Improvements in the Production of Coloring Matters.
Year: 1890

page_text: Date of Application, 28th June, 1890
Complete Specification Left, 27th Feb.. 1891-Accepted, 28th Mar., 1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by the SOCIETY OF CHEMICAL INDUSTRy, in Basle,
Switzerland, Chemical Manufacturers.]
Improvements in the Production of Coloring 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 to be as follows:-
...
The production of red basic coloring matters by condensation of the alkyl
derivates of meta-amidophenol with succinic acid anhydride, has already formed the
subject matter of a series of patents (see United States Patents No. 402436 and
No. 425504, French Patent No. 195930, German Patent No. 51983 and
others).
According to the present invention, analogous dye stuff's are obtained from the
condensation product of resorcine with succinic acid, (resorcine-succincine) by the
action of secondary amines at a higher temperature. The re-action with
dimethylamine proceeds hereby in quite an analogous manner as with the
fluoresceine, as, firstly, at 170° Centigrade chiefly only one hydroxyl group is
substituted by the remainder of the dimethylamine, in forming an intermediate
product which possesses both basic and acid qualities; only by the further action of
dimethylamine on the resorcine-succinëine or on the intermediate product obtained.
that is to say, the succinic acid-rhodaminol, the tetramethylmetaamidophenol-
succinëine or succinic acid-rhodamine is formed.
For the production of the succinic acid-rhodaminol or the succinic acid-
rhodamine the following may serve as an example:-13.2 parts of resorcine-
succincine, and 13.8 parts of a solution of 40 per cent. of dimethylamine are heated
together with 70 parts of alcohol in the autoclave up to from 170° to 200° Centigrade
during fourteen hours. The product of the reaction is then diluted with water, and,
after the addition of 21.9 parts of soda-lye of 33 per cent., is heated in the water
bath for the purpose of the evaporation of the alcohol and of the superfluous
dimethylamine.
The alkaline solution is then agitated repeatedly with ether or toluol, by
which operation the colouring base of the succinic acid-rhodamine passes over
into the ether, whilst in the aqueous solution the succinic acid rhodamine remains
dissolved in the form of its soda-salt.
The latter is separated by common salt forming a red-brown mass; by filtering
off, pressing and drying and re-dissolving in soda-solution, it is finally obtained
pure.
The soda-salt and the potassium-salt dissolve casily in water, showing a red
colour, also in alcohol, and they dye on silk in the soap bath a light-pink colour.
From the aqueous solutions acetic acid and dilute mineral acids precipitate the
disengaged succinic acid-rhodaminol in the form of a red-brown magma, which
dissolves with difficulty in water and dilute mineral-acids, but easily in alcohol.
For the separation of the succinic acid-rhodamine the above mentioned ethereal
extract of the reaction-mass is agitated with a little warm dilute muriatic acid or is
treated with muriatic acid gas, whereby the dissolved colouring-base is eliminated
n the form of its hydrochlorate. This latter separates out as a green-glistening
crystalline mass, which purified by re-dissolving in dilute muriatic-acid.

page_text: It dyes cotton and silk a beautiful pink; the silk shows a strong cinnabar-red
fluorescence.
It shows all qualities which are characteristic for a succinic acid-rhodamine.
Dated this 28th day of June 1890..
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Coloring Matters.
1, 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 :-
The production of red basic coloring matters by condensation of the alkyl
derivates of meta-amidophenol with succinic acid anhydride, has already formed the
subject matter of a series of patents (see United States Patents No. 402436 and
No. 425504, French Patent No. 195930, German Patent No. 51983 and others).
According to the present invention, analogous dye stufts are obtained from the
condensation product of resorcine with succinic acid, (resorcine-succinëine) by the
action of secondary amines at a higher temperature. The re-action with
dimethylamine proceeds in this operation in a manner quite analogous to that with
the fluoresceine, as, firstly, at 170° C. for one hydroxyl group is substituted the
remainder of the dimethylamine, forming an intermediate product which possesses
both basic and acid qualities; it is by the further action of dimethylamine on the
resorcine-succincine or on the intermediate product obtained, that is to say, the
succinic acid-rhodaminol, that the tetramethylmetaamidophenol-succincine or
succinic acid-rhodamine is formed.
For the production of the succinic acid-rhodaminol or the succinic acid-
rhodamine the following may serve as an example:-13-2 parts of resorcine-
succinëine, and 13-8 parts of a solution of 40 per cent. of dimethylamine are heated
together with 70 parts of alcohol in a close vessel up to from 170° to 200° C. during
fourteen hours. The product of the reaction is then diluted with water, and, after
the addition of 21.9 parts of soda-lye of 33 per cent., is heated in the water bath for
the purpose of the evaporation of the alcohol and of the superfluous dimethylamine.
The alkaline solution is then agitated repeatedly with ether or toluol, by which
operation the colouring base of the succinic acid-rhodamine passes over into the
ether, whilst in the aqueous solution the succinic acid rhodaminol remains dissolved
in the form of its soda-salt.
The latter is separated by common salt forming a red-brown mass; by filtering
off, pressing and drying and re-dissolving in soda-solution, it is finally obtained
pure.
The soda-salt and the potassium-salt dissolve easily in water, showing a red colour,
also in alcohol, and they dye on silk in the soap bath a light-pink colour. From
the aqueous solutions acetic acid and dilute mineral acids precipitate the disengaged
succinic acid-rhodaminol in the form of a red-brown magma, which dissolves with
difficulty in water and dilute mineral-acids but easily in alcohol.
For the separation of the succinic acid-rhodamine the above mentioned extract
in ether of the reaction-mass is agitated with a little warm dilute hydrochloric acid
or is treated with hydrochloric acid gas; whereby the dissolved colouring-base is
eliminated in the form of its hydrochlorate. This latter separates out as a green-
glistening crystalline mass, which is purified by re-dissolving in dilute hydrochloric
acid.
It dyes cotton and silk a beautiful pink; the silk shows a strong cinnabar-red
fluorescence.
It shows all qualities which are characteristic of a succinic acid-rhodamine.

page_text: Having now particularly described and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
1. The preparation of succinic acid-rhodaminol and succinic acid-rhodamine
from the condensation product of resorcine with succinic acid, by the action of
dimethylamine at a temperature of 170° to 200° C. substantially as herein described.
2. The succinic acid-rhodaminol coloring matter produced as above described.
Dated this 27th day of February 1891.
ABEL & IMRAY,
Agents for the Applicant.