Manufacture of Colouring Matters of the Rosinduline-series.
Year: 1895

page_text: Date of Application, 29th Aug., 1895
Complete Specification Left, 22nd May, 1896-Accepted, 27th June, 1896
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR ANILIN
FABRIKATION, of Berlin, in the Empire of Germany, Chemical Manufacturers.]
Manufacture of Colouring Matters of the Rosinduline-series.
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 to be as follows:-
Colouring matters of the rosinduline-series have hitherto been obtained either by
melting together benzol-azo-a-naphthylamine or the nitroso-derivatives of a-naphthol
or naphthoquinonediimid with aniline and aniline hydrochloride; or by the
condensation of the derivatives of oxynaphthoquinonediimid with ortho-amido-
diphenylamine or the sulpho acids thereof in an alcoholic or aqueous solution.
My foreign correspondents have discovered a new process for the production of
derivatives belonging to the rosinduline-series which process consists in treating
with oxidizing agents in an aqueous solution equi-molecular proportions of
a-naphthylamine and ortho-amidodiphenylamine-sulphonic acid or derivatives of
these substances respectively. Instead of carrying out the process in the above
mentioned way by means of suitable oxidizing agent the formation of corresponding
rosinduline derivatives may further be brought about by melting together at raised
temperatures equi-molecular proportions of a-naphthylamine and ortho-nitro-
diphenylamine-sulphonic acid, the nitro-group thus acting as an oxidizing agent.
Both reactions above indicated take place smoothly and require but cheap and
easily accessible starting products. From this it is obvious that this invention
offers a great advantage over the methods hitherto used for the manufacture of
dyes of the rosinduline-series.
In order to illustrate the nature of this invention the following is given as typical
examples, but it is not intended to limit the application of this invention to them,
as the methods of operating and the products used may be varied without departing
from the scope of this invention.
1. 14.3 kilos. of a-naphthylamine and of 26.5 kilos. of orthoamidodiphenylamine-
sulphonic acid are dissolved in water and hydrochloric acid or acetic acid. To
the mixture the aqueous solution of 20 kilos. of bichromate of sodium is slowly
added. The rosinduline sulphonic acid thus formed precipitates as a brown
crystalline powder with a metallic lustre, sparingly soluble in water.
If in the above example for a-naphthylamine the equimolecular proportion of
ethyl-a-naphthylamine or of a-naphthylamine ẞ3-sulphonic acid be substituted
corresponding rosinduline derivatives are obtained. Instead of bichromate of
potassium similar oxidizing agents viz. ferric chloride, potassium ferricyanide,
and the like may also be used.
11. 25 kilos. of a-naphthylamine, 10 kilos. of a-naphthylamine hydrochloride
16 kilos. of nitrodiphenylaminesulphonic acid and 5 kilos. of chloride of zinc are
well stirred together in a finely ground state and heated to from 140 to 150° C.
for 4-5 hours. After having cooled down, the brittle melt is pulverised and
extracted with dilute hydrochloric acid. The rosinduline sulphonic acid remains
ndissolved as a greenish powder. It is sparingly soluble in soda-lye and dilute
acids. The above condensation can also be performed in absence of chloride of
zine or of any other suitable condensing agent.

page_text: The rosinduline derivatives obtained by either of the ways indicated may be
easily transformed into readily soluble sulphonic acids by subsequent sulphonation.
Dated this 29th day of August 1895.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Colouring Matters of the Rosinduline-series.
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 manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
Colouring matters of the rosinduline-series have hitherto been obtained either
by melting together benzol-azo-a-naphthylamine or the nitroso-derivatives of
a-naphthol or naphthoquinonediimid with aniline and aniline hydrochloride; or
by the condensation of the derivatives of oxynaphthoquinonediimid with
ortho-amidodiphenylamine or the sulpho acids thereof in an alcoholic or aqueous
solution.
My foreign correspondents have discovered a new process for the production of
derivatives belonging to the rosinduline-series which process consists in treating
with oxydizing agents in an aqueous solution equi-molecular proportions of
a-naphthylamine and ortho-amidodiphenylamine-sulphonic acid or derivatives of
these substances respectively.
Instead of carrying out the process in the above mentioned way by means of
suitable oxidizing agents, the formation of corresponding rosinduline derivatives
may further be brought about by melting together at raised temperatures equi-
molecular proportions of a-naphthylamine and ortho-nitro-diphenylamine-sulphonic
acid, the nitro-group thus acting as an oxidizing agent. Both reactions above
indicated take place smoothly and require but cheap and easily accessible starting
products. From this it is obvious, that this invention offers a great advantage
over the methods bitherto used for the manufacture of dyes of the rosinduline-
series.
In order to illustrate the nature of this invention the following are given as
typical examples, but it is not intended to limit the application of this invention to
them, as the methods of operating and the products used may be varied without
departing from the scope of this invention.
1. 14.3 kilos. of a-naphthylamine and 26.5 kilos. of orthoamidodiphenylamine-
sulphonic acid are dissolved in water and hydrochloric acid or acetic acid. To the
mixture the aqueous solution of 20 kilos. of bichromate of sodium is slowly added.
The rosinduline sulphonic acid thus formed precipitates as a brown crystalline
powder with a metallic lustre, sparingly soluble in water.
11. 17.1 kilos. of ethyl-a-naphthylamine and 26-5 kilos. of ortho-amido-
diphenylamine sulphonic acid are dissolved in diluted hydrochlori
记
A solution of ferric chloride is added, and the ethylrosinduline-sulphonic acid,
which is sparingly soluble in water, is completely separated.
III. 22.3 kilos, of a-naphthylamine-6-sulphonic acid and 26.5 kilos. of ortho-
amidodiphenylamine sulphonic acid are dissolved in a solution of carbonate of
soda. A solution of ferricyanide of potassium is added until the intensity f
the colour is not yet increased. The rosinduline disulphonic acid is precipitated
by means of common salt.
IV. 25 kilos. of a-naphthylamine, 10 kilos. of a-naphthylamine hydroch! ride

page_text: 16 kilos. of nitrodiphenylaminesulphonic acid and 5 kilos. of chloride of zinc are
well stirred together in a finely ground state and heated to from 140° to 150° C.
for 4 to 5 hours.
After having cooled down, the brittle melt is pulverised and extracted with
dilute hydrochloric acid. The rosinduline sulphonic acid remains undissolved
as a greenish powder. It is sparingly soluble in soda-lye and dilute acids.
The above condensation can also be performed in absence of chloride of zinc or
of any other suitable condensing agent.
The rosinduline derivatives obtained by either of the
ways indicated may
be easily transformed into readily soluble sulphonic acids by subsequent
sulphonation.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is:
:-
1. The manufacture of colouring matters of the rosinduline series,-
(a) by simultaneous oxidation of equimolecular proportions of a-naphthylamine
or its derivatives and ortho-amidodiphenylamine sulphonic acid or its
homologues or :
(b) by melting together a-naphthylamine or its derivatives and ortho-
nitrodiphenylamine sulphonic acid or its homologues either in presence
or in absence of chloride of zinc or any other suitable condensing agent.
2. The new colouring matters manufactured as above set forth.
Dated this 22nd day of May 1896.
ABEL & IMRAY,
Agents for the Applicant.