Manufacture of Green-blue Colouring Matters.
Year: 1899

page_text: Date of Application, 23rd Oct.,
4000
Complete Specification Loft 20th June 1000 Accented 11th Aug
1900
Complete Specification Loft 20th June 1000 Accepted 11th Aug 1900
PROVISIONAL SPECIFICATION.
Manufacture of Green-blue Colouring Matters.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, 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) to be as follows:-
This invention relates to the manufacture of green-blue dyestuffs belonging
to the triphenylmethane series and is based on the following observations.
My foreign correspondents have found that the leuco-bases obtained by the
process described in the Specification No. 8959 of 1899 by the action of tetra-
alkyldiamidobenzhydrols upon ortho-toluidine can easily be diazotised and con-
verted with very good yield into the corresponding oxyleuco-bases by boiling the
diazotised solutions obtained. When the oxyleuco-bases thus produced are
treated with sulphonating agents, a sulphonic group is readily introduced and
there are formed sulphonic acids of the oxyleuco-bases.
They have further found that by treating these sulphonic acids with oxidising
agents there are produced fine green-blue dyestuffs, which are distinguished by
valuable tinctorial properties. These dyestuffs are also obtained by first oxidis-
ing the oxyleuco-bases and afterwards sulphonating the colouring matters thus
formed.
The invention is further illustrated by the following example:
A solution of 3.5 kilos. of sodium nitrite in 30 litres of water is allowed to
run slowly into a solution of 18 kilos. of the base produced by the process above
mentioned from ortho-toluidine and tetramethyldiamidobenzhydrol, in 300 litres
of water and 24 kilos. of concentrated sulphuric acid. Large quantities of
nitrogen are given off at low temperature and the reaction is completed by
heating the liquid for a short time at 60° to 70° C. After refrigeration the
solution is neutralised by addition of caustic soda lye or sodium carbonate and
the oxybase is thereby precipitated in the form of white flakes. The vield is
quantitative. The new oxyleuco-base crystallises from alcohol in the form of
thin needles forming spheric aggregates, melting at 141° C. By the action of
the usual oxidising agents on this oxyleuco-base a dyestuff is formed which is
distinguished from the corresponding dyestuff obtained from the amido-base by
its far more greenish shade.
In order to transform the oxyleuco-base into the sulphonic acid the process
is as follows:-
18 kilos. of the oxyleuco-base are dissolved in the cold in 75 kilos. of concen-
trated fuming sulphuric acid containing 10 per cent. SO,. The mixture is allowed
to stand at a temperature of 30° to 40° C. until a sample does not become turbid
on addition of diluted ammonia. The calcium and sodium salt of the sulphonic
acid are obtained by the usual methods. The sodium salt is precipitated from
its aqueous solution on addition of common salt. From the solution of the
sodium salt the free sulphonic acid is obtained in the form of white flakes by

page_text: addition of an excess of acetic acid or of a quantity of sulphuric acid equivalent
to the sodium.
The sulphonic acid thus produced is converted by treatment with peroxide of
lead or some other oxidising agent into a clear blue-green dyestuff remarkably
fast to alkalies and distinguished by its equalising power.
The sodium salt of the dyestuff is readily soluble in water; from this solution
it is precipitated by the addition of common salt.
It forms in dry state a powder of coppery. lustre.
By substituting in the above example for the base obtained by the action of
tetramethyldiamidobenzhydrol on ortho-toluidine the corresponding base obtained
by the action of tetraethyldiamidobenzhydrol on ortho-toluidine, a dyestuff of
similar properties is produced.
The same dyestuffs are likewise obtained by first oxidising the oxyleuco-bases
prepared as above described, and afterwards sulphonating the colouring matters
formed by the oxidation.
:I
1
30
1000
ABEL & IMRAY,.
Agents for the Applicant.
Manufacture of Green-blue Colouring Matters.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, 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
following statement:―
This invention relates to the manufacture of green-blue dyestuffs belonging
to the triphenylmethane series and is, based on the following observations.
My foreign correspondents have found that the leuco-bases obtained by the
process described in the Specification No. 8959 of 1899 by the action of tetra-
alkyldiamidobenzhydrols upon ortho-toluidine can easily be diazotised and con-
verted with very good yield into the corresponding oxyleuco-bases by boiling the
diazotised solutions obtained. When the oxyleuco-bases thus produced are
treated with sulphonating agents, a sulphonic group is readily introduced and
there are formed sulphonic acids of the oxyleuco-bases.
They have further found that by treating these sulphonic acids with oxidising
agents there are produced fine green-blue dyestuffs, which are distinguished by
valuable tinctorial properties. These dyestuffs are also obtained by, first oxidis-
ing the oxyleuco-bases and afterwards sulphonating the colouring matters thus.
formed.
The invention is further illustrated by the following example:
A solution of 3.5 kilos. of sodium nitrite in 30 litres of water is allowed to
run slowly into a solution of 18 kilos. of the base produced by the process above
mentioned from, ortho-toluidine and tetramethyldiamidobenzhydrol, in 300 litres
of water and 24 kilos. of concentrated sulphuric acid. Large quantities of
nitrogen are given off at low temperature and the reaction is completed by
heating the liquid for a short time at 60° to 70°C. After refrigeration the
solution is neutralised by addition of caustic soda lye or sodium carbonate and
the oxybase is thereby precipitated in the form of white flakes. The yield is

