Improvements in the Production of Colouring Matters from Meta-amido-phenol-phthalëines.
Year: 1893

page_text: Date of Application, 22nd July, 1893
Complete Specification Left, 21st May, 1894-Accepted, 23rd June, 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUCIUS
AND BRUNING, of Hoechst a/ Main, Germany, Chemical Manufacturers.]
Improvements in the Production of Colouring Matters from
Meta-amido-phenol-phthalëines.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention to be as
follows:-
My foreign correspondents have discovered that by the action of aromatic bases,
such as, for example, dimethyl and diethylaniline, ethyl benzylaniline, methyl
diphenylamine, mono methyl and mono ethylaniline, mono ethyl ortho-toluidine,
aniline, toluidine, quinoline etc., upon the di and tetra-alkylised meta-amido-phenol
phthalëines under suitable conditions, are obtained a series of novel colouring
matters, excelling the alkylised meta amido phenyl-phthaleines, from which they
are derived, by bluer shade, and some of these by considerably greater affinity to
vegetable fibres.
The colouring matters obtained from the tetra alkylised meta amido phenol
phthalëines and aromatic bases produce considerably bluer tints than the colouring
matters produced from the same bases and dialkylised meta-amido-phenyl
phthaleines.
The production of the novel colouring matters is described more fully in the
EXAMPLE
10 parts by weight of tetra-ethyl-meta amido phenol phthalëine or its hydro-
chlorate are dissolved in 20 parts by weight of aniline and, under precautions,
mixed with 4 parts by weight of phosphorus oxy chloride and the mixture is
beated to from 80° to 100° C., for some time.
The product of the reaction is dissolved in diluted hydrochloric acid, and the
novel compound is separated from the solution by means of sodium acetate.
For purifying, it is recrystallised from alcohol or benzene.
derivative of tetra-ethyl-meta-amido-phenol phthalëine, thus obtained, is insoluble
The aniline

page_text: in water but soluble in alcohol and benzene, from which solvents it crystallises in
the form of colourless leaves or needles. In acetic acid it dissolves with feeble
blue red colour and yellow red fluorescence. It melts at 222° C.
The compounds obtained by means of other primary bases from the tetra
alkylised and dialkylised meta amido phenol phthaleines possess analogous
qualities.
Dated his 001 1
TI
1000
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Colouring Matters from
Meta-amido-phenol-phthalëines.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, 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 :-
My foreign correspondents have discovered that the alkylised meta-amido
phenol-phthaleines can be condensed with aromatic bases to form new compounds.
By the action of secondary and tertiary base such as dimethylaniline, diethylaniline,
ethylbenzylaniline, methyldiphenylamine, monomethyl- and monoethyl-aniline, mono-
ethyl-ortho-toluidine and the like upon the alkylized meta-amido-phenol-phthaleines,
there are obtained red colouring matters, soluble in water, which surpass the
alkylized meta-amido phenol-phthaleines, from which they are derived, in their
bluer shades and much greater affinity to vegetable fibre.
The colouring matters obtained from the tetraalkylised meta-amido-phenol-
phthaleines give considerably bluer tints than the colouring matters prepared from
the dialkylised meta-amido-phenol-phthaleines with the same aromatic bases.
The condensation products of the tetra alkylised meta-amido-phenol-phthaleines
with primary aromatic bases as aniline, ortho- and para-toluidine and the like are
in contrast to the above mentioned products almost colourless substances insoluble
in water, but soluble in excess of mineral acids, forming almost colourless solutions,
from which they are completely precipitated by sodium acetate, and, by sufficient
addition of water, the greater part is precipitated in almost colourless flakes.
They are soluble in strong acetic acid, alcohol and benzene. The last mentioned
bodies dye in shades which are unstable when treated with alkalies and strong
acids, but produce bluer tints than the mother dyes from which they are obtained.
The condensation products of primary aromatic bases with the symmetrically
dialkylized meta-amido-phenol-phthaleines are red crystals with brassy metallic
lustre, which are soluble in alcohol and glacial acetic acid with yellowish red
colour and yellowish green fluorescence. They are less soluble than the tetra-
alkylized compounds. The condensation of the alkylized meta-amido-phenol-
phthaleines with the secondary and tertiary aromatic bases is effected by heating
with addition of phosphorus oxychloride. In the case of the primary bases, it is
sufficient to heat the components for a considerable time to high temperatures,
- without phosphorus oxychloride.
The following examples illustrate the process according to this invention.

page_text: to 60°-80° C. then dissolved in dilute hydrochloric acid, and the colouring matter
The colouring matter is
is precipitated from the filtered solution with salt.
purified by dissolving and precipitating again, and, when dried, it is a dark red
brown powder, easily soluble in water, alcohol and glacial acetic acid, which dyes
cotton mordanted with tannin in shades unusually fast to soap.
The colouring matters obtained by means of other tertiary or secondary bases
from the tetra-alkylised and also from the dialkylized meta-amido-phenol-
phthaleines have analogous properties.
10 kilos. tetra-ethyl-meta-amido-phenol-phthaleine or its hydrochlorate are
iled with from 20 to 30 kilos. aniline for eight hours, by which reaction water is
rmed.
The melt is dissolved in hot, not too dilute, hydrochloric acid, any unchanged
tra-ethyl-meta-amido-phenol-phthaleine is removed by precipitation with salt,
d in the filtrate the new compound is precipitated with sodium acetate and
rified by crystallisation from alcohol.
The corresponding derivatives of other primary aromatic bases are obtained in a
milar manner. The orthotoluidine derivative of tetra-ethyl-meta-amido-phenol-
thalëine melts at 179° C., the paratoluidine derivative at 196° C.
In the above examples, for the tetraalkylised meta-amido-phenolphthaleine or
hydrochlorate may be substituted symmetrical dialkylized meta-amido-phenol-
thalëine or its hydrochlorate, without other alteration of the process.
Having now particularly described and ascertained the nature of my said inven-
on and in what manner the same is to be performed I declare that what 1
aim is :-
1. The manufacture of new derivatives of the di- and tetraalkylised meta-amido-
nenol-phthaleines :
a) By heating the di- and tetra-alkylized meta-amido-phenol phthalëines or
their hydrochlorates with secondary and tertiary aromatic bases, such as
dimethylaniline, diethylaniline, ethylbenzylaniline, methyldiphenylamine,
monomethylaniline, monoethylaniline, monoethylorthotoluidine with addition
of phosphorus oxychloride to a temperature of 60°-80° C., thus producing
red colouring matters soluble in water which surpass the colouring matters
from which they are derived by their bluer shades and their much greater
affinity for vegetable fibre.
b) By heating the di- and tetra-alkylized meta-amido-phenol-phthalëines with
primary aromatic bases such as aniline, orthotoluidine and paratoluidine
with addition of phosphorus oxychloride to 80°-100° C., or by boiling the
said alkylized meta-amido-phenol-phthaleines or their hydrochlorates with
primary aromatic bases, without phosphorus oxychloride, thus converting
the tetra-alkylized meta-amido-phenol-phthalëines into almost colourless

page_text: bodies which are insoluble in water but soluble in alcohol, strong acetic acid
and benzene, forming faintly coloured solutions, which dye with bluer
shades than the colouring matters from which they are derived, the
analogous bodies derived from the dialkylised meta-amido-phenol-phthaleines
being yellowish red crystals with brassy metallic lustre, soluble in alcohol
and glacial acetic acid with yellowish-red colour and yellowish-green
fluorescence.
The colouring matters produced as set forth in the preceding claim.
Doted this 15th day of M1004
ABEL & IMRAY,
Agents for the Applicant.