Methods or Processes of Treating Oxynaphtol and Aniline or its Homologues, Obtaining Certain Products and Utilizing the same in the Manufacture of Dyes.
Year: 1886

page_text: Date of Application, 5th Nov., 1886.
Complete Left, 4th Aug., 1887.
Complete Accepted, 6th Sept., 1887.
Methods or Processes of Treating Oxynaphtol and Aniline or its
Homologues, Obtaining Certain Products, and Utilizing the same
in the Manufacture of Dyes.
I, JOSEPH ANNAHEIM of 58, Johannvorstadt, Basel, Switzerland, Doctor of
Philosophy do hereby declare the nature of this Invention to be as follows:-
This invention has reference to Methods or processes of treating oxynaphtol and
aniline or its homologues, obtaining certain new products, and utilizing the same in
the manufacture of dyes. The products in question will be hereinafter called products
of condensation.
They are obtained as follows:-
Oxynaphtol is heated with and under the influence of a suitable condensing
medium and with a primary aromatic amine such as, aniline, para- or ortho-toluidine,
xylidine, cumidine, alpha-naphtylamine, beta-naphtylamine etc.; water is produced
and a series of new compounds is obtained. If aniline be employed
Oxyphenylnaphtylamine
Co He
OH
N
H
-
- U H³ or
Diphenylnaphtylendiamine
H
N-CH
C'¹º H*
\N-C H
H
will be obtained according to the equations―
[Price 6d.

page_text: As solvents there may be employed water either slightly alkaline, neutral or
acidulated (preferably with acetic acid) alcohols, glacial acetic acid etc.
(b) The nitroso compound such as hydro-chloric nitroso-dimethylaniline, is reduced
in the usual manner with zine dust and hydrochloric acid. One or other of the above
mentioned products of condensation is then added, and oxidation thereof produced
with the necessary quantity of bichromate of potash or chloride of iron, etc.
Dated this Fifth day of November 1886.
W. LLOYD WISE,
46, Lincoln's Inn Fields, London, W.C.,
Agent for the Applicant.

page_text: Cio H
NCH
✓ NC H5
H
+ 2 H2O.
As the result of experience it is found that if the conditions mentioned below are
observed the reaction appears to take place chiefly according to the second equation,
that is, both the hydroxyl groups are replaced by phenylamine compound C H³ NH.
As condensation media there may be used calcic chloride, zinc chloride, hydrochloric-
acid, either alone or in the form of hydrochloric amines, aluminium chloride etc.
To make the nature of this part of my invention understood it will suffice to
describe the manufacture of aniline derivatives as follows:-16 Kilogs of oxynaphtol
(produced according to Ebert and Merz Report of the German Chemical Society
Vol. IX pg. 609) are mixed with 37 Kilogs of aniline-and 13 Kilogs of hydro-
chlorate of aniline, and the mixture heated for several hours either in an open or in a
closed vessel up to nearly the boiling point of the aniline. When the reaction is
finished the mass is treated according to the methods heretofore usually employed for
the separation of the excess of aniline, and the resulting substance is pressed, purified,
and dried.
Although I have indicated certain definite proportions of substances they may be
varied and therefore I do not limit myself to such proportions.
The new compound produced according to the above process is a white solid body
insoluble in water and alkalies, soluble with difficulty in cold ethylic-methylic- and
amylic-alcohol, and readily soluble in ether, boiling benzol, toluol, glacial acetic
acid etc.
It can be readily obtained in a crystallized state with the help of the above
mentioned solvents. Its melting point is 163° C.
The toleridine and xyledine derivatives may be produced as easily as those of
aniline and in a manner that will be readily understood from the foregoing description.
If apha and beta-naphtylamine be used, the reaction is less favourable, owing to the
formation of di-naphtylamine.
The product obtained by heating paratoluidine according to the process hereinabove
described is much less easily soluble in all the above mentioned solvents than the
aniline derivatives; it has also a much higher melting point namely 237° C.
Dyes may be obtained chiefly according to two methods, from the above mentioned
products of condensation of aniline and its homologues with the oxynaphtol, and the
tertiary nitroso-amines as follows:-
(a) One or other of the above mentioned products of condensation according to
the dye desired is (as I prefer) united generally in molecular proportions, with the
free nitroso-compound or a salt of the same such as nitroso dimethylaniline hydro-
chloride in conjunction with a suitable solvent the mixture being gradually heated
until a complete conversion into the dye has taken place. As solvents there may be
employed water either slightly alkaline neutral or acidulated (preferably with acetic
acid), alcohols, glacial acetic acid etc.
(b) The nitroso compound such as hydo-chloric nitroso-dimethylaniline, is reduced
in the usual manner with zinc dust and hydrochloric acid. One or other of the above
mentioned products of condensation is then added and oxidation thereof produced
with the necessary quantity of bichromate of potash, or chloride of iron etc.
Having now particularly described and ascertained the nature of this invention, and
in what manner the same is to be performed I declare that what I claim is :-
1. The hereinbefore described process for the manufacture of the products of

page_text: condensation of bioxynaphtaline with aniline, paratoluidine, orthotoluidine, xylidine;
cumidine, alpha- and beta-naphtylamine or other like compounds the said process being
carried out by the aid of calcic chloride, chloride of zinc, hydrochloric acid, hydro-
chloric amines, chloride of aluminium or other suitable mediums of condensation.
2. The hereinbefore described process for the manufacture of dyes from the products
of condensation referred to in claim 1 by direct treatment of the same with the nitroso-
compounds of tertiary aromatic amines.
3. The hereinbefore described process for the manufacture of dyes from the products
of condensation referred to in claim 1 by reduction of the said nitroso-compounds, and
subsequent oxydation together of the resulting diamines and bodies of condensation.
4. A dye obtained by the use of the herein before described products of condensation
of aniline and its homologues in combination with the oxynaphtol and the tertiary
nitroso amines, the manufacture being carried out by either of the processes described
or by a modification of either of them substantially as set forth.
1
CA
1007