page_text: quantitative. The new oxyleuco-base crystallises from alcohol in the form of
thin needles forming spheric aggregates, melting at 141° C. By the action of
the usual oxidising agents on this oxyleuco-base a dyestuff is formed which is
distinguished from the corresponding dyestuff obtained from the amido-base by
its far more greenish shade.
In order to transform the oxyleuco-base into the mono sulphonic acid the
process is as follows:-
18 kilos. of the oxyleuco-base are dissolved in the cold in 75 kilos. of concen-
trated fuming sulphuric acid containing 10 per cent. SO. The mixture is allowed
to stand at a temperature of 30° to 40° C. until a sample does not become turbid
on addition of diluted ammonia. The calcium and sodium salt of the sulphonic
acid are obtained by the usual methods. The sodium salt is precipitated from
its aqueous solution on addition of common salt. From the solution of the
sodium salt the free sulphonic acid is obtained in the form of white flakes by
addition of an excess of acetic acid or of a quantity of sulphuric acid equivalent
to the sodium.
The sulphonic acid thus obtained is converted into the corresponding dyestuff
by means of peroxide of lead or some other oxidising agent. This oxidation
may be performed as follows:
46.1 kilos. of the sodium salt of the oxyleucosulphonic acid are dissolved in
500 litres of water, and the theoretical quantity of sulphuric acid and peroxide
of lead are added thereto. After filtering off the lead sulphate, the product of
the oxidation is precipitated from the solution by means of common salt.
The sodium salt of the new dyestuff thus produced forms in dry state a
powder of coppery lustre. It is readily soluble in water; from this solution it
is precipitated by means of common salt. It produces on wool and silk fine
green-blue shades remarkably fast to alkalies and is distinguished by its power
of dyeing evenly.
The sodium salt of the dyestuff is readily soluble in water; from this solution
it is precipitated by addition of common salt.
It forms in dry state a powder of coppery lustre.
By substituting in the above example for the base obtained by the action of
tetramethyldiamidobenzhydrol on ortho-toluidine the corresponding base obtained
by the action of tetraethyldiamidobenzhydrol on ortho-toluidine, a dyestuff of
similar properties is produced.
The same dyestuffs are likewise obtained by first oxidising the oxyleuco-bases
prepared as above described, and afterwards sulphonating the colouring matters
formed by the oxidation.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The herein described manufacture of green-blue colouring matters by first
transforming the leuco bases obtained by the action of tetra-alkyldiamido-
benzhydrols on ortho-toluidine, as described in Specification No. 8959 of 1899,
into the corresponding oxyleuco-bases by diazotisation and subsequent boiling,
then sulphonating these oxyleuco-bases and finally converting the sulphonic acids
thus produced into colouring matters by means of oxidising agents.
2. The colouring matters manufactured as above set forth.
1000
ABEL & IMRAY,
Agents for the Applicant.