Manufacture of Blue Gallocyanin Colouring Matters.
Year: 1894

page_text: -Date of Application, 23rd July, 1894
Complete Specification Left; 22nd Apr., 1895-Accepted, 24th May, 1895
:
PROVISIONAL SPECIFICATION.
Manufacture of Blue Gallocyanin Colouring Matters.
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN, and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Co., of St. Fons, Rhone, France, Manufacturers, do hereby declare
the nature of this invention to be 'as 'follows:-
This invention relates to the manufacture of.blge 'gallocyaninecolouring matters
by causing dialkylamidoazobenzol or hydrochlorate of dialkylamidoazobenzol, or
sulphonate- df dialkylamidoazobenzol,. inwhich the sulpho group: is: inethe first
benzol nucleus, to reacts upon gallamide..
Under the firsti-nucleus off sulphonated dialkylamidoazobenzol is understood a
body of the formula:
CH.NN.CH.N(R),
where R means an alkyl rest such as the methyl rest.
If dialkylamidoazobenzol or its.above named salt or sulpho-derivative, is made to
react upon gallamide in the presence of suitable solvents, such: forexample : as
alcohol, glacial acetic acid, ordinary acetic acid, methylalcohol, at a temperature
approaching the boiling point of these solvents; there will be produced, under
splitting off of anilin, or anilin sulpho acid, blue colouring matters which like the
usual gallocyanin colouring matters, have a great affinity for metallic mordants and
in particular for chrome mordants .but, which differ from: the usual gallocyanin
colouring matters in that they are easily..soluble in water in the form of:a+salt, and
consequently must not be converted into bisulphite.compounds for use.
The manufacture of these colouring, matters will be understood from the following
example:
are heated under stirring to.about.120° in an oil bath.
After a short time-therreaction commences and as soon as a sample of the reaction
mass no longer shows any free amidoazo-derivative, it is poured into waters From
the solution of the colouring matter thus obtained. the colouring matter is
precipitated by means of common salt. The precipitate can then be pressed and
dried.
It is however preferable to keep the colouring matter as a paste, which is better
suited for dyeing purposes.
In the example given the dialkylamidoazobenzol or its hydrochloratestcan be
replaced by an equivalent quantity of the above..named sulpho derivative.
If ordinary acetic acid, methyl or ethyl alcohol, berused in place of «glacial
acetic acid for the production of these colouring matters, the reaction will not take
place so rapidly and the mass requires to be heated for a longer time.
The use of glacial acetic acid allows of the use of free dialkylamidoazobenzol,
While when ordinary alcohol or methylalcohol is used, the reaction. takes place
more rapidly and smoothly if hydrochlorate of dialkylamidoazobenzol be used.
D

page_text: The colouring matters produced as above described are easily soluble in water as
a salt, and dye chromed wool in blue tints.
The aqueous solutions of their salts are blue.
The solutions of the colouring matters in concentrated sulphuric acid are blue,
and with the addition of water they assume a red-violet tint. On the addition of
an excess of alkalies to the solutions of the colouring matters, the tint becomes
red-violet and the colouring matter is precipitated.
Dated this 23rd day of July 1804
Manufacture of Blue Gallocyanin Colouring Matters.
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN, and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Co., of St. Fons, Rhone, France, Manufacturers, 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 manufacture of blue gallocyanin colouring matters
by causing dialkylamidoazobenzol or hydrochlorate of dialkylamidoazobenzol, or
sulphonate of dialkylamidoazobenzol, in which the sulpho group is in the first
benzol nucleus, to react upon gallamide.
Under the first nucleus of sulphonated dialkylamidoazobenzol is understood a
body of the formula :
where R means an alkyl rest such as the methyl rest or ethyl rest.
If dialkylamidoazobenzol or its above named salt or sulpho-derivative, is made
to react upon gallamide in the presence of suitable solvents, such for example as
alcohol, glacial acetic acid, ordinary acetic acid, methylalcohol, at a temperature
approaching the boiling point of these solvents, there will be produced, under
splitting off of anilin, or anilin sulpho acid, blue colouring matters which, like the
usual gallocyanin colouring matters, have a great affinity for metallic mordants and
in particular for chrome mordants, but which differ from the usual gallocyanin
colouring matters in that they are easily soluble in water in the form of a salt, and
consequently must not be converted into bisulphite compounds for use.
The manufacture of these colouring matters will be understood from the following
.
17 kil. gallamide
32 kil. hydrochlorate of demethylamidoazobenzol, and
150 kil. glacial acetic acid ..
are heated under stirring to about 120° C. in an oil bath.
After a short time the reaction commences and as soon as a sample of the
reaction-mass no longer shows any free amidoazoderivative it is poured into water.
From the solution of the colouring matter thus obtained the colouring matter is
precipitated by means of common salt. The precipitate can then be pressed and
dried.
It is however preferable to keep the colouring matter as a paste, which is better

page_text: In the example given, the dialkylamidoazobenzol or its hydrochlorate, can be
replaced by an equivalent quantity of the above named sulpho derivative.
If ordinary acetic acid, methyl- or ethyl alcohol be used in place of glacial acetic
acid for the production of these colouring matters, the reaction will not take place
so rapidly and the mass requires to be heated for a longer time.
The use of glacial acetic acid allows of the use of free dialkylamidoazobenzol,
while when ordinary alcohol or methylalcohol is used, the reaction takes place
more rapidly and smoothly if hydrochlorate of dialkylamidoazobenzol be used.
The colouring matters produced as above described are easily soluble in water as
a salt, and dye chromed wool in blue tints.
The aqueous solutions of their salts are blue.
The solutions of the colouring matters in concentrated sulphuric acid are blue,
and with the addition of water they assume a red-violet tint. On the addition of
an excess of alkalies to the solutions of the colouring matters, the tint becomes
red-violet and the colouring matter is precipitated.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, we declare that what we
claim is:-
1. Manufacture of gallocyanin colouring matters by causing dialkylamidoazo-
benzol or its hydrochlorate, or its sulpho derivative in which the sulpho group is
contained in the first benzol neucleus, to react, under heating, with gallamide in the
presence of a suitable solvent such as glacial acetic acid, common acetic acid,
ethyl- or methyl-alcohol, at a temperature approaching that of the boiling point of
the solvent employed, substantially as described.
2. As a new article of manufacture, the blue gallocyanin colouring matters
obtained by the process referred to in the first claim.
Dated this 22nd day of April 1895.
ABEL & IMRAY,
Agents for the Applicants.