Production of Green and Blue to Blue Green Colouring Matters of the Triphenylmethan Series.
Year: 1892

page_text: Date of Application, 10th Oct., 1892
Complete Specification Left, 10th July, 1893-Accepted, 19th Aug., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUCIUS
AND BRUNING, of Hoechst a/ Main, in the Empire of Germany, Chemical
Manufacturers.]
Production of Green and Blue to Blue Green Colouring Matters of
the Triphenylmethan Series.
I, OLIVER IMRAY, of No. 28 Sonthampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
This invention relates to the production of green basic colouring matters from
the ethers of the dialkylised meta-oxy-para-amido-benzo-phenones by condensation
of the same with tertiary bases by means of phosphorus oxychloride vi bodies of
similar action and conversion of these green basic colouring matters into acid
colouring matters of blue to blue green shades by treating them with sulphuric acid
or fuming sulphuric acid.
UI
UL
of the same with tertiary Dases by means of phosphor окусшог
similar action and conversion of these green basic colouring matters into acid
colouring matters of blue to blue green shades by treating them with sulphuric acid
or fuming sulphuric acid.
EXAMPLE I.
10 parts by weight of meta-ethoxy-para-dimethyl-amido-benzophenone
6.8 parts by weight of methyldiphenylamine
10 parts by weight of phosphorus-oxy-chloride
are cautiously heated in an enamelled or copper vessel to 95° C. and are kept under
agitation at a temperature.between 90° and 100° C. for about 3 hours.
The mixture of the three substances soon liquefies forming a thin mass which,
towards the end of the operation, becomes thick and tenacious and assumes feebly
metallic lustre. It is then poured into about 100 parts by weight of cold water
and the whole is heated to 50° or 60° C. and stirred until all has become liquid and
well mixed with the water.
After standing about 12 hours, the green coloured acid liquid is separated from
the semi-solid colouring matter, which lies on the bottom of the vessel and which is
quickly dried on a flat copper vessel at water bath temperature.
The colouring matter is thus obtained in form of its hydrochlorate, an amorphous
mass of dark green feebly metallic exterior; it is readily soluble in alcohol with
green colour and, when in the form of its neutral salt, it can be dissolved without
much difficulty in water.
By treatment with sulphuric acid the green basic colouring matter is converted
into a blue sulphonic acid readily soluble in water.
For producing this sulphonic acid 10 parts by weight of the colouring matter are
introduced at ordinary temperature under agitation into 30 parts by weight of
sulphuric acid containing 20 per cent. of anhydride.
After the whole mass has dissolved, the mixture is poured into about 500 parts
by weight of cold water. There results a deep blue solution, which is neutralised
by adding lime or carbonate of lime, filtered and evaporated to dryness either as it
is produced, or after being converted into the sodium salt.
The neutral calcium or sodium salt of the colouring matter sulphonic acid thus
obtained is in form of a dark cherry red mass, very readily soluble in water, giving
a beautiful blue colour; when a small quantity of soda lye is added to the solution
the colour becomes more red violet; when it is super saturated with ammonia there
is little or no change from the original colour.
The colouring matter dyes wool and silk in acid bath a greenish blue which is
fast in washing.

page_text: EXAMPLE II.
10 parts by weight of meta-ethoxy-para-dimethyl-amido-benzophenone
8.8 parts by weight of alpha-methyl-phenyl-naphthylamine
10 parts by weight of phosphorus-oxy-chloride
are treated in the manner described in Example I and by the same operation and
in exactly the same manner the green basic colouring matter is obtained.
This basic colouring matter on being treated with sulphuric acid is also
transformed into its readily soluble sulphonic acid. For this purpose there are
introduced, at ordinary temperature and while agitated, 10 parts by weight of the
basic colouring matter into 30 parts by weight of sulphuric acid containing
20 per cent. of anhydride, and the mixture is farther treated exactly as described in
Example I.
The colouring matter-sulphonic acid-thus obtained or its neutral salt dissolves
easily in water, giving a somewhat bluer shade than the sulphonic acid previously
described; with soda lye and ammonia it behaves in the same manner as the other
sulphonic acid previously described.
Wool and silk are dyed in an acid bath a blue shade which is also fast in
washing but of less greenish shade than that produced by the colouring matter
described in Example J..
Dated this 10th day of October 1892.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Production of Green and Blue to Blue Green Colouring Matters of
the Triphenylmethan Series.
I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, 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 :-
This invention relates to the production of green basic colouring matters from
the ethers of the dialkylised meta-oxy-para-amido-benzo-phenones by condensation
of the same with tertiary bases by means of phosphorus oxychloride or bodies of
similar action and conversion of these green basic colouring matters into acid
colouring matters of blue to blue green shades by treating them with sulphuric acid
or fuming sulphuric acid.

page_text: amorphous mass of dark green feebly metallic exterior; it is readily soluble in
alcohol with green colour and when in the form of its neutral salt it can be.
dissolved without much difficulty in water.
By treatment with sulphuric acid the green basic colouring matter is converted
into a blue sulphonic acid readily soluble in water.
For producing this sulphonic acid, 10 parts by weight of the colouring matter are
introduced at ordinary temperature under agitation into 30 parts by weight of
sulphuric acid containing 20 per cent. of anhydride.
After the whole mass has dissolved, the mixture is poured into about 500 parts.
by weight of cold water. There results a deep blue solution, which is neutralised
by adding lime or carbonate of lime, filtered and evaporated to dryness, either as it
is produced or after being converted into the sodium salt.
The neutral calcium or sodium salt of the colouring matter-sulphonic acid thus
obtained is in form of a dark cherry-red mass very readily soluble in water, giving
a beautiful blue colour; when a small quantity of soda-lye is added to the solution,
the colour becomes more red-violet; when it is super-saturated with ammonia there
is little or no change from the original colour. The colouring matter dyes wool.
and silk in acid bath a greenish-blue which is fast in washing.
10 parts by weight of meta-ethoxy-para-dimethyl-amido-benzophenone
8-8 parts by weight of alpha-methyl-phenyl-naphthylamine
10 parts by weight of phosphorus-oxy-chloride
are treated in the manner described in Example I, and, by the same operation and
in exactly the same manner, the green basic colouring matter is obtained.
This basic colouring matter, on being treated with sulphuric acid, is also
transformed into its readily soluble sulphonic acid.
For this purpose, there are introduced at ordinary temperature and while
agitated, 10 parts by weight of the basic colouring matter into 30 parts by weight
of sulphuric acid containing 20 per cent. of anhydride and the mixture is farther
treated exactly as described in Example I.
The colouring matter sulphonic acid thus obtained or its neutral salt dissolves.
easily in water giving a somewhat bluer shade than the sulphonic acid previously
described; with soda-lye and ammonia it behaves in the same manner as the other
sulphonic acid previously described.
Wool and silk are dyed in an acid bath a blue shade which is also fast in washing,
but of less greenish shade than that produced by the colouring matter described in
Example I.
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 production of green basic colouring matters by condensing the ethers of
the dialkylised meta-oxy-para-amido-benzophenones with tertiary aromatic bases
by means of phosphorus-oxy-chloride or bodies of similar action, and the conversion
of these green basic colouring matters into blue to blue green acid-colouring matters
by treating the same with sulphuric acid or fuming sulphuric acid.
2. The green basic colouring matters and the blue to blue green acid colouring
matters produced in the manner above referred to.
Dated this 4th day of July 1893.
ABEL & IMKAY,
Agents for the Applicant.