Improvements in the Manufacture of Colouring Matters.
Year: 1890

page_text: Date of Application, 19th Aug., 1890
Complete Specification Left, 16th May, 1891-Accepted, 4th July, 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
I, Dr. WILHELM MAJERT, of 10, Madi-strasse Berlin in the Empire of Germany,
Chemist, do hereby declare the nature of this invention to be as follows:-
:-
The rhodamines (meta amidophenolphthaleins) derived from the meta amido-
phenols which are at present known are mainly employed for dyeing: wool and silk..
As is the case with alkyl derivatives of rhodaniline the alkyl rhodamines ar
prepared with difficulty.
Acid rhodamines of first class industrial importance, and of a quality fully equal
to that of the basic rhodamines may be prepared by condensing the two sulpho-
phthalic acids' together with the meta amidophenol and its alkyl-derivatives and
with the ethers of the meta amidophenols and their alkyl derivatives.
The products of the two sulphophthalic acids and their ethers differ from one
another so little as regards shade and other industrial qualities that no difference is
technically made between them but a mixture of both of them is usually made
use of
The dye-stuffs obtained from the sulpho-phthalic acids possess great industrial
value especially
1. meta ethylamidophenol
2. meta dimethylamidophenol.
3. meta di-ethylamido phenol
4. meta methy ethyl amido phenol
5. meta phenyl amido phenol
6. meta partolylamidophenol
7. meta orthatolylamidophenol
8. meta xylylamidophenol
9. meta -naphthyl amido phenol
and the ethers of the above named bodies.
The rhodamines are prepared by allowing the secondary acid salts of the sulpho-
phthalic acids or their anhydrides or the free (uncombined) sulphophthalic acids or
their anhydrides to act upon the meