Manufacture of New Colouring Matters.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
Manufacture of New Colouring Matters.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineor and Chartered
Patent Agent, do hereby declare the nature of this invention (as communicated to
me from abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in
the Empire of Germany, Chemical Manufacturers,) to be as follows:-
My foreign correspondents have discovered that imido-thiodiphenylimide de-
scribed by Bernthsen (Liebigs Anualen 230, 103) is very easily acted upon by primary,
secondary or tertiary amines even at ordinary temperature, alkylated or alphylated
thionines being formed.
For instance the action of aniline upon the above named imide may be represented
by the following formula :-
The leuco-derivative of imidothiodiphenylimide which is formed as intermediate
product is immediately oxidized by the atmospheric air, imide being formed again,
which reacts with a new quantity of amine; thus at the end of the reaction the whole
quantity of imide becomes transformed into dyestuff.

page_text: Instead of imidothiodiphenylimide its leuco-derivative, p-amidothiodiphenyl-
amine (Liebigs Annalen 230, 101) may be used, which is oxidized in the presence of
an amine. While the action of primary and secondary amines is generally
effected at ordinary temperature without difficulty, proceeds a little more slowly
with tertiary amines.
Generally the new process may be effected by acting upon imidothiodiphenyl-
imide or its salts with an excess of amine, which at the same time is used as a
solvent. With liquid amines the reaction is generally effected at ordinary tempera-
ture; otherwise the mixture must be heated, a convenient solvent being added if
necessary.
As amines not only monamines and polyamines may be used, but also their halo-
gen or nitro-derivatives, amidoazo-compounds and any other substituted amines may
likewise be introduced into the new process. Imidothiodiphenylimide is preferably
used in the form of a salt, for instance of its zinc chloride double salt, which can
easily be obtained. Salts of the leuco derivatives, for instance its hydrochloride
may also be used. The mixture is well stirred and preferably a current of air is
introduced in order to facilitate the oxidation. Naturally also, other oxidizing
agents may be used. The reaction being complete the dyestuff is isolated
by pressing the mixture and washing the residue with dilute hydrochloric
acid.
new colouring matters produce on silk, wool and mordanted cotton in
a bath acidified with acetic acid, voilet-blue to pure blue shades fast to light, acids
and soap.
The
The dyestuffs obtained by means of ammonia, methylamine, diethylamine,
trimethylamine, piperidine &c. produce shades varying from violet blue to blue,
while those produced with aniline, toluidine, anisidine, ethylaniline, dimethylto-
luidine, chloraniline, nitraniline, amidoazobenzene, benzidine, diamidoacetanilide
metatoluylenediamine, a-naphthylamine, and the like, produce pure blue to
greenish blue tints.
Dated this 18th day of November 1807
ABEL & IMRAY,
Agents for the Applicant.
Colouring Matters.
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 The 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 follow-
ing statement :-
My foreign correspondents have discovered that imido-thiodiphenylimide described
by Bernthsen (Liebigs Annalen 230, 103) is very easily acted upon by primary,
secondary or tertiary amines even at ordinary temperature, alkylated or alphylated
thionines being formed.
For instance the action of aniline upon the above named imide may be represented
by the following formula :-

page_text: The leuco-derivative of imidothiodiphenylimide which is formed as intermediate
product is immediately oxidized by the atmospheric air, imide being formed again,
which reacts with a new quantity of amine; thus at the end of the reaction the
whole quantity of imide becomes transformed into dyestuff.
Instead of imidothiodiphenylimide its leuco-derivative, p-amidothiodiphenylamine
(Liebigs Annalen 230, 101) may be used, which is oxidized in the presence of an
amine. While the action of primary and secondary amines is generally effected
at ordinary temperature without difficulty, it proceeds a little more slowly with
tertiary amines.
Generally the process may be effected by acting upon imidothiodiphenylimide or
its salts with an excess of amine, which at the same time is used as a solvent.
With liquid amines the reaction is generally effected at ordinary temperature;
otherwise the mixture must be heated, a convenient solvent being added if
necessary.
As amines not only monamines and polyamines may be used, but also their
halogen or nitro-derivatives, amidoazo-compounds and any other substituted
amines may likewise be introduced into the new process. Imidothiodiphenylimide
is preferably used in the form of a salt, for instance of its zinc chloride double salt,
which can easily be obtained.
Salts of the leuco derivatives, for instance its hydrochloride may also be used.
The mixture is well stirred and preferably a current of air is introduced in order to
facilitate the oxidation. Naturally also, other oxidizing agents may be used.
The reaction being complete the dyestuff is isolated by pressing the mixture and
washing the residue with dilute hydrochloric acid.
The new colouring matters produce on silk, wool and mordanted cotton in a bath
acidified with acetic acid, violet-blue to pure blue shades fast to light, acids and
soap.
The following examples may serve to illustrate the new process; the parts are
by weight.
(1). 1 part of the zinc-chloride double salt of imidothiodiphenylimide is
introduced into 10 parts of aniline, while constantly stirring. If after stirring for
several hours the mixture does not thicken any further the colouring matter formed
The dyestuff
is pressed off, washed with diluted hydrochloric acid and dried."
obtained produces on silk, wool and mordanted cotton in bath acidified with acetic
acid violet blue shades, fast to light, acids and soap.
(2) The same dyestuff may also be produced in the following manner:-1 part
of the hydrochloride of leuco-imidothiodiphenylimide is suspended in alcohol and
2 parts of aniline are added thereto. A current of air is passed through the
mixture until the formation of the dyestuff is completed; the latter is then pressed

page_text: off, washed with hydrochloric acid, and dried. Another portion of the colouring
matter formed may be obtained by concentrating the filtrate, pressing and drying.
As above stated, instead of aniline, other amines or their derivatives may be
used in this new process. Colouring matters producing violet-blue to blue
shades are, for instance, obtained with the following amines :
Ammonia, methylamine, ethylamine, benzylamine, dimethylamine, diethylamine,
trimethylamine, piperidine.
Analogous colouring matters,, producing from pure blue to greenish-blue shades,
are obtained by using the following amines:
Aniline, o-toluidine, p-toluidine, m-xylidine, o-anisidine, p-phenetidine,
methylaniline, ethylaniline, dimethylaniline, diethylaniline, ethyl-o-toluidine,
dimethyl-o-toluidine, dimethyl-p-toluidine, o-chloraniline, m-chloraniline, p,
chloraniline, m-nitraniline, diamidoazobenzene, benzidine, tolidine, dianisidine,
diamido-acetanilide, monoamidoacetanilide, m-toluylenediamine, methyl-ethyl- or
benzyl-m-tyluzlenediamine, a-naphthylamine, ethyl- or benzyl-a-naphthylamine,
B-naphthylamine.
The dyestuffs manufactured as above described generally appear in the dry state
as crystalline powders of dark blue or dark brown colour and of metallic lustre,
soluble in hot water, alcohol and acetic acid with blue colour. Caustic alkali or
ammonia produces the free bases, which are all more or less soluble in water with
violet colour; on shaking such solutions with ether the latter assumes a magenta-
red coloration. The dyestuffs dissolve in concentrated sulphuric acid with a dull
green colour, which, on addition of water, turns blueish-green or blue; their
acidified solutions are decolourised on addition of stannous chloride, the colouring
matters being converted into their leuco-derivatives.
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 herein described manufacture of new colouring matters of the thinonine
series by the action of ammonia or primary, secondary or tertiary amines of the
fatty or aromatic series on imido-thiodiphenylimide.
2. The herein described manufacture of new colouring matters of the thionine
series by the action of ammonia, or primary secondary or tertiary amines of the
fatty or aromatic series on the leuco-derivative of imidothiodiphenylimide in the
presence of an oxidising agent.
3. The new colouring matters manufactured as set forth in the preceding
claims.
0001
+000
ABEL & IMRAY,
Agents for the Applicant.