Year: 1893

page_text: Date of Application (in United Kingdom), 23rd Dec., 1893
Complete Specification Left, 23rd Dec., 1893-Accepted, 27th Jan., 1854
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN, and
ADOLPHE JEAN JAMES D'ANDIRAN, trading as the Firm L. Durand Huguenin
& Cie., Manufacturers, of St. Fons, Rhone, 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 :-
Our invention relates to a new class of colouring matters obtained by the
reaction of phenols and their derivatives on the oxazines and the gallocyanines.
Among the derivatives of the phenoles we include the bodies containing, besides
one or more groups of free hydroxyle, the radicals "amido" (NH,), or "sulpho
(SO₂OH).
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The oxazines and the gallocyanines are bodies obtained by the condensation of
the nitroso-compounds of the tertiary aromatic amines or of " dialkylamido-azo
combinations of the aromatic hydro-carbons on the one hand, with phenoles,
carboxylised phenoles, and the substitution products of the phenoles and
carboxylised phenoles, on the other hand.
As typical examples we take the gallocyanines obtained by the reaction of
hydrochlorate of nitrosodimethylaniline upon gallic acid, and its derivatives. We
react upon these with different phenoles in a mauner suitable to their solubility,
for example: ordinary phenole simply in a molten condition; resorcine dissolved
in water; naphtholes and dioxynaphthalines in the presence of sulphuric acid.
The latter acts simultaneously as a solvent and as condensing agent.
All these reactions can be effected at ordinary temperatures or in slightly
heating to the temperature of the water bath, according to the substances
employed.
300 parts of gallocyanine, obtained with gallic acid and hydro-
chlorate of nitro-sodimethyl-aniline, with:
150 parts of resorcine,
200 parts of water,
900 parts of commercial muriatic acid, at the temperature of the
water bath, until all blue-violet coloration has disappeared
and the crystals, in the form of greenish yellow lamina, have
been precipitated.
We then dilute with water and wash repeatedly for removing the resorcine i
excess and the muriatic acid, as also secondary bodies formed at the same time.
The green body thus obtained gives, by oxidation of its alkaline solution in th
air, a blue-violet colouring matter, much bluer than the gallocyanine from whic
we started.

page_text: In order to render it more readily applicable we transform it into its sulpho
conjugated acid. We proceed indifferently according to the one or the other of the
following methods.
1. We first oxidise the green body in an alkaline aqueous solution, by the oxygen
of the air, and then precipitate by an addition of acid the blue-violet coloring
matter formed, this is separated by filtration and sulphonised by the usual method.
2. The yellow compound is dissolved in sulphuric acid, and oxidised at the same
time that the sulpho acid is formed, by adding the necessary quantity of an
oxydiser, for example ferric oxide.
3. Sulphuric acid may also be used simultaneously as coupler and oxydiser, as
the sulphuric acid acts already at 100° C. as oxydiser.
In the three cases, the product of the reaction is precipitated by means of water
and the free sulphuric acid is removed by washings. But if a polysulpho acid has
been formed by the use of a fuming sulphuric acid, which polysulphuric acid is
then more soluble in water, the product is neutralised by means of lime, and the
usual method is employed for isolating the colouring matter in the form of a
sulpho salt.
If, in place of resorcine, we employ for example the sulpho acid of ẞ naphthol,
known by the name of "Schäffers acid" the mode of operation is, in principle, the
same, only we form this acid directly by causing to react, firstly, sulphuric acid
of 85 p.c. of monohydrate upon the ẞ3 naphtol, and when the sulpho acid in question
is formed, we introduce therein, the gallocyanine.
When this latter is transformed, the mass is diluted with water. As the product
formed is a sulpho acid slightly soluble in water, it is necessary to wash with salt
water for removing the excess of free acid.
It only remains to subject the mass to oxidation for transforming it into colouring
matter. The colouring matters produced according to these examples, as also the
others first herein mentioned, are bodies soluble in alkalies in tints ranging from
blue to violet, precipitated by means of acids, and forming violet-blue lakes with
the metallic mordants employed in dyeing or printing.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is :-
1. The manufacture of condensation products by the action of the phenoles and
their derivatives herein mentioned, upon oxazines and gallocyanines.
2. The transformation of the condensation products referred in the preceding
claim into colouring matters by oxidation and eventually by sulpho-conjugation, in
principle as herein described.
3. As new manufactures, the products obtained by the processes set forth in the
two preceding claims.
Dated this 23rd day of December 1909
ABEL & IMRAY,
Agents for the Applicants.