Manufacture of Green and Blue-green Colouring Matters from Triphenylmethan.
Year: 1897

page_text: Date of Application, 31st July, 1897
Complete Specification Left, 5th Apr., 1898-Accepted, 11th June, 1898
PROVISIONAL SPECIFICATION.
Manufacture of Green and Blue-green Colouring Matters from
Triphenylmethan.
I, JOHN IMRAY, of No. 28, Southampton Buildings, Chancery Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (as communicated to me from abroad by
La Société Anonyme des Matières Colorantes et Produits Chimiques de St. Denis,
of 105, Rue Lafayette, Paris, France), to be as follows:-
My foreign correspondents have discovered that metanitrobenzaldehyde heated
with sodium sulphite in aqueous solution becomes transformed into an amido-
sulphoconjugate derivative. This has not been isolated as it is neither useful
nor necessary for the purpose of this invention, but the properties of leucobases
and those of the corresponding colouring matters derived from them by condensa-
tion with aromatic amines leave no doubt as to the nature of the product obtained.
The reaction is effected in the following manner.
EXAMPLE.
15 kilos. of nitrobenzaldehyde, 100 kilos. of crystallised sodium sulphite and
300 to 400 kilos. of water are heated to boiling for 2 hours while a current of
carbonic anhydride is passed through them. 25 kilos. of sulphuric acid at
550 Be. are added, then 20 to 30 kilos. of diethylaniline. The whole is boiled
in a reflux apparatus for 15 to 20 hours, it is alkalised with sodium carbonate
and a current of steam is passed through it.
When all the excess diethylaniline is removed, the remaining liquid has
added to it 15 to 20 per cent. of salt, precipitating the leucobase.
This leucobase is then transformed into colouring matter in the usual way;
by oxidising with lead binoxide, for example, in a hydrochloric sulphuric or
acetic acid medium. After precipitating the lead by sodium sulphate, the coloured
solution is evaporated to dryness.
The residue constitutes the colouring matter, in form ready for use.
wool in acid bath a blue green fast to alkalies.
It dyes
In this operation, for the diethylaniline may be substituted dimethylaniline,
ethylbenzylaniline, dibenzylaniline, or any other tertiary aromatic amine, or a
secondary amine which can act as a tertiary, as, for example the monoalcoyl
derivatives of orthotoluidine, monomethyl, monoethyl, mono-benzyl-orthotolui-
dine.
Certain amines may in the first place be sulphoconjugated, as ethylbenzylaniline
methylbenzylaniline, or dibenzylaniline.
These amines may also be substituted in the ring in meta position, as for
example dimethylmeta-amidophenol &c.
When sodium sulphite is made to act not on metanitrobenzaldehyde but on the
leuco base derived from it, the results are very inferior; furthermore, if sodium

page_text: sulphite be made to react under most varying conditions on leucobases containing
two electronegative groups, one of which is NO, (acording to Nietzki,--Berichte
1896, vol. 3, 2448) the results are in this case also very inferior.
Dated this 31st day of July 1897.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Green and Blue-green Colouring Matters from
Triphenylmethan.
I, JOHN IMRAY, formerly of No. 28, Southampton Buildings, but now of Birk-
beck Bank Chambers, Southampton Buildings, Chancery Lane, in the County of
London, Consulting Engineer and Chartered Patent Agent, do hereby declare
the nature of this invention (as communicated to me from abroad by
La Societe Anonyme des Matieres Colorantes et Produits Chimiques de St. Denis,
of 105, Rue Lafayette, Paris, France), 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 metanitrobenzaldehyde heated
with sodium sulphite in aqueous solution becomes transformed into an amido-
sulphoconjugate derivative. This has not been isolated as it is neither useful
nor necessary for the purpose of this invention, but the properties of leucobases
and those of the corresponding colouring matters derived from them by condensa-
tion with aromatic amines leave no doubt as to the nature of the product obtained.
The reaction is effected in the following manner.
EXAMPLE.
15 kilos. of nitrobenzaldehyde, 100 kilos. of crystallised sodium sulphite and
300 to 400 kilos. of water are heated to boiling for 2 hours while a current of
carbonic anhydride is passed through them. 25 kilos. of sulphuric acid at
55° Be. are added, then 20 to 30 kilos. of diethylaniline. The whole is boiled
in a reflux apparatus for 15 to 20 hours, it is alkalised with sodium carbonate
and a current of steam is passed through it.
When all the excess diethylaniline is removed, the remaining liquid has
added to it 15 to 20 per cent. of salt, precipitating the leucobase.
This leucobase is then transformed into colouring matter in the usual way;
by oxidising with lead binoxide, for example, in a hydrochloric sulphuric or
acetic acid medium. After precipitating the lead by sodium sulphate, the coloured
solution is evaporated to dryness.
The residue constitutes the colouring matter, in form ready for use.
It dyes wool in acid bath a blue-green fast to alkalies.
In this operation, for the diethylaniline may be substituted dimethylaniline,
ethylbenzylaniline, dibenzylaniline, or any other tertiary aromatic amine, or a
secondary amine which can act as a tertiary, as for example the monoalkyl
derivatives of orthotoluidine, monomethyl-, monoethyl-, mono-benzyl-orthotolui-
dine.
Certain amines may in the first place be sulphoconjugated, as ethylbenzylaniline.
methylbenzylaniline, or dibenzylaniline.
These amines may also be substituted in the ring in meta position, as for
example dimethylmeta-amidophenol &c.

page_text: When sodium sulphite is made to act not on metanitrobenzaldehyde but on the
leuco-base derived from it, the results are very inferior; furthermore, if sodium
sulphite be made to react under most varying conditions on leucobases containing
two electronegative groups, one of which is NO, (acording to Nietzki,-Berichte
1896, vol. 3, 2448) the results are in this case also very inferior.
Having now particularly described and ascertained the nature of this
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The herein described process for the manufacture of colouring matters
derivatives of triphenylmethane, by heating metanitrobenzaldehyde or its homo-
logues with sodium sulphite and condensing the products thus obtained with
simple or substituted secondary or tertiary amines or with sulphoconjugated
amines their sulpho-conjugation being effected either on the amines before con-
densation or on the products of condensation.
2. The colouring matters obtained as above set forth.