the Manufacture of New Colouring Matters Derived from Condensation Products of Formic Aldehyde with Benzidine, Tolidine, or Dianisidine.
Year: 1893

page_text: Date claimed for Patent under Sect. 103 of Act,
being date of first Foreign Application (in
France),
27th Jan., 1893
Date of Application (in United Kingdom), 8th May, 1893
Complete Specification Left. 8th May. 1893-Accepted. 15th July, 1893
COMPLETE SPECIFICATION.
the
Manufacture of New Colouring Matters Derived from
Condensation Products of Formic Aldehyde with Benzidine,
Tolidine, or Dianisidine.
We, JEAN CLAude Louis Durand, Daniel EDOUARD HUGUENIN, and
ADOLPHE JEAN JAMES D'ANDERAN constituting the Firm of L. Durand
Huguenin & Cie. of Basle, Switzerland, 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 :-
Our present application for Patent has for its object the manufacture of new
substantive colouring matters for cotton derived from the condensation products of
formic aldehyde with benzidine, tolidine or dianisidine, which have been described
in the Specification No. 9360 of 1892. These new colouring matters are obtained
by combining the tetrazo derivatives of the said condensation products with the
sulphonaphthylamines, the sulphonaphthols or the carboxylic acids. By way of
example we shall describe some of the colouring matters.
I. Colouring matter obtained by the combination of salicylic acid with the
tetrazo derivative of the condensation product of formic aldehyde and benzidine.
3-8 kilo. of the new base obtained by condensation of formic aldehyde (formal-
dehyde) and benzidine are diazotised in the usual way by means of 8 kilo. hydro-
chloric acid at 21° Bé. and 1-4 kilo. sodium nitrite. The tetrazo derivative thus
obtained is then poured into a solution of 2.8 kilo. salicylic acid in 20 kilo. caustic
soda lye of 20 or 3 per cent. care being taken to agitate well. In a short time the
formation of the colouring matter is completed, being deposited as a brown
precipitate, which is separated by filtration, pressed and dried. It then appears as
a brown powder easily soluble in water and dyeing non-mordanted cotton in an
alkaline bath a yellow tint. Its solution in concentrated sulphuric acid is coloured
red brown.
II. Colouring matter obtained by the combination of salicylic acid with the
tetrazo derivative of the condensation product of formic aldehyde and tolidine.
By substituting for the 3.8 kilo. of the condensation product of formic aldehyde
and benzidine stated in the preceding example, 4.3 kilos. of the condensation
product of formic aldehyde and tolidine, there is obtained a new yellow colouring
matter dyeing unmordanted cotton with a tint somewhat redder than that
produced by the former dye. The solution of this colouring matter in concentrated
sulphuric acid is also coloured red brown.
III. Colouring matter obtained by the combination of naphthionic acid with the
tetrazo derivative of the condensation product of formic aldehyde and tolidine.
The tetrazo derivative obtained by diazotising 4-3 kilo. of the condensation product
of formic aldehyde and tolidine by means of 8 kilo. hydrochloric acid at 21° Bé.
and 1-4 kilo. sodium nitrite is poured into a solution containing 4.9 kilo. naphthionate
and 8 kilo. acetate of soda, care being taken to agitate. After leaving the mass to
itself for 12 hours, the product of the reaction is supersaturated by a solution of

page_text: carbonate of soda, it is heated to ebullition, and the colouring matter formed is
precipitated by adding sea salt. After drying, this colouring matter appears as a
red powder dyeing unmordanted cotton in an alkaline bath a red tint.
concentrated sulphuric acid this colouring matter has a violet solution.
With
IV. Colouring matter obtained by the combination of a-naphthol-a-sulphonic
acid with the tetrazo derivative of the condensation product of formic aldehyde
and tolidine.
The tetrazo derivative mentioned in the preceding example is poured into a
solution containing 4.5 kilo. a-naphthol, a-sulphonic acid and 6 kilo. carbonate of
soda. After leaving the mass to itself for some hours, it is heated to ebullition,
and the colouring matter is precipitated by addition of sea salt. When dried, this
colouring matter is a dark brown powder with metallic lustre, dyeing unmordanted
cotton in an alkaline bath, a violet tint. Its solution in concentrated sulphuric
acid has a grey violet colour.
V. Colouring matter obtained by the combination of a-naphthol-a sulphonic
acid with the tetrazo derivative of the condensation product of formic aldehyde
and dianisidine.
The condensation product of formic aldehyde and dianisidine weighing 5 kilo. is
diazotised by means of 8 kilo. bydrochloric acid at 21° Bé. and 14 kilo. sodium
nitrite, and the tetrazo product obtained is poured into a solution containing
4-5 kilo. a-naphthol-a sulphonic acid and 6 kilo. carbonate of soda. After leaving
the mass to itself for several hours, it is heated to ebullition, and the colouring
matter is precipitated by addition of sea salt. This colouring matter when dried
appears as a deep brown powder with metallic lustre, and dyes unmordanted cotton
in an alkaline bath a blue tint. Its solution in concentrated sulphonic acid is
grey-blue.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is :-
1. The manufacture of new colouring matters by combining with the naphthyl-
amine sulphonic acids, the naphthol sulphonic acids or the carboxylic acids the
tetrazo derivatives of the condensation products of formic aldehyde with benzidine,
tolidine or dianisidine.
2. As new products, the colouring matters obtained by the process set forth in
the preceding claim.
Dated this 8th day of May 1902
ABEL & IMRAY,
Agents for the Applicants.