Improvements in the Production of Blue-green Colouring Matters of the Malachite Green Series.
Year: 1890

page_text: Date of Application, 19th June, 1890
Complete Specification Left, 14th Mar., 1891-Accepted, 18th Apr., 1891
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 Blue-green Colouring Matters of
the Malachite Green Series.
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 to be as follows :-
-
My foreign correspondents have discovered that the sulphonic acids derived from
the metachlorotetralkyldiamidotriphenylcarbinols are also fast blue-green acid
colouring matters just like the sulphonic acids deriving from the meta-oxy- and meta-
amido-derivatives of the colouring matters of the malachite green series (see
Patents 1279688 and 1482288).
These sulphonic acids are produced in quite a similar way to the corresponding
meta-oxy- and meta-amido derivatives, namely by oxydising the sulphonic acids
derived from the metachlorotetralkyldiamidotriphenylmethans or by sulphonising
the meta-chloro-tetralkyldiamidotriphenylcarbinols.
In working according to the methods at present known one will only with difficulty
succeed in producing pure leucobases of the malachitgreen series chloruretted in the
meta-position alone.
Pure meta-chlorobenzaldehyde is a body very high in price, so that no paying
manufacture could be carried on if this body were chosen as raw-material for
producing those bases.
My foreign correspondents have discovered a simple process for the production
of the meta-chlorotetralkyldiamidotriphenylmethans
PRODUCTION OF META-CHLOROTETRALKYLDIAMIDOTRIPHENYLMETHANS.
401 parts by weight of meta-amido tetraethyldiamidotriphenylmethan are
dissolved in 100 parts by weight of hydrochloric acid of 30 per cent. HCI and
100 parts by weight of water.
This solution is cooled down to 0° C. and then a cold solution of 72 parts by
weight of nitrite of 962 per cent. NaNO, is slowly mixed therewith. The conversion
of the diazo compounds into the chloro-substitution-products, may be carried out in
two different ways.

page_text: a. According to Sandmeyer's method.
20 parts by weight of copper chloride Cu, Cl, are dissolved in 300 parts by weight
of concentrated hydrochloric acid. The solution is heated to from 70 to 80° C. and
then the solution of hydrochlorate of meta-diazotetraethyldiamidotriphenylmethan
produced as described above is caused to slowly flow into it, when there will be an
impetuous development of nitrogen. After the reaction is completed, it is filtered
off from the copper chloride that has separated. From the filtrate the copper may
be separated by sulphuretted hydrogen and then the meta-chloroleuco base be
precipitated by means of alkali; or the solution may be mixed with a small
quantity of alkali in order to deaden the acid, and then the leuco base be precipitated
in the form of its hydrochlorate by the addition of common salt.
b. According to Gattermann's method.
The conversion of the diazo-compound into the halogen compound is carried out
to much greater advantage in the following way:
The cold solution of hydrochlorate of metadiazotetraethyldiamidotriphenylmethan
is mixed very slowly and while being kept well agitated, with a paste of molecular
copper (ride Gattermann Berl. Ber. XXIII, 1219) the weight of which corresponds
to 4 parts by weight of copper. An impetuous development of nitrogen will set in
on account of which the addition of the copper, must be proceeded with very slowly.
After the reaction is completed, it is filtered off from the residue consisting of
copper and copper chloride. In order to deaden the acid, the filtrate is admixed
with a small quantity of soda and from the still acid solution the hydrochlorate of
the meta-chloroleuko base is precipitated by means of common salt. The hydro-
chlorate is dissolved in water and the base precipitated by means of soda.
The
reaction mass can also be treated in the following way, namely separating the small
quantity of dissolved copper by means of sulphuretted hydrogen and precipitating
the base from the filtrate by means of soda. In both cases there is obtained a
nearly colourless crystalline powder, which however on exposure to the air, and still
more on being dried on the water bath, assumes a dark colour. The base meta-
chlorotetraethyldiamidotriphenylmethan is nearly insoluble in cold alcohol, of
difficult solubility in hot alcohol, but easily soluble in ether and hydrocarbons.
With mineral acids it forms easily soluble salts.
My foreign correspondents have prepared in this way up to this day the following
meta-chlorolencobases,
metachlorotetramethyldiamidotriphenylmethan,
metachlorodimethyldibenzyldiamidotriphenylmethan

page_text: 20 parts by weight of metachlorotetraethyldiamidotriphenylmethan are dissolved
in 100 parts by weight of fuming sulphuric acid of 20 per cent. SO,. The solution
is heated to from 60 to 70° C., until a sample is completely taken up by hot diluted
ammonia. The completion of the reaction is recognised with still greater certainty
by infusing by drops a sample in soda-lye, filtering off and observing if the salt
which separates gives a clear solution with water.
The reaction-mass is poured into water and is with advantage, treated further as
described hereafter.
To the solution is added soda until alkaline reaction ensues and when necessary
for the complete precipitation of the sodium salt of the novel sulphonic acid, there
is added common salt solution. Then it is filtered off from the precipitated leuco
salt, the salt dissolved again in hot water, filtered and precipitated by means of
common salt: the precipitated salt is filtered off and dried.
The sodium salt of the lencosulphonic acid thus obtained is in form of a powder
slightly colored green, of difficult solubility in water and insoluble in salt solutions.
On the addition of a mineral acid to the aqueous solution the acid precipitates in
crystalline form.
In this way my foreign correspondents have produced also the sulphonic acid
from metachlorotetramethyldiamidotriphenylmethan.
The sulphonation of the benzylised leucobases mentioned in I is carried out in a
different way, as described in the following example
:―
20 parts by weight of meta-chloro-diethyldibenzyldiamidotriphenylmethan are
dissolved in 100 parts by weight of fuming sulphuric acid of 20 per cent. SO3.
Already at ordinary temperature the greater part of the base is sulphonised. In
order to complete the sulphonising it is heated to from 50 to 60° C., until a sample
gives a clear solution in water and in diluted ammonia. The reaction-mass
is poured into water and converted into the calcium or sodium salt in well known
manner. By the same method the sulphonic acid is produced from the meta-chloro-
dimethyldibenzyldiamidotriphenylmetlian.
III.
OXIDATION OF THE SULPHONIC ACIDS FROM THE
META-CIILOROTETRALKYL-
DIAMIDOTRIPHENYLMETHANS.
5 parts by weight of sodium salt of the sulphonic acid from meta-chlorotetraethyl
diamidotriphenylmethan are dissolved in 1000 parts by weight of water, the solution
heated to boiling point and mixed with the calculated quantity of diluted sulphuric
acid and peroxide of lead. It is filtered off from the sulphate of lead which will
have separated, and the colouring matter solution evaporated to dryness.
The novel colouring matter is in the form of a copper-red powder with metallic
lustre. It dissolves easily in water with green coloration and dyes wool and silk
in an acid bath very fast and level green-blue shades.
In the same way the other sulphonic acids described in II are oxidised to
colouring matters:
Dated this 19th day of June 1890.
ABEL & IMKAI,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Blue-green Colouring Matters of
the Malachite Green Series.
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 :-
My foreign correspondents have discovered that the sulphonic acids derived from

page_text: the metachlorotetralkyldiamidotriphenylcarbinols are also fast blue green acid
colouring matters just like the sulphonic acids deriving from the meta-oxy- and
meta-amido-derivatives of the colouring matters of the malachite green series (see
Patents 12796 and 148228).
These sulphonic acids are produced in quite a similar way to the corresponding
meta-oxy and meta-amido derivatives namely by oxidising the sulphonic acids
derived from the metachlorotetralkykliamidotriphenylmethans or by sulphonising
the metachlorotetralklydiamidotriphenylcarbinols.
In working according to the methods at present known one will only with
difficulty succeed in producing pure leuco bases of the malachite green series
chloruretted in the meta position alone.
Pure metachlorobenzaldehyde is a body very high in price, so that no paying
manufacture could be carried on if this body were chosen as raw material for
producing those bases.
My foreign correspondents have discovered a simple process for the production of
the metachlorotetralkyldiamidotriphenylmethans
PRODUCTION OF META-CBLOROTETRALKYLDIAMIDOTRIPHENYLMETHANS.
401 parts by weight of meta-amidotetraethyldiamidotriphenylmethan are dissolved
in 100 parts by weight of hydrochloric acid of 30 per cent. HCI and 100 parts by
weight of water.
This solution is cooled down to 0° C. and then a cold solution of 72 parts by
weight of nitrite of 96-2 per cent. NaNO, is slowly mixed therewith. The con-
version of the diazo compounds into the chloro substitution products may be carried
out in two different ways.
a. According to Sandmeyer's method.
20 parts by weight of copper chloride CuCl are dissolved in 300 parts by
weight of concentrated hydrochloric acid. The solution is heated to from 70
to 80° C. and then the solution of hydrochlorate of meta diazotetraethyldiamidotri-
phenylmethan produced as described above is caused to slowly. flow into it, when
there will be an impetuous development of nitrogen. After the reaction is com-
pleted it is filtered off from the copper chloride that has separated. From the
filtrate the copper may be separated by sulphuretted hydrogen and then the meta-
chloroleuco base be precipitated by means of alkali; or the solution may be mixed
with a small quantity of alkali in order to deaden the acid, and then the leuco
base be precipitated in the form of its hydrochlorate by the addition of
common salt.
b. According to Gattermann's method.
The conversion of the diazo compound into the halogen compound is carried out
to much greater advantage in the following way.
The cold solution of hydrochlorate of metadiazotetraethyldiamidotriphenyl-
methan is mixed very slowly and while being kept well agitated with a paste of
molecular copper (ride Gattermann Berl. Ber. XXIII 1219) the weight of which

page_text: corresponds to 4 parts by weight of copper. An impetuous development of
nitrogen will set in on account of which the addition of the copper must
be proceeded with very slowly. After the reaction is completed, it is filtered
off from the residue consisting of copper and copper chloride. In order to
deaden the acid, the filtrate is admixed with a small quantity of soda and
from the still acid solution the hydrochlorate of the meta-chloro leuco base is
precipitated by means of common salt. The hydrochlorate is dissolved in water
and the base precipitated by means of soda. The reaction mass can also be treated
in the following way, namely, separating the small quantity of dissolved copper by
means of sulphuretted hydrogen and precipitating the base from the filtrate by
means of soda. In both cases there is obtained a nearly colourless crystalline
powder, which however on exposure to the air, and still more on being dried on the
water bath, assumes a dark colour. The base meta-chlorotetraethyldiamidotri-
phenylmethan is nearly insoluble in cold alcohol, of difficult solubility in hot alcohol,
but easily soluble in ether and hydrocarbons. With mineral acids it forms easily
soluble salts.
My foreign correspondents have prepared in this way up to this day the following
meta-chloro-leuco bases.

page_text: ABEL & IMRAY,
Agents for the Applicant.