Manufacture of New Red and Blue Colouring Matters.
Year: 1889

page_text: Date of Application, 20th July, 1889
Complete Specification Left, 22nd Mar., 1890-Accepted, 26th Apr.,
1890
TRUVIDIONAL DI BOLTIVATI
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY, in Basle, of
Basle, Switzerland, Chemical Manufacturers.]
Manufacture of New Red and Blue Colouring Matters.
I, OLIVER IMRAY of No. 28 Southampton Buildings, in the County of London,
Fellow of the Institute of Patent Agents, do hereby declare the nature of this inven-
tion to be as follows:-
This invention relates to the production of red and blue coloring matters of the
group of metaamidophenolbenzëine.
The coloring matters of this new group are produced by the action of benzotri-
chloride upon the alkyl derivatives and the phenyl derivatives of the metaamido-
phenol.
Their production may be explained by the following equation:
R and R¹ mean to express generally the alkyl radicles methyl, ethyl, amyl, benzyl,
as well as the aromatic radicles phenyl, tolyl, naphthyl.
The methyl and ethyl derivatives of metaamidophenolbenzeïn give a more bluish
shade than the respective derivatives of the rhodamingroup, but as regards beauty of
colour and fluorescence they are very similar to these. In their taking to the fibre
there are sensible differences. Whilst rhodamines, for instance do not shew much
affinity to vegetable fibre, the benzeïnes are quickly and entirely absorbed by
mordanted cotton. The color of the alkylderivatives of metaamidophenolbenzeïne
varies from red to violet, they are soluble in water; the phenylated derivatives (from
benzotrichloride and metaoxydiphenylamine and its homologues and substitution product
of alkyl) gives shades varying from blue violet to blue, they are soluble in alcohol
but to render them soluble in water they must first be transformed by sulphuring
agents.
In contrast with rhodamines the methyl and ethly derivatives of metaamidophenol-
benzcine are easily converted into sulphur-acids by the action of fuming sulphuric
acid.
According to the present invention a red coloring matter is produced by con-
densation of dimethylmetaamidophenol with benzotrichloride which is the
For this purpose, 10 kilos of benzotrichloride
13 ,, dimethylmetaamidophenol
50
"
"
"1
sand
are well mixed in an enamelled vessel and the mixture while agitated is heated up to
from 50° to 60° C. As soon as the beginning of the reaction shews itself by the
changing of the color of the mixture, first from grey to a bluish violet, afterwards to

page_text: a reddish violet, as well as by rapid elevation of the temperature above 60° C), the
heating has to be interrupted.
The production of the coloring matter proceeds generally without heating any
more, at from 65° to 70° C. Finally the mixture is heated for some hours up to 100°
to 120° C.
If during the condensation no diluter such as sand, common salt &c. is added, a
turbulent reaction takes place, the temperature exceeding 180° and sub products are
formed rendering the purification of the coloring matter very difficult.
In order to remove volatile products, the molten mass is treated with water vapour
and the coloring matter is extracted by boiling with 50 kilos of water and 2 kilos of
concentrated muriatic acid.
After cooling, the liquor is purified by filtering from the red and resinous sub-
stances.
By addition of 20 kilos of caustic soda-lye of 38° Beaume the coloring base is
separated out, filtered and purified by washing in water. The colouring base is then
rendered soluble in hot diluted muriatic acid, the cooled solution is filtered again and
the coloring matter is precipitated by addition of common salt in form of its hydro-
chloride. The coloring matter is purified by solution in hot water; the liquor is left
alone for some time and small quantities of a product that is soluble with difficulty
separate out. Finally by addition of caustic soda-lye the coloring base is pre-
cipitated out of the filtrate. By dissolving it in an aqueous solution of oxalic acid
the coloring base is converted into its oxalato-salt. Out of a hot concentrated solution
the oxalate crystallises on cooling in form of thin needles of a green metallic lustre.
There is also another way of purification by extracting the coloring base with benzol
or toluol, and agitating the extract with warm diluted muriatic acid. Thus the
hydrochloride of dimethylmietaamidophenolbenzeïne passes over into the aqueous
solution and on cooling separates out in small green needles of a metallic lustre.
By dissolving the coloring base in sulphuric acid or acetic acid, the sulphuric and
acetic salts which are also easily soluble in water are obtained. The salts of tho
dimethylmetaamidophenolbenzeïne dissolve in water and alcohol with a splendid pink
color and a yellowish red fluorescence. The solution in concentrated sulphuric acid
is of an orange-yellow color, by addition of water it changes its color to red.
By adding caustic soda lye to the aqueous solutions of the coloring matter the
coloring base separates out in pink flakes.
The coloring case is nearly insoluble in water, but easily soluble in alcohol, ether,
benzol, and toluol. It crystallises out of benzol in needles of a pale pink color.
Wool and silk are dyed crimson by it without mordant. On silk the fluorescence
shows a yellowish red tint. The dye haths are entirely exhausted by wool as well as
by cotton. Cotton must be mordanted with tannin, and the dyes are of a more bluish
tint.
SULPHOACID OF THE DIMETHYLMETA AMIDOPHENOLBENZEÏNE.
For producing this substance 10 kilos of the coloring base are pulverized and
added to 40 kilos of fuming sulphuric acid of 20% while cooling. This mixture
is heated to about 60° C. until completely dissolved, and is then heated to about 90°
to 100° C. When by testing a sample with addition of caustic soda and diluted
with water, the coloring base does not precipitate any more, the melt is put into
cold water and treated with lime; and the sodium salt, is obtained in the usual
manner. Or the mixture may be diluted with water and caustic soda-lye added
until the solution is nearly neutralized, whereupon the sulphoacid of the coloring
matter will separate out..
It is filtered off and dissolved in caustic soda-lye for transformation into the
easily soluble sodium-salt. The latter is obtained in a compact form by evaporation
of the solution or by precipitation with common salt. It is a green powder of a
metallic lustre, easily soluble in water producing a fine crimson tint with yellowish
fluorescence. The solution with concentrated sulphuric acid is of a yellow tint with
a fine greenish yellow fluorescence. The dyes produced by the sulphoacid of

page_text: dimethylmetaamidophenolbenzeïne are similar to those obtained by the dimethylmeta-
amidophenolbenzeïno.
.adi1
CT1
1000
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of New Red and Blue Colouring Matters.
I, OLIVER IMRAY, of No. 28 Southampton Buildings Chancery Lane in the County
of London, Fellow of the Institute of Patent Agents, 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 red and blue colouring matters of the
group of metaamidophenolbenzeïne.
The colouring matters of this new group are produced by the action of benzo-
trichloride upon the alkyl derivatives and the phenyl derivatives of the metaamido-
phenol.
Their production may be explained by the following equation
Rand R mean to express generally the alkyl radicles methyl, ethyl, amyl, benzyl,
as well as the aromatic radicles phenyl, tolyl, naphthyl.
The methyl and ethyl derivatives of metaamidophenolbenzeïne give a more bluish
shade than the respective derivatives of the rhodamine group, but, as regards beauty
of colour and fluorescence, they are very similar to these. In their taking to the fibro
there are sensible differences. Whilst rhodamines, for instance, do not shew much
affinity to vegetable fibre, the benzeïnes are quickly and entirely absorbed by mordanted
cotton. The color of the alkyl derivatives of metaamidophenolbenzeīne varies from
red to violet, they are soluble in water; the phenylated derivatives (from benzo-
trichloride and metaoxydiphenylamine and its homologues and substitution products
of alkyl) give shades varying from blue violet to blue, they are soluble in alcohol
but, to render them soluble in water, they must first be transformed by sulphuring
agents.
In contrast with rhodamines the methyl and ethyl derivatives of metaamidophenol-
benzeïne are casily converted into sulphur acids by the action of fuming sulphuric
acid.
According to the present invention a red colouring matter is produced by condensa
tion of dimethylnictaamidophenol with benzotrichloride which is the
DIMETHYLMETA AMIDOPHENOLBENZEÏNE.
11
purposes
10 hilos of benzotrichloride
13
50
"
"
"
dimethylmetaamidophenol
sand
are well mixed in an enamelled vessel and the mixture, while agitatod, is heated up
to from 50° to 60° C. As soon as the beginning of the reaction shews itself by rapid
elevation of the temperature above 60° C., the heating has to be interrupted.
The production of the colouring matter proceeds generally without heating any
more at from 65° to 70° C. Finally the mixture is heated for some hours up to 100°
to 130° i's

page_text: If during the condensation no diluter such as sand, common salt &c. is added, a
turbulent reaction takes place, the temperature exceeding 180°, and sub products are
formed rendering the purification of the colouring matter very difficult.
In order to remove volatile products, the molten mass is treated with water vapour
and the coloring matter is extracted by boiling with 50 kilos of water and 2 kilos of
concentrated muriatic acid.
After cooling, the liquor is purified by filtering from the red and resinous
substances.
By addition of 20 kilos of caustic soda lye of 38° Beaume the coloring base is
separated out, filtered and purified by dissolving in diluted muriatic acid and
precipitating by addition of chloride of zinc and common salt. The hydrochlorate of
the colouring matter separates out in form of long green needles. By dissolving
it in an aqueous solution of oxalic acid the coloring base is converted into its
oxalate salt.
Out of a hot concentrated solution the oxalate crystallises on cooling in form of
thin needles of a green metallic lustre.
There is also another way of purification by extracting the coloring base with
benzol or toluol, and agitating the extract with warm diluted muriatic acid. Thus
the hydrochloride of dimethylmetaamidophenolbenzeïne passes over into the aqueous
solution and on cooling separates out in sinall green needles of a metallic lustre.
By dissolving the coloring base in sulphuric acid or acetic acid, the sulphuric and
acetic salts which are also easily soluble in water are obtained. The salts of the
dimethylmetaamidophenolbenzeïne dissolve in water and alcohol with a splendid pink
colour and a yellowish red fluorescence. The solution in concentrated sulphuric acid
is of an orange yellow colour, by addition of water it changes its colour to red.
By adding caustic soda lye to the aqueous solutions of the coloring matter the
coloring base separates out in pink flakes!
The coloring base is nearly insoluble in water, but easily soluble in alcohol, ether,
benzol, and toluol. It crystallizes out of bonzol in needles of a pale pink colour.
Wool and silk are dyed crimson by it without mordant. On silk the fluorescence
shows a yellowish red tint. The dye baths are entirely exhausted by wool as well as
by cotton. Cotton must be mordanted with tannin, and the dyes are of a more bluish
tint. In an analogous manner dye stuffs are obtained from diethylmetaamidophonol
and the other derivatives of metaamidophenol and benzotrichloride. By the action of
fuming sulphuric acid these colouring matters are transformed into sulpho acids.
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 manufacture of red and blue colouring matters by the action of benzo-
trichloride on the alkyl or phonyl derivatives of metaamidophenol, substantially as
described.
2. The colouring matters produced in the manner referred to in the preceding
claim.
ABEL & IMRAY,
Agents for the Applicant.