Manufacture of New Colouring Matters Derived from .Dioxydiphenylmethan.
Year: 1893

page_text: being date of first Foreign Application (in 13th Apr., 1893
France),
Date of Application (in United Kingdom), 4th Nov., 1893
Complete Specification Left, 4th Nov., 1893-Accepted, 9th Dec., 1893
Date of Application (in United Kingdom), 4th Nov., 1893
Complete Specification Left, 4th Nov., 1893-Accepted, 9th Dec., 1893
COMPLETE SPECIFICATION.
Manufacture of New Colouring Matters Derived from
.Dioxydiphenylmethan.
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 :-
According to the process set forth in our Specification No. 9182 of 1893 we have
obtained yellow polyazoic colouring matters hereinafter described in which one at
least of the two molecules of diazo combinations combined with one molecule of
dioxydiphenylmethan, is formed by the intermediate product resulting from the
union of one molecule of tetrazo diphenyl or tetrazo ditolyl with one molecule of
salicylic acid.
I. Colouring matter obtained with one molecule of dioxydiphenylmethan and
two molecules of the intermediate product resulting from the union of equivalent
quantities of tetrazodiphenyl and salicylic acid.
18.4 kilos. benzidine are transformed in the known manner into the tetrazo
derivative by means of 60 kilos. hydrochloric acid at 21° Bé. and 13.8 kilos. sodium
nitrite.
The tetrazodiphenyl thus obtained is poured into a solution containing 13-8 kilos.
salicylic acid and 60 kilos. carbonate of soda, care being taken to agitate. The
intermediate product formed at the end of two or three hours is introduced into a
solution of 10 kilos. dioxydiphenylmethan and 3.5 kilos. caustic soda in about
500 litres of water. After leaving the mass for about 12 hours to itself, it is heated
to boiling and the colouring matter is precipitated by sea salt. After drying
the colouring matter appears in the form of a brown powder soluble in hot water;
and it dyes unmordanted cotton in an alkaline bath a yellow tint. The solution of
the colouring matter in concentrated sulphuric acid is violet.
II. Colouring matter obtained with a molecule of dioxydiphenylmethan and two
molecules of the intermediate product resulting from the union of equivalent
quantities of tetrazoditolyl and salicylic acid.
E
This colouring matter is obtained by substituting 21-2 kilos. tolidine for the
18-4 kilos. benzidine in the preceding examples unmordanted cotton in an alkaline
The dry colouring matter forms a
brown powder soluble in hot water and
bath a yellow tint.
The solution of the colouring matter in concentrated sulphuric acid has a blue
violet colour.
III. Colouring matter obtained with a molecule of dioxydiphenylmethan, a
molecule of diazo benzene chloride and a molecule of the intermediate product
resulting from the union of equivalent quantities of tetrazodiphenyl and salicylic
cid.

page_text: The intermediate product prepared as described in Example I, is introduced into
a solution of 20 kilos. dioxydiphenylmethan and 7 kilos. caustic soda in about
800 litres of water. After a short time there are added to this mass 40 kilos.
carbonate of soda and a solution of diazo benzene chloride prepared by means of
9.3 kilos. aniline, 30 kilos. hydrochloric acid and 6.9 kilos. sodium nitrite.
After the mass has been left to itself for about 12 hours at ordinary temperature
it is heated to boiling to complete the reaction and the colouring matter is
separated by filtration. The dry colouring matter appears in the form of a brown
powder not easily soluble in hot water; it dyes unmordanted cotton in an alkaline
bath a yellow tint.
IV. Colouring matter obtained with a molecule of dioxydiphenylmethan, a
molecule of the intermediate product resulting from the union of equivalent
quantities of tetrazodiphenyl and salicylic acid, and a molecule of the intermediate
product resulting from the union of equivalent quantities of tetrazo diphenyl and
sulpho-anilic acid.
The product mentioned in Example III and obtained by the combination of a
molecule of dioxydiphenylmethan with a molecule of an intermediate product
resulting from the union of equivalent quantities of tetrazodiphenyl and salicylic
acid has added to it 40 kilos. carbonate of soda, and to this mixture is then added
the intermediate product formed by the union of equivalent quantities of tetrazo-
diphenyl and sulphoanilic acid, and obtained by means of 18.4 kilos. benzidine,
60 kilos. hydrochloric acid, 13.8 kilos. sodium nitrite, 19.5 kilos. sulphoanilate of
soda and 40 kilos. acetate of soda. At the end of about 12 hours the product of
reaction is heated to boiling and the colouring matter formed is precipitated by sea
salt. The colouring matter after being dried appears as a deep red brown powder
soluble in hot water and it dyes unmordanted cotton in an alkaline bath yellow.
The colour of the solution of the colouring matter in concentrated sulphuric acid-is
red violet.
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 preparation of polyazoic colouring matters according to the process set
forth in our previous Specification No. 9182 of 1893, by the action of a molecule
of dioxydiphenylmethan on two molecules of diazo combinations of which one at
least constitutes the intermediate product resulting from the union of a molecule of
tetrazo diphenyl or tetrazo ditolyl and a molecule of salicylic acid.
2. The preparation of yellow colouring matters dyeing unmordanted cotton by
the combination of a molecule of dioxydiphenylmethan with two molecules of the
intermediate product resulting from the union of a molecule of tetrazodiphenyl or
tetrazoditolyl and a molecule of salicylic acid.
3. The preparation of a yellow colouring matter dyeing unmordanted cotton by
the combination of a molecule of dioxydiphenylmethan with a molecule of the
intermediate product resulting from the union of a molecule of tetrazodiphenyl
and a molecule of salicylic acid, and with a molecule of the intermediate product
resulting from the union of a molecule of tetrazodiphenyl and a molecule of sulpho-
anilic acid.
4. The preparation of a yellow colouring matter dyeing unmordanted cotton by
the combination of a molecule of dioxydiphenylmethan with a molecule of the
intermediate product resulting from the union of a molecule of tetrazodiphenyl and
a molecule of salicylic acid and with a molecule of diazobenzene chloride.
5. As new products the colouring matters hereinbefore described.
Dated this 1th dow of Narambon 1902
ABEL & IMRAY,
Agents for the Applicants.