Manufacture of New Condensation Products and Colouring Matters for Dyeing and Printing.
Year: 1894

page_text: Date of Application, 7th Aug., 1894-Accepted, 8th Sept., 1894
COMPLETE SPECIFICATION.
Manufacture of New Condensation Products and Colouring Matters
for Dyeing and Printing.
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Co., 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 :-
In the Specification to Patent No. 24,802 of 1893, was described a process for
the manufacture of new colouring matters based on the general reaction of the
gallocyanines upon the phenols and certain derivatives thereof, and by way of
example there was indicated in the Specification of the said Patent the colouring
matters that could be obtained by the condensation of resorcine and of the
B-naphthol sulphonic acid of Schaeffer with gallocyanine obtained by means of
gallic acid and hydrochlorate of nitroso-dimethylaniline.
Our present invention relates to the production of other novel colouring matters
obtained by the process described in the above named Patent:
Firstly. By causing phenoles and their sulphonated derivatives to react upon the
gallocyanines obtained by the condensation of the salts of nitroso-diethylaniline, of
dialkylamidoazo benzols, and of the salts and sulphonated derivatives of the
dialkylamidoazo benzols with gallic acid and its derivatives.
Secondly. By causing pyrogallol or dimethylmetamidophenol to react upon
gallocyanine obtained by the condensation of hydrochlorate of nitroso-dimethyl-
aniline with gallic acid.
Thirdly. By causing resorcine to react upon gallocyanines obtained by the con-
densation of the hydrochlorate of nitroso-dimethylaniline with methyloallic ether
I.-REACTION OF PHENOLES AND THEIR SULPHONATED DERIVATIVES UPON THE
GALLOCYANINES DERIVED FROM THE SALTS OF NITROSO DIETHYLANILINE,
FROM DIALKYLAMIDOAZOBENZOLS, AND FROM THE SALTS AND SULPHO-
NATED DERIVATIVES OF THE DIALKYLAMIDO AZO BENZOLS.
By way of example we will describe the preparation of the products obtained
by means of B-naphthol-mono sulphonic acid of Schaeffer and gallocyanine derived
from gallamic acid and hydrochlorate of nitroso diethylaniline or of diethylamido-
azobenzol.
Example. In a solution of 40 kilos. ẞ-naphtholmonosulphonic-acid of Schaeffer
in 160 kilos. of sulphuric acid at 66° Be. there are gradually introduced 33 kilos. of
the colouring matter obtained by the action of gallamic acid upon hydrochlorate of
diethylamidoazobenzol or upon hydrochlorate of nitrosodiethylaniline.
When this admixture has been completed the compound is heated on the water
bath for completing the reaction, and the product is run into water.
There is thus obtained a greenish insoluble product which is filtered and which
represents a leuco-derivative of the new colouring matter, which can be applied
directly for printing, by developing the colour on the fibre by means of oxidation.
This oxidised leuco derivative, by preference in alkaline solution, furnishes a blue
colouring matter of acid character, soluble in alkalies, dyeing wool and silk blue
in acid bath, and having also a great affinity for metallic mordants, especially
those of chromium. The tints obtained on chrome mordants are fast to light and
vashing.

page_text: IV.-ACTION OF RESORCINE UPON THE GALLOCYANINES OBTAINED BY THE
REACTION OF HYDROCHLORATE OF NITROSODIMETHYLANILINE UPON 4
GALLAMIC ACID OR METHYLGALLIC ETHER.
3 parts of the one or the other of these gallocyanines are condensed with 2 parts
of resorcine and 9 parts of commercial hydrochloric acid, the resorcine having been
previously dissolved in a little water, and the process is then carried on as in II.
The colouring matters obtained are, as to their tinctorial properties, similar to

page_text: that obtained with resorcine and gallocyanine derived from gallic acid and hydro-
chlorate of nitroso dimethyl aniline, described in the before mentioned prior
Patent.
The colouring matters described under II, III and IV can also be converted
into sulpho conjugated derivatives in the manner indicated in the Specification to
Patent No. 24802 of 1893.
In order to clearly characterise the products of condensation (leuco-compounds.),-
as also, the colouring matters derived therefrom, as described in II, III and IV we
have given their principal reactions in the two foliowing tables, of which one
refers to the products of condensation, and the other to the colouring matters
derived therefrom.

page_text: 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. The manufacture of products of condensation applicable for printing and for
the production of colouring matters:
a) By the condensation of phenols and of their sulphonated derivatives and in
particular the ẞ naphtholmonosulphonic acid of Schaeffer with the gallo-
cyanines resulting from the action of the salts of nitroso diethylaniline or of
dialkylamido azo benzol or of its salts or sulpho conjugated derivatives upon
gallic acid and its derivatives such as gallamic acid, gallanilide, the
gallonaphthylamides and methylgallic ether.
6) By the condensation of pyrogallol or of dimethylmetaamidophenol with the
gallocyanine resulting from the action of hydrochlorate of nitrosodimethyl-
aniline upon gallic acid.
c) By the condensation of resorcine with the gallocyanines resulting from the
action of hydrochlorate of nitrosodimethylaniline upon gallamic acid or
methyl gallic ether.
2. The conversion of the products of condensation mentioned in the preceding
claim into colouring matters by oxidation and eventually by sulphonation, sub-
stantially as above described.
3. As new manufactures, the products obtained by the processes referred to in
the preceding claims.
Dated this 7th day of August 1894.
ABEL & IMRAY,
Agents for the Applicants.