THE PRO- DUCTION OF NEW COLORING MATTERS FOR DYEING AND PRINTING
Year: 1878

page_text: LETTERS PATENT to Charles Denton Abel, of No. 20, Southampton Buildings,
Chancery Lane, in the County of Middlesex, for the Invention of "THE PRO-
DUCTION OF NEW COLORING MATTERS FOR DYEING AND PRINTING." A com-
munication from abroad by The Actien Gesellschaft fuer Anilin Fabrikation, of
Berlin, in the German Empire.
Sealed the 7th May 1878, and dated the 1st March 1878.
PROVISIONAL SPECIFICATION left by the said Charles Denton Abel at the
Office of the Commissioners of Patents on the 1st March 1878.
CHARLES DENTON ABEL, of No. 20, Southampton Buildings, Chancery Lane, in
the County of Middlesex. "THE PRODUCTION OF NEW COLORING MATTERS FOR
DYEING AND PRINTING." [A communication from abroad by The Actien Gesell-
schaft fuer Anilin Fabrikation, of Berlin, in the German Empire.]
The present Invention consists,--
Firstly. In the production of green coloring matters by the action of benzotri-
chloride on aromatic tertiary amines in the presence of metallic chlorides, such
as chloride of zinc, cadmium, tin, mercury, iron, &c.
Secondly. In the production of yellowish, orange, and red coloring matters by
the action of benzotrichloride on phenoles, all coloring matters produced in such
manner being suitable for dyeing and printing.
Under the name "benzotrichloride" is to be understood the substance to which
chemists give the formula C., H., C. Cl,, having an average boiling point of 215° C.,
and which is obtained by treating the vapours of toluole or chloride of bensile with
chlorine.
1. Production of Green Coloring Matters by the Action of Bensotrichloride on
Aromatic Tertiary Amines-All so-called aromatic tertiary monamines, of which
bimethyle-aniline (bimethylephenylamine) and methylediphenylamine are typical
compounds, yield by the action of bensotrichloride, in presence of metallic chlorides,
green coloring matters, which dye in shades similar to methyle-green, although they

page_text: are not identical with them, and also differ in their resistance to higher temperatures.
The presence of metallic chlorides is not absolutely necessary for the production of
smaller quantities of coloring matter, as benzotricbloride and the amines alone, if
heated together, already yield a green coloration, but for the production on a manu-
facturing scale, and for a perfect conversion, the addition of chloride is needed.
In producing the coloring matter from bimethyle-aniline 3 parts of bimethyle-
aniline, 2 parts of benzotrichloride, and 1 parts of dry chloride of zinc are heated
in an enamelled vessel for 3 hours, to 110° C., under constant stirring. The product
obtained is treated by direct steam to distill all volatile substances over; the residue
is then extracted by boiling water. From the filtered solution the coloring matter
is precipitated by sodic chloride. The coloring matter thus obtained may be used
dissolved in water or spirit directly for dyeing and printing.
By the same process methylediphenylamine is equally converted into a green
coloring matter.
In working on a large scale it is advantageous to moderate the very energetic
action by adding powdered or liquid substances like sand, salt, or hydrocarbons,
that serve to dilute without having any chemical action.
2. Production of Yellow, Orange, and Red Coloring Matters by the Action of
Benzotrichloride on Phenoles.--All so-called phenoles, of which phenole, napthole,
and resorcine may be considered as typical compounds, if heated with benzotri-
chloride are converted into yellow coloring matters, of which the compounds derived
from phenole or napthole are very similar in their chemical properties to amine,
whilst the compound derived from resorcine forms a substance very similar to fluor-
esceine, yielding with bromine, in the same way as fluoresceine, orange and red
colored products of substitution.
In producing the latter compound on a manufacturing scale 6 parts of resorcine
and 5 parts of benzotrichloride are heated in an enamelled vessel for several hours,
at a temperature from 100°-120° C. The product of the reaction is extracted by
means of boiling water, and forms a substance similar to fluoresceine, insoluble in
water, soluble in spirit or alkali. The solution in alkali diluted with water shows
also fluoresceine, and dyes wool and silk, under addition of acids or alum, yellow.
If this product, suspended in glacial acetic acid, is treated with a solution of
bromine in the same solvent, and then treated with an excess of water, a brominated
product is obtained, which is soluble in alkali, with a red color, and which can be
purified in the well-known process used for eosine, and yields a coloring matter of
similar properties.
Benzotrichloride has been exclusively mentioned above as the re-agent, but it is to
be particularly noted that instead of benzotrichloride also the corresponding bromine
compound or mixtures of both may be used, and that also instead of the metallic
chlorides mentioned above other metallic compounds may be applied to accelerate
the reaction.
Of the tertiary aromatic bases yielding the characteristic reaction with benzotri-
chloride only those have been mentioned above that are at present actually com-
mercially produced, as bimethyle-aniline and methyledyphenylamine; and also of
the phenoles, only phenole, napthole, and resorcine have been mentioned as being
now accessible to manufacturing chemists, but it is to be distinctly understood that
the present Invention includes as well the use of the corresponding ethylated bases,
as well as the homologues of phenole and the isomeric compounds of resorcine, as
they all yield coloring matter benzotrichloride.
Although certain proportions of the various materials have been given above it
is to be understood that these proportions may be varied within considerable
limits.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Charles Denton Abel in the Great Seal Patent Office on the 24th
May 1878.
CHARLES DENTON ABEL, of No. 20, Southampton Buildings, Chancery Lane, in
the County of Middlesex. "THE PRODUCTION OF NEW COLORING MATTERS FOR
DYEING AND PRINTING." A communication from abroad by The Actien Gesell-
schaft fuer Anilin Fabrikation, of Berlin, in the German Empire.
The present Invention consists,—
Firstly. In the production of green coloring matters by the action of benzotri-
chloride on aromatic tertiary amines in the presence of metallic chlorides, such as
chloride of zinc, cadmium, tin, mercury, iron, &c.
Secondly. In the production of yellowish, orange, and red coloring matters by
the action of benzotrichloride on phenoles, all coloring matters produced in such
manner being suitable for dyeing and printing.
Under the name "benzotrichloride is to be understood the substance to
which chemists give the formula C, H., C. Cl, having an average boiling point of
215° C., and which is obtained by treating the vapours of toluole or chloride of
bensile with chlorine.
1. Production of Green Coloring Matters by the Action of Benzotrichloride on
Aromatic Tertiary Amines.-All so-called aromatic tertiary monamines, of which
bimethyle-aniline (bimethylephenylamine) and methylediphenylamine are typical
compounds, yield by the action of benzotrichloride, in presence of metallic chlorides,
green coloring matters, which dye in shades similar to methyle-green, although they
are not identical with them, and also differ in their resistance to higher tem-
peratures. The presence of metallic chlorides is not absolutely necessary for the
production of smaller quantities of coloring matter, as benzotrichloride and the
amines alone, if heated together, already yield a green coloration, but for the pro-
duction on a manufacturing scale, and for a perfect conversion, the addition of
chloride is needed.
In producing the coloring matter from bimethyle-aniline 3 parts of bimethyle-
aniline, 2 parts of benzotrichloride, and 14 parts of dry chloride of zinc are heated
in an enamelled vessel for 3 hours to 110° C., under constant stirring. The product
obtained is treated by direct steam to distill all volatile substances over; the residuo
is then extracted by boiling water. From the filtered solution the coloring matter
is precipitated by sodic chloride. The coloring matter thus obtained may be used
dissolved in water or spirit directly for dyeing and printing.
By the same process methylediphenylamine is equally converted into a green
coloring matter.
In working on a large scale it is advantageous to moderate the very energetic
action by adding powdered or liquid substances, like sand, salt, or hydrocarbons,
that serve to dilute without having any chemical action.
2. Production of Yellow, Orange, and Red Coloring Matters by the Action of
Benzotrichloride on Phenoles.-All so-called phenoles, of which phenole nupthole
and resorcine may be considered as typical compounds, if heated with benzotri-
chloride are converted into yellow coloring matters, of which the compounds derived
from phenole or napthole are very similar in their chemical properties to amine,
whilst the compound derived from resorcine forms a substance very similar to fluor-
esceine, yielding with bromine, in the same way as fluoresceine, orange and red
colored products of substitution.
In producing the latter compound on a manufacturing scale 6 parts of resorcine
and 5 parts of benzotrichloride are heated in an enamelled vessel for several hours
at a temperature from 100° to 120° C. The product of the reaction is extracted
by means of boiling water, and forms a substance similar to fluoresceine, insoluble
in water, soluble in spirit or alkali. The solution in alkali diluted with water

page_text: shows also fluoresceine, and dyes wool and silk, under addition of acids or alum,
yellow.
If this product, suspended in glacial acetic acid, is treated with a solution of
bromine in the same solvent, and then treated with an excess of water, a brominated
product is obtained which is soluble in alkali with a red color, and which can be
purified in the well-known process used for eosine, and yields a coloring matter of
similar properties.
Benzotrichloride has been exclusively mentioned above as the re-agent, but it is
to be particularly noted that instead of benzotrichloride also the corresponding
bromine compound, or mixtures of both, may be used, and that also instead of the
metallic chlorides mentioned above other metallic compounds may be applied to
accelerate the reaction.
Of the tertiary aromatic bases, yielding the characteristic reaction with benzotri-
chloride only, those have been mentioned above that are at present actually com-
mercially produced, as bimethyle-aniline and methylediphenylamine, and also of the
phenoles only phenole, napthole, and resorcine have been mentioned as being now
available to manufacturing chemists, but it is to be distinctly understood that the
present Invention includes as well the use of the corresponding ethylated bases as
well as the homologues of phenole and the isomeric compounds of resorcine, as they
all yield coloring matter with benzotrichloride.
Although certain proportions of the various materials have been given above
it is to be understood that these proportions may be varied within considerable
limits.
Having thus described the nature of the said Invention, and in what manner
the same is to be performed, as communicated to me by my foreign correspondents,
I claim,-
First. The production of green coloring matter by the action of benzotrichloride,
or its corresponding bromine compound, or their mixture, on aromatic tertiary
amines, or their homologues, in the presence of metallic chlorides, substantially as
herein described.
Second. The production of yellow, orange, and red coloring matters by the
action of benzotrichloride, or its corresponding bromine compound, or their mixture,
on phenoles, or the corresponding ethylated bases, or their homologues, substantially
as herein described.
In witness whereof, I, the said Charles Denton Abel, have hereunto set my
hand and seal, this Fourteenth day of May, in the year of our Lord One
⚫ thousand eight hundred and seventy-eight.