in the meta-bisulphite by
the sulphuric acid. The sulphurous acid is driven off by ebullition.
The colouring matter is separated by filtration and desiccated..
This product constitutes the mono-carboxylated derivative of aurin.
The di- and tri-carboxylated products are obtained in the same manner by merely
changing the proportions of the salicylic acid and phenol.
For the di-carboxylated acid I employ:

page_text: vis fast product I use no prenot.
In both cases the proportions of the oxalic acid and sulphuric acid are the same as
for the mono-carboxylated acid.
The carboxylated group is situated in ortho with relation to the phenolic function.
I am able to obtain products in which the carboxylated group is situated in meta
by employing met-oxy-benzoic-acid.
Oxy-ẞ-naphthoic acid reacts in the same conditions as salicylic acid and oxy-
benzoic acids.
If I replace the oxycarboxylated products by amido-carboxylated products, such as
the acids ortho- and metamido-benzoic, proceeding under the same conditions, I
obtain products in which the phenolic functions are replaced either wholly or in part
by amido functions.
The acids oxy- and amido-cinnamic react in the same conditions.
In all the preceding reactions, I may substitute for sulphuric acid and oxalic acid
as condensing agents, chloride of zinc and formic acid.
The mono- and di-carboxylated products constitute, in the acid state, products of a
bright yellow, and in the state of salts, products of a very bright scarlet red.
The colouration of tri-carboxylated products tends towards a dark red.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that
what I claim is :-
1. A method of manufacturing moncarboxylated products derived from phenolic
compounds or amidated and phenolic compounds of triphenylmethane, consisting in
heating two molecules of phenol and one molecule of oxy or amido-carboxylated
(ortho and meta) derivatives of benzene and of naphthaline in the presence of oxalic
acid and sulphuric acid or of chloride of zinc and formic acid.
2. A method of manufacturing dicarboxylated products derived from phenolic
compounds or amidated and phenolic compounds of triphenylmethane consisting in
heating one molecule of phenol and two molecules of oxy or amido-carboxylated
(ortho and meta) derivatives of benzene and naphthaline in the presence of oxalic
acid and sulphuric acid or of chloride of zinc and formic acid.
3. A method of manufacturing tri-carboxylated products derived from phenolic
or amidated compounds or again from phenolic and amidated compounds of
triphenylmethane, consisting in heating three molecules of oxy acids or amidobenzoic
(ortho and meta) acids of benzene and naphthaline, or a mixture of these acids, in
the presence of oxalic acid or sulphuric acid or chloride of zinc and formic acid.
4. The purification of the products obtained by the methods ascertained in the
1st, 2nd and 3rd claims, consisting in dissolving them in an aqueous solution of meta
bisulphite and in precipitating the product thus purified by an acid.
Dated this 2nd day of December 1897.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.