Manufacture of Polyazo Colouring Matters Derived from Dioxy- diphenylmethan and Condensation Products of Formic Aldehyde with Benzidine, Tolidine, or Dianisidine.
Year: 1893

page_text: COMPLETE SPECIFICATION.
[Communicated from abroad by the firm of L. DURAND HUGUENIN & Co., of Bâle,
Switzerland, Manufacturers.]
Manufacture of Polyazo Colouring Matters Derived from Dioxy-
diphenylmethan and Condensation Products of Formic Aldehyde
with Benzidine, Tolidine, or Dianisidine.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane,
in the County of London, Consulting Engineer and Chartered Patent Agent, do
hereby declare the nature of this invention and in what manuer the same is to be
performed, to be particularly described and ascertained in and by the following
statement:-
When a molecule of the tetrazo derivative of one of the condensation products of
formic aldehyde with benzidine, tolidine or dianisidine, described in my
Specification No. 9360 of 1892, is made to act on a molecule of a naphthylamine
sulphonic acid or an oxybenzoic acid, intermediate products are obtained which are
insoluble, containing still a free diazo group. These intermediate products may be
employed in the manufacture of polyazo colouring matters. If two molecules,
either the same or different, of such intermediate products are made to act on a
molecule of dioxydiphenylmethan, bodies are obtained which contain the diazo
group fourfold. The colouring matter obtained, for instance, with 1 molecule of
dioxydiphenylmethan and 2 molecules of the intermediate product resulting from
1 molecule of tetrazo-tolidine formaldehyde and 1 molecule of salicylic acid has a
constitution acccording to the formula:
Ou
OH
CH, N N C,H. C,H, NH CH, NH C,H,C,H,N : N C.H,
COOH

page_text: and 5 kilos. caustic soda in about 200 litres of water.
The new colouring matter is
soon formed as a precipitate of clear red brown colour. It is separated by filtration,
washed with cold water until the wash has neutral reaction, pressed and dried.
The colouring matter then appears as a brown powder soluble in hot water, and
dyes unmordanted cotton a yellow tint. Its solution in concentrated sulphuric
acid is red violet. On heating the colouring matter with soda lye, it becomes
partially decomposed, disengaging formic aldehyde.
II. Colouring matter obtained with 1 molecule of dioxydiphenylmethan,
1 molecule of chloride of diazobenzol and 1 molecule of the intermediate product
resulting from the combination of 1 molecule of salicylic acid and I molecule of
the tetrazo derivative of the condensation product of tolidine with formic aldehyde.
The intermediate product obtained as in the preceding example is added to a
solution of 10 kilos. dioxydiphenylmethan, and 10 kilos. caustic soda in about
400 litres of water. After leaving the mass for some time to itself, there is added
to it a solution of chloride of diazobenzol prepared with 4-6 kilos. aniline, 15 kilos.
hydrochloric acid, and 3.5 kilos. sodium nitrite. The mass soon. becomes lemon
yellow in colour, and the triazo colouring matter is soon formed. This colouring
matter is scarcely soluble in hot water, and is preferably used in form of paste. It
dyes unmordanted cotton yellow. When dried it dissolves in concentrated
sulphuric acid giving a brown red solution. On heating the colouring matter
with soda lye, it becomes partially decomposed disengaging formic aldehyde.
III. Colouring matter obtained with 1 molecule of diazobenzol sulphonic acid,
1 molecule of dioxydiphenylmethan and 1 molecule of the intermediate product
resulting from the combination of 1 molecule of salicylic acid and 1 molecule of
the tetrazo derivative of the condensation product of tolidine and formic aldehyde.
For preparing this colouring matter, for the 4-6 kilos. aniline in the preceding
example are substituted 9.7 kilos. sulphanilate of soda. The triazo-colouring
matter produced is scarcely soluble in hot water, and is preferably used in form of
paste. It dyes unmordanted cotton yellow, and its solution in concentrated
sulphuric acid is of carmine tiut. On heating the colouring matter with soda lye,
it is also partially decomposed.
IV. Colouring matter obtained with 1 molecule of dioxydiphenylmethan and
2 molecules of the intermediate product resulting from the combination of 1 molecule
of a-naphthionic acid with 1 molecule of the tetrazo derivative of the condensation
product of tolidine with formic aldehyde.
The tetrazo derivative obtained by diazotising 21.8 kilos. tolidine-formaldehyde
or the condensation product of tolidine with formic aldehyde, by means of 40 kilos.
hydrochloric acid at 21° Be. and 7 kilos. sodium nitrite, is poured into a solution of
12.3 kilos, naphthionate of soda and 20 kilos. acetate of soda in about 300 litres of
water. After 3 hours the intermediate product formed, consisting of a deep brown
precipitate, is introduced into a solution containing 5 kilos. dioxydiphenylmethan,
5 kilos. caustic soda, and 40 kilos. carbonate of soda in about 200 litres of water.
After some hours of reaction at ordinary temperature the mass is heated to 60°
or 70° C. to finish the reaction, and is filtered.
The new colouring matter when dried, is a bright red powder soluble in hot
water; it dyes unmordanted cotton an orange tint. Its solution in concentrated
sulphuric acid is red violet.
V. Colouring matter obtained with 1 molecule of dioxydiphenylmethan and
2 molecules of the intermediate product resulting from the combination of
1 molecule of naphthionic acid with 1 molecule of the tetrazo derivative of the
condensation product of dianisidine with formic aldehyde.
For the 218 kilos. tolidine formaldehyde in example IV are substituted 25 kilos.
dianisidineformaldehyde or the condensation product of dianisidine with formic
aldehyde. The dry colouring matter is a greenish brown powder with metallic
lustre, soluble in hot water, and dyeing unmordanted cotton red. Its solution in
concentrated sulphuric acid is blue violet.

page_text: Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
:-
1. The manufacture of intermediate products, suitable for the production of
colouring matters, by combining 1 molecule of salicylic acid or naphthionic acid
with 1 molecule of the tetrazo-derivative of the condensation product of benzidine,
tolidine or dianisidine with formic aldehyde.
2. The manufacture of polyazo colouring matters by the action of 1 molecule
of dioxydiphenylmethan on 2 molecules of diazo combinations, of which one at least
is the intermediate product resulting from the combination of 1 molecule of salicylic
or naphthionic acid with molecule of the tetrazo derivative of the condensation
product of formic aldehyde with benzidine, tolidine or dianisidine.
3. The manufacture of yellow, orange and red colouring matters, dyeing un-
mordanted cotton, by a process as set forth in the preceding claim, combining
1 molecule of dioxydiphenylmethan with molecules of the intermediate product
resulting from the combination of 1 molecule of salicylic acid with 1 molecule of
the tetrazo derivative of the condensation product of tolidine with formic aldehyde,
or of 1 molecule of naphthionic acid with one molecule of the tetrazo derivative of
the condensation product of tolidine with formic aldehyde, or of 1 molecule of
naphthionic acid with 1 molecule of the tetrazo derivative of the condensation
product of dianiside with formic aldehyde.
4. The manufacture of yellow colouring matters dyeing unmordanted cotton,
by a process as set forth in Claim 2, combining 1 molecule of dioxydiphenylmethan
with 1 molecule of the intermediate product obtained with 1 molecule of salicylic
acid and 1 molecule of the tetrazo derivative of the condensation product of tolidine
with formic aldehyde and with 1 molecule of chloride of diazobenzol or diazobenzol
sulphonic acid.
5. The intermediate products and the colouring matters obtained by the
processes set forth in the preceding claims.
Dated thig 27th day of Annil 1902
ABEL & IMRAY,
Agents for the Applicant.