Manufacture of Naphthophenazonium Compounds.
Year: 1899

page_text: Date of Application, 29th May, 1899
Complete Specification Left, 15th Feb., 1900-Accepted, 24th Mar., 1900
PROVISIONAL SPECIFICATION.
Manufacture of Naphthophenazonium Compounds.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered
Patent Agent, do hereby declare the nature of this invention (as communicated
to me from abroad by Actien-Gesellschaft für Anilin-Fabrikation, of Berlin, in the
Empire of Germany, Chemical Manufacturers,) to be as follows:-
O. N. Witt has described a process for the production of naphthophenazine (com-
pare Berichte der deutschen chemischen Gesellschaft XX, 571) which is based on
the observation that azo-compounds obtained with secondary bases derived from B-
naphthylamine, such as phenyl- tolyl- or xylyl-6-naphthylamine, when boiled with
diluted mineral acids are completely split up according to the following equation:
The compounds obtained by the above process have not found any technical appli-
cation nor could more valuable derivatives of the same be obtained owing to their
great stability and want of reactive power.
My correspondents have now found that azo-compounds obtained by means of
certain tertiary B-naphthylamine bases when split up by boiling with mineral acids
yield azonium compounds according to the following equation:
Contrary to the naphthophenazine, the azonium compounds obtained in the manner
20 described are most reactive substances as has already been stated in regard to other
derivatives of the same series (compare Kehrmann and Schaposchnikoff, Berichte der

page_text: deutschen chemischen Gesellschaft XXX, 2620). The new products accordingly form
valuable parent compounds for the manufacture of safranine or rosinduline colouring
matters.
The following derivatives have been proved suitable for the new process: methyl-
phenyl-6-naphthylamine, methyltolyl-ẞ-naphthylamine, ethylphenyl-6-naphthyl-
amine, ethyltolyl-ẞ-naphthylamine and the sulphonic acids of these compounds.
The invention is illustrated by the following example.
1 kilo. of the dyestuff obtained from diazotised sulphanilic acid and phenylmethyl-
B-naphthylamine is digested with 10 kilos. of hot water and 1 kilo. of concentrated
hydrochloric acid. The methylnaphthophenazonium chloride thus formed is dis-
solved with yellow coloration. The solution is filtered from the separated sulphanilic
acid and some resinous matter and the new colouring matter is precipitated by means
of zinc chloride or common salt. The dyestuff separates in the form of orange coloured
needles. It dyes tannin mordanted cotton orange yellow tints.
In quite analogous manner other azo-compounds derived from tertiary naphthyl-
amine bases can be split up into the corresponding azonium compounds.
Dated this 29th day of May 1899.
ABEL
& IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Naphthophenazonium Compounds.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered
Patent Agent, do hereby declare the nature of this invention (as communicated to
me from abroad by Actien-Gesellschaft für Anilin Fabrikation, of Berlin, in the
Empire of Germany, Chemical Manufacturers,) and in what manner the same is
to be performed to be particularly described and ascertained in and by the following
statement :-
0. N. Witt has described a process for the production of naphthophenazine
(compare Berichte der deutschen chemischen Gesellschaft XX, 571) which is based
on the observation that azo-compounds obtained with secondary bases derived from
B-naphthylamine, such as phenyl-, tolyl- or xylyl-6-naphthylamine, when boiled
with diluted mineral acids are completely split up according to the following
equation
The compounds obtained by the above process have not found any technical
application nor could more valuable derivatives of the same be obtained owing to
their great stability and want of reaction power.
My correspondents have now found that azo-compounds obtained by means of

page_text: certain tertiary B-naphthylamine bases when split up by boiling with mineral acids
yield azonium compounds according to the following equation:-

page_text: concentrated solution of diazobenzene-sulphonic acid obtained from 35 parts of
sulphanilic acid.
The azo-dyestuff produced at first is slowly decomposed, the azonium compound
being formed, part of which crystallises from the liquid together with large
quantities of regenerated sulphanilic acid. In order to isolate the rest of the
azonium-compound, remaining in the solution, the liquid is diluted with 2 to 3 parts
of water, filtered from some resinous matter and precipitated by means of common
salt or chloride of zinc. The dyestuff thus obtained resembles by its properties that one
described in Example 1.
For the methyl-derivatives employed in Examples 1 and 2 the corresponding ethyl-
compounds can be substituted.
EXAMPLE 3.
The dyestuff obtained from diazotised para-nitraniline and methyl-para-tolyl-
B-naphthylaminesulphonic acid is digested for twelve hours with two parts of
sulphuric acid and twenty parts of water at about 80° C. After filtering off
some resinous matter the sulphonic acid of the ozonium-compound is precipi-
tated from the solution obtained as brown crystals, which dye wool orange-yellow
tints.
In the process described in the preceding examples other azo-compounds derived
from tertiary-ẞ-naphthylamines of the alkyl-alphyl series or from their sulphonic
acids may be employed with a similar result.
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 herein described manufacture of naphthophenazonium compounds by
heating with diluted mineral acids the azo-compounds obtained from methyl-phenyl-
B-naphthyl-amine or from its homologues or from sulphonic acids of these
compounds.
2. The new naphthophenazonium compounds manufactured as above set forth.
ABEL & IMRAY,
Agents for the Applicant.