Improvements in the Production of Green and Blueish-green Coloring Matters.
Year: 1888

page_text: Date of Application, 4th Sept., 1888
Complete Specification Left, 27th May, 1889-Accepted, 6th July, 1889
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS AND
BRUNING, of Hoechst-am-Maine, in the Empire of Germany, a Company
carrying on business as Chemical Manufacturers.]
Improvements in the Production of Green and Blueish-green
Coloring Matters.
1, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane in the
County of Middlesex Fellow of the Institute of Patent Agents, do hereby declare
the nature of this invention to be as follows:-
This invention relates to the production of green and blueish-green colouring
matters which are to be considered as derivatives of the meta-oxy-diamidotri-
phenylmethan
C, H. OH (3)
( HẠC H.. NH,
Cε H. NH₂
The leuco bases of these coloring matters are produced by condensing meta-nitro-
benzaldehyde with tertiary aromatic amines, (Berichte der deutschen chemischen
Gesellschaft 12.802) reducing and converting the amidobases into the corresponding
oxy-compounds by means of nitrous acid, or by condensing directly the metaoxy-
benzaldehyde with tertiary aromatic amines.
From the leucobasos thus obtained the corresponding coloring matters are produced
by oxydation by means of superoxides or similar agents.
The sulphonic acids of these coloring matters are produced by sulphonating the
leucobases mentioned and oxydising the leucosulphonic acids or by the direct action
of sulphuric acid on the coloring matters themselves.
There have also been produced the corresponding ether compounds deriving from
the meta-methoxy- or meta-ethoxy-diamido-triphenylmethan.
33
The sulphonic acids of the coloring matters mentioned excel the various sorts of
Acid green
offered in the trade by their special resistance to the influence of
light and also by their special fastness in washing.
A. PROCESS
DIAMIDO-
FOR THE CONVERSION OF META AMIDO-TETRA-ALKYL
TRIPHENYLMETHANS
THE CORRESPONDING META-OXY-TETRALKYL-
DIAMIDO-TRIPHENYLMETHANS BY MEANS OF NITROUS ACID.
INTO
The following is given as an example of the manner of carrying out the
conversion.
50 parts by weight of meta-amido-tetra-ethyldiamido-triphenylmethan are dissolved
in 35 parts by weight of hydrochloric acid (of 33%) and 5000 parts by weight of
water. The solution is cooled down to 0° centigrade and while it is kept well stirred
there is slowly added a cold solution of 80 parts by weight of nitrite (of 96.5 per cent.).
The solution of the hydrochlorate of meta-diazo-tetra-ethyl-diamido-triphenylmethan
is heated slowly and kept at 60° Centigrade for some time, until the liberation of
nitrogen bas become rather feeble; it is then boiled until the liberation of nitrogen
ceases. To the acid solution is added soda-lye until it shows a slight alkaline reaction;
by these means the meta-oxy-leucobase is precipitated in the form of a crystalline
powder, it is filtered off, boiled with water and afterwards dried.

page_text: re heated in a lead-lined boiler furnished with an agitator to 130° Centigrade
or 3 x 24 hours; the mass resulting is supersaturated with soda lye and the excess of
iethylaniline expelled by a current of steam.
The oxyleucobase remaining is repeatedly boiled with water and afterwards dried.
In a similar manner are obtained by this process the leucobases mentioned above if
or the diethylaniline is substituted,
III
PROCESS FOR THE PRODUCTION OF SULPHONIC ACIDS OF THE METAOXY-TETRALKY!
DIAMIDO-TRIPHENYLMETHANS.
The metahydroxylised leucobases of the generic formula

page_text: From the calcium salts of the leucosulphonic acids mentioned in III are prepared
by oxidation with superoxides or similar agents, in presence of the calculated quantity
of mineral acids, the corresponding coloring matters; for example:
10 parts by weight of the calcium salt of the sulphonic acid prepared from
meta-oxy-tetra-ethyl-diamido-triphenylmethan are dissolved in about 300 parts by
weight of, water, then there are added the calculated quantities of diluted sulphuric
acid and superoxide of lead, filtered off from the precipitated sulphate of lead, and
the blue solution of the colouring matter is evaporated to dryness.
The new coloring matters are copper-red powders of metallic lustre which dissolve
quite easily in water giving blue color. The aqueous solution turns green on the
addition of an excess of mineral acid. The blue color of the aqueous solution does
not disappear on the addition of soda lye when cold, not even when it is boiled with
a solution of ammonia or soda and it turns violet only when it is boiled with soda lye.
This characteristic quality of the new coloring matters, namely their great resistance
to action of alkalies is of great advantage for technical purposes, and constitutes a
great merit of their invention. These compounds dye wool and silk in an acid bath
a blueish-green and excel in dyeing an even tint, in which respect they equal the
sulphonic acids of indigo. In consequence of their resistance to alkalies, the tints

page_text: B. The ether compounds obtained by the process just described may also be
produced by methylising or ethylising the oxy leucobases of the malachite green
series described in I.
These oxyleucobases are to this effect heated for several days in a close vessel in a
water bath with. 3 or 4 times their quantity of alcohol, caustic soda (1 molecule) and
an excess of chloro,- bromo,- or iodo-methyl or chloro,- bromo,- or iodo-ethyl.
Thus for example:
PROCESS FOR THE CONVERSION OF THE SULPHONIC
ACIDS OF THE METAOXY-
TETRALKYLDIAMIDO-TRIPHENYLMETHANS INTO THE CORRESPONDING SULPHONIC
ACIDS OF THE METHOXY- AND ETHOXY- COMPOUNDS BY COUPLING THEM WITH
ETHERS.
The sulphonic acids of the methoxylised and ethoxylised leucobases mentioned above
in VII. may be produced also by treating the calcium and sodium salts of the oxy-
tetralkyl-diamido-triphenylmethans described in III. with methyl or ethylhaloginides.
Example: 30 parts by weight of the calcium salt of meta-oxy-tetraethyldianido-
triphenylmethan, 20 parts by weight of bromo-ethyl and 100 parts by weight of
alcohol in a close vessel in a water bath are heated to boiling point for 20 to 24 hours.
The excess of bromo-ethyl and the alcohol are distilled off. To the remaining (aqueous)
solution is added a small quantity of diluted sulphuric acid and the whole is left at rest
for several days when the greatest part of the leuco sulphonic acid of the ethoxylised
base will have crystallised out. This is pressed off and converted into the calcium
salt.

page_text: PROCESS FOR THE OXYDATION OF THE METHOXYLISED AND ETHOXYLISED LEUCO-
*SULPHONIC ACIDS MENTIONED IN VII. AND VIII.
The oxydation of the sulphonic acids prepared from the methyl- and ethylethers of
the meta-oxy-tetralkyldiamido-triphenylmethans (see VII. and VIII.) is carried out in
the way described in IV.
The coloring matters produced from the sulphonic acids of the methyl- and ethyl-
ethers of the metaoxy leucobases of the malachite green series are in a dry state
coppery bodies with metallic lustre. They dye tints more beautiful and more blue
than the acid coloring matters produced from the oxy-leucobases described in IV., and
they are quite as fast. They behave with alkalies and acids in the same manner as the
non etherised (oxy) coloring matters.
Dated this 1th day of Santambas 1000
COMPLETE SPECIFICATION.
Improvements in the Production of Green and Bluish Green
Coloring Matters.
I, OLIVER IMKAY, of No. 28 Southampton Buildings, Chancery Lane, in the County
of Middlesex, 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 green and bluish green coloring
matters which are to be considered as derivatives of the meta-oxy-diamido-
triphenylmethan
C, H. OH (3)
CHÚC H. NH
C, H.. NH₂
The leuco bases of these coloring matters are produced by condensing meta-nitro-
benzaldehyde with tertiary aromatic amines (Berichte der deutschen chemischen
Gesellschaft 12.802) reducing and converting the amido bases into the corre-
sponding oxy compounds by means of nitrous acid, or by condensing directly the.
meta-oxy-benzaldehyde with tertiary aromatic amines.
From the leuco bases thus obtained the corresponding coloring matters are produced
by oxydation by means of superoxides or similar agents.
The sulphonic acids of these coloring matters are produced by sulphonating the
leuco bases mentioned and oxydising the leucosulphonic acids or by the direct action
of sulphuric acid on the coloring matters themselves.
There have also been produced the corresponding ether compounds deriving from
the meta-methoxy or meta-ethoxy-diamido-triphenylmethan.
The sulphonic acids of the coloring matters mentioned excel the various sorts of
"acid green" offered in the trade by their special resistance to the influence of light
and also by their special fastness in washing.
I.
A.
PROCESS FOR THE
CONVERSION OF META-AMIDO-TETRA-ALKYL-DIAMIDO-TRIPHE-
NYLMETHANS INTO THE CORRESPONDING
META-OXY-TETRALKYL-DIAMIDO-
TRIPHENYLMETHANS BY MEANS OF NITROUS AOID.

page_text: 50 parts by weight of meta-amido-tetra-ethyldiamido-triphenylmethan are dissolved
in 35 parts by weight of hydrochloric acid (of 33 %) and 5000 parts by weight of
water. The solution is cooled down to 0° C and while it is kept well stirred there is
slowly added a cold solution of 8.9 parts by weight of nitrite (of 96.5 per cent.) The
solution of the hydrochlorate of meta-diazo-tetra-ethyldiamido-triphenylmethan is
heated slowly and kept at 60° C for some time, until the liberation of nitrogen has
become rather feeble; it is then boiled until the liberation of nitrogen ceases.
To the
acid solution is added soda lye until it shows a slight alkaline re-action; by these means
the metaoxy leuco base is precipitated in the form of a crystalline powder, it is filtered
off, boiled with water and afterwards' dried.
In a similar manner is carried out the production of the other meta-oxy-tetralkyl-
diamido-triphenylmethans (obtained from the meta-amido-leuco bases) which like the
ethyl-compound mentioned before have relatively strong basic qualities, viz. of :-
Metaoxy - tetramethyldiamido-triphenylmethan, symmetric metaoxy-diamethyl-
diethyl-diamido-triphenylmethan

page_text: may be converted into sulphonic acids by being heated with concentrated sulphuric
acid. But principally in consideration of the purity of the products to be obtained it,
is more advantageous to use fuming sulphuric acid instead of the ordinary acid. The
process is as follows:-
are
Example 1. 30 parts by weight of meta oxytetraethyldiamidotriphenylmethan
dissolved in 150 parts by weight of fuming sulphuric acid of 10 per cent. SO, and the
solution is left standing at ordinary temperature until a sample gives with diluted
ammonia a clear solution. The product of the reaction is then poured into water and
the solution is converted into the calcium salt in well known manner. The calcium
salt is a powder very easily soluble in alcohol and in water.
In the same manner is carried out the production of the sulphonic acids or of
their calcium salts of :-
:-.
Meta oxy-tetramethyldiamido-triphenylmethan.
Symmetric meta oxy-dimethyl-diethyl-diamido-triphenylmethan.
Unsymmetric meta oxy-dimethyl-diethyl-diamido-triphenylmethan.
Meta oxy-tetramethyl-diamido-diorthotolyl-phenylmethan.
Meta
oxy-tetraethyl-diamido-diorthotolyl-phenylinethan.
Example 2. Somewhat different is the process for the preparation of the sulphonic
acids of those leuco bases which in the aimido group still contain aromatic residues
capable of being sulphonated, such as benzyl or phenyl. The compounds belonging
to this class are the following
Meta oxy-dibenzyl-diethyl-diamido-triphenylmethan.
Meta oxy-dibenzyl-dimethyl-diamido-triphenylmethan.
Meta oxy-diphenyl-diethyl-diamido-triphenylmethan.
Meta oxy-diphenyl-dimethyl-diamido-triphenylmethan.
In the following example is described the way in which the sulphonation of these
leuco bases is effected.
30 parts by weight of meta oxy-dibenzyl-diethyl-diamido-triphenylmethan are
dissolved in 150 parts by weight of fuming sulphuric acid of 20 per cent. SO.. At
ordinary temperature is formed a sulphonic acid scarcely soluble in water. Then the
solution is heated for several hours to about 70° C until a sample dissolves easily in
water with blue coloring and gives with diluted ammonia a pure blue solution having
the shade of a diluted ammoniacal solution of oxide of copper. The product of the
reaction is then poured into water and converted into the calcium salt in the well
known manner.
From the calcium salts of the leuco sulphonic acids mentioned in III. are prepared
by oxidation with superoxides or similar agents, in presence of the calculated
quantity of mineral acids, the corresponding colouring matters; for example:
:-
10 parts by weight of the calcium salt of the sulphonic acid prepared from meta
oxy-tetraethyl-diamido-triphenylmethan are dissolved in about 300 parts by weight
of water, then there are added the calculated quantities of diluted sulphuric acid and
superoxide of lead, the product is filtered off from the precipitated sulphate of lead
and the blue solution of the coloring matter is evaporated to dryness.
The new coloring matters are copper-red powders of metallic lustre which dissolve
quite easily in water giving blue colour. The aqueous solution turns green on the
addition of an excess of mineral acid. The blue color of the aqueous solution does
not disappear on the addition of soda lye when cold, not even when it is boiled
with a solution of ammonia or soda and it turns violet only when it is boiled with
soda lye.
This characteristic quality of the new coloring matters, namely their great
resistance to action of alkalies, is of great advantage for technical purposes and con-
stitutes a great merit of their invention. These compounds dye wool and silk in an

page_text: These oxy-leuco bases are to this effect heated for several days in a close vessel
in a water bath with three or four times their quantity of alcohol, caustic soda
(1 molecule) and an excess of chloro- bromo- or iodo-methyl, or of chloro-bromo-
or iodo-ethyl.
Thus for example :-
30 parts by weight of metaoxy-tetraethyldiamido-triphenylmethan.
20 parts by weight of bromo-ethyl.
100
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alcohol.
And the calculated quantity of caustic soda are heated in a vessel in a water bath for
48 hours.
Afterwards, the alcohol and the excess of bromo ethyl are distilled off, .the residue
is boiled with water and dried.
The meta-methoxylised and ethoxylised tetralkyl-diamido-triphenylmethans are when
hot semi liquid, when cold they are brittle, pulverisable resinous bodies, which show
⚫ but little inclination to crystallise, and in consequence of these qualities it is rather
<difficult to obtain them in a perfectly pure state. The one relatively most easy to be
obtained in small colorless crystals is the meta-ethoxy-diethyl-dibenzyl-diamido-
triphenylmethan. These bases dissolve readily in ether, benzol and toluol; less
readily in alcohol. Against diluted mineral acids they behave in the same way as the
corresponding non-alkylised bases.
Those bases deriving from dimethylaniline, diethylaniline, ethylmethylaniline,
dimethylortho-toluidine, diethylorthotoluidine are relatively stronger bases, which
dissolve readily in diluted mineral acids, whereas the bases deriving from methyl
and ethylbenzylaniline and from methyl and ethyldiphenylamine show scarcely any
basic qualities.
PROCESS FOR THE SULPHONATION OF THE METHOXYLISED AND. ETHOXYLISED LEUCO
BASES MENTIONED IN VI.
The sulphonation of the meta-methoxylised and meta ethoxylised tetralkyl-diamido-
triphenylmethans is carried out in the same manner as described for the conversion
of the meta oxy tetralkyldiamido-triphenylmethans into their sulphonic acids in III,
examples 1 and 2. The sodium and calcium salts are crystalline bodies, colorless in
pure state and readily soluble in water and alcohol.
PROCESS FOR THE CONVERSION OF THE SULPHONIC ACIDS OF THE METAOXYTETRALKYL-
DIAMIDO-TRIPHENYLMETHANS INTO THE CORRESPONDING SULPHONIC ACIDS OF THE
METHOXY AND ETHOXY COMPOUNDS BY COUPLING THEM WITH ETHERS.
.
The sulphonic acids of the methoxylised and ethoxylised leuco bases mentioned
above in VII. may be produced also by treating the calcium and sodium salts of the
oxy-tetralkyl-diamido triphenylmethans described in III. with methyl or ethy}
halogenides..
Example. 30 parts by weight of the calcium salt of meta-oxy-tetraethyldiamido-
triphenylmethan, 20 parts by weight of bromo-ethyl and 100 parts by weight of
alcohol in a close vessel in a water bath are heated to boiling point for 20 to 24 hours.
The excess of bromo-ethyl and the alcohol are distilled off. To the remaining aqueous
solution is added a small quantity of diluted sulphuric acid and the whole is left at
rest for several days when the greatest part of the leuco sulphonic acid of the
ethoxylised base will have crystallised out. This is pressed off and converted into the
calcium salt.

page_text: ETHOXYLISED LEUCO
PROCESS FOR THE OXYDATION OF THE METHOXYLISED AND
SULPHONIC ACIDS MENTIONED IN VII. AND VIII.
The oxydation of the sulphonic acids prepared from the methyl and ethyl ethers of
the meta-oxy-tetralkyldiamido-triphenylmethans (see VII. and VIII.) is carried out
in the way described in IV.
The coloring matters produced from the sulphonic acids of the methyl and ethyl
ethers of the meta-oxy-leuco bases of the malachite green series are in a dry state
coppery bodies with metallic lustre. They dye tints more beautiful and more blue
than the acid coloring matters produced from the oxyleuco bases described in IV. and
they are quite as fast. They behave with alkalies and acids in the same manner as
the non etherised (oxy) colouring matters.
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 :-
that
1. The production of meta oxytetraalkyl - diamidotriphenylmethans,
(a) the production of meta-oxytetramethyldiamido-triphenylmethan
is; to say:
C. H. OH (3)
CH
CH—CH. N (C H₂),
`C¿ H₁. N (CH3)2
Meta-oxytetraethyldiamidotriphenylmethan.
Meta-oxydimethyldiethyldiamidoiriphenylmethau symmetric.
Meta-oxydimethyldiethyldiamidotriphenylmethan
Meta-oxytetramethyldiamido-diorthotolyl-phenylmethan.
non-symmetric.
Meta-oxytetraethyldiamido diorthotolyl-phenylmethan.
Meta-oxydimethyldibenzyldiamidotriphenylmethan.
Meta-oxydiethyldibenzyldiamidotriphenylinethan.
Meta-oxydimethyldiphenyldiamidotriphenylmethan.
Meta-oxydiethyldiphenyldiamidotriphenylmethan by adding to the diluted cold
acid solution of the corresponding meta-amidotetraalkyldiamido-triphenylmethans
nitrite of sodium (1 molecule) and replacing amide by hydroxyl by heating the
solution until the liberation of nitrogen ceases; (b) the production of the meta-
oxytetra-alkyl-diamidotriphenylmethans enumerated above by causing meta-
oxybenzaldehyde to act at higher temperature and in presence of dehydrating agents,
such as concentrated sulphuric acid or chlorzine upon two molecules of :-dimethyl-
aniline, diethylaniline, methylethylaniline, dimethyl-o-toluidine, diethyl-o-toluidine,
methylbenzyl-aniline, ethylbenzylaniline, methyldiphenylamine, ethyldiphenylamine.
2. The conversion of the meta-oxytetra-alkyl-diamidotriphenylmethans, soluble in
diluted mineral acids, that is to say:
:-
Meta-oxytetramethyldiamidotriphenylmethan.
Meta-oxytetraethyldiamidotriphenylmethan.
Meta-oxy-dimethyldiethyldiamidotriphenylmethan
Meta-oxydimethyldiethyldiamidotriphenylmethan non symmetric.
Meta-oxytetramethyldiamidodiorthotolylphenylmethan.
symmetric.
Meta-oxytetraethyldiamidodiorthotolylphenylmethan, into coloring matters, by adding
to the diluted hydrochloric or sulphuric solution a suitable agent of oxydation, such
as peroxide of lead or peroxide of manganese and separating the coloring matter thus
formed from its solution by evaporation or precipitation by means of common
salt.
3. The production of the sulphonic acids of the leuco bases mentioned in claim 1
by subjecting these leuco bases to the action of sulphuric acid or fuming sulphuric
acid.

page_text: 4. The production of solid acid coloring matters by oxidating by means of peroxides
(such as peroxide of lead, manganese or barium) or similar agents, the sulphonic
acids of
Meta
oxytetramethyldiamidotriphenylmethan.
Meta oxytetraethyldiamidotriphenylmethan.
Meta oxydimethyldiethyldiamidotriphenylmethan symmetric.
Meta oxydimethyldiethyldiamidotriphenylmethan non symmetric.
Meta oxytetramethyldiamidodiorthotolylphenylmethan.
Meta oxytetraethyldiamidodiorthotolylphenylmethan.
Meta oxydimethyldibenzyldiamidotriphenylmethan.
Meta oxydiethyldibenzyldiamidotriphenylmethan.
Meta oxydimethyldiphenyldiamidotriphenylmethan.
Meta oxydiethylliphenyldiamidotriphenylmethan.
5. The production of these acid coloring matters by converting the coloring matters
mentioned in claim 2, into their sulphonic acids by treatinent of these coloring
matters of the oxy-malachite green series with sulphuric acid or fuming sulphuric
acid.
6. The production of the alkyl ethers of the meta-oxytetra alkyldiamidotriphenyl-
methans :-
(a) by condensing meta-methoxybenzaldehydė or meta-ethoxybenzaldehyde with the
tertiary aromatic amines, mentioned in (b) claim 1, in presence of dehydrating agents,
such as concentrated sulphuric acid or chlorzine.
(b) by the action of methyl and ethyl halogenides upon the meta oxytetra alkyl-
diamidotriphenylmethans mentioned in claim 1.
7. The production of the sulphonic acids of these alkyl ethers of the meta oxy-
tetraalkyldiamidotriphenylmethans referred to in the preceding claim by treating the
alkyl ethers with sulphuric acid or fuming sulphuric acid.
8. The poduction of the sulphonic acids of the alkyl ethers of the meta oxytetra
alkyl-diamidotriphenylmethans by treating a salt of the sulphonic acids referred to in
claim with methyl or ethyl halogenides.
9. The conversion of the sulphonic acids of the alkylethers of the metaoxytetra
alkyldiamidoiriphenylmethans referred to in claim 7 into solid coloring matters by
their oxidation by means of peroxides such as peroxide of lead or peroxide of
manganese.
Dated this 27th day of May 1889.
ABEL & IMRAY,
Agents for the Applicant.