Manufacture of New Blue Gallocyanine Colouring Matters.
Year: 1895

page_text: Date of Application, 22nd Feb., 1895-Accepted, 6th Apr., 1895
[Communicated from abroad by JOSEPH BIERER, Chemist, of Basle, and
LA SOCIÉTÉ L. DURAND HUGUENIN & CIE., Manufacturers, of Basle,
Switzerland.]
Manufacture of New Blue Gallocyanine Colouring Matters.
I, JOHN IMRAY, of No. 28 Southampton Buildings, in the County of London,
Consulting Engineer and Chartered Patent Agent, 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 :-
By the action of an aromatic amine, such for instance as aniline, toluidine or
the like, upon the gallocyanine colouring matter produced by the reaction of
hydrochlorate of diethylamido-azo-benzol, or of hydrochlorate of nitroso-diethyl-
aniline upon gallamic acid, there are obtained new colouring matters which can be
readily converted into sulpho acids, and the soda salts of which are readily
soluble in water, and produce blue shades of colour upon non-mordanted wool or
silk, and also upon chrome mordants.
10 kilos. of the colouring matter obtained by the action of hydrochlorate of
diethyl-amido-azo-benzol or of hydrochlorate of nitroso diethylaniline upon
gallamic acid, are heated together with 20 kilos. of aniline for about three
hours to a temperature of 50° C. with constant agitation.
After the mixture has stood for a day and has become cool, it is filtered off.
The colouring matter thus produced is only slightly soluble in alcohol; it is
washed in alcohol to remove the last traces of aniline; then pressed and dried.
Or, after the reaction is compléted the mixture is poured into water acidulated
with hydrochloric acid, in order to neutralize the aniline with hydrochloric acid;
it is then filtered, pressed and dried.

page_text: The following tabular statement sets forth some of the main characteristics.
which serve to distinguish the product of condensation thus produced from the
original colouring matter.
of
Colouring matter from
gallamic acid and
hydrochlorate
diethyl-amido-azo-
of
Colouring matter from
gallamic acid and
hydrochlorate
diethyl- amido-azo-
benzol, or hydro-
chlorate of nitroso-
diethyl-aniline.
benzol, or hydro-
chlorate of nitroso-
diethyl-aniline con-
densed with aniline.
Instead of employing the colouring matter to be condensed with aniline, in the
form of a hydrochlorate as in the preceding example, it may be employed in the
form of a base, but in this case hydrochlorate of aniline and aniline are employed,
instead of aniline alone.
Furthermore, if the temperature at which the reaction takes place in the
preceding example, be varied, (without however exceeding the temperature that
can be obtained with a water bath) then products of condensation are produced
which vary in colour from reddish blue to greenish blue.
The higher the temperature employed at which the condensation takes place,
the greener is the product of condensation obtained.
Finally, if in the preceding example the colouring matter produced by
condensation of gallamic acid with diethylamido-azo-benzol or nitroso-diethyl-
aniline is employed in the form of a base or of an acetate instead of a hydro-
chlorate salt, products of condensation are obtained the blue colour of which has
a redder tinge.
For use for industrial purposes, the new colouring matters are usually converted
into sulpho acids.

page_text: Example. 25 kilos. of the new product of condensation (produced as stated in
the preceding example, by condensation of aniline with the colouring matter from
gallamic acid and hydrochlorate of diethyl-amido-azo-benzol or hydrochlorate of
nitrosodiethylaniline) are heated together with 75 kilos. of sulphuric acid
containing 96% of SO.H, to a temperature of 90°, until a sample of the mixture
completely dissolves in alkaline water. The product of the reaction is then
poured into water or brine, the acid in excess is neutralised with soda, and the
precipitated sulpho acid of the new colouring matter is obtained by filtering,
pressing, and if necessary, by drying. It is insoluble in water and is converted in
the well known manner into a salt of soda, which is readily soluble in water.
The soda salt of this sulpho acid dyes non-mordanted wool or silk in an acid
bath, blue. On mordants, and in particular on chrome mordants, it produces
greenish blue tints.
When fuming sulphuric acid is employed for sulphonating the new colouring
matter, polysulpho acids are produced which are directly soluble in water, and the
soda salts of which can be readily precipitated from their aqueous solutions by the
addition of common salt.
The solutions of the soda salts of the sulpho acids of the new colouring matter
in concentrated sulphuric acid, and also in hydrochloric acid, are red, and by the
addition of a little water, become yellow, and by the addition of much water,
become blue.
According as the one or the other of the hereinbefore mentioned products of
condensation is sulphonated, there are produced sulpho acids the alkaline salts of
which give different blue tints in dyeing.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
:-
1. The herein described manufacture of new blue colouring matters by
condensation of an aromatic amine, such for instance as aniline, with the gallo-
cyanine colouring matter obtained by the action of hydrochlorate of nitrosodiethyl-
aniline or of hydrochlorate of diethylamido-azo-benzol upon gallamic acid.
2. The conversion herein described of the products of condensation produced as
set forth in Claim 1, into sulpho acids, by heating these products with sulphuric
acid, and, if required the conversion of these sulpho acids into alkaline salts.
3. The colouring matters produced according to the processes herein described.
Dated this 22nd day of February. 1895.
ABEL & IMRAY,
Agents for the Applicant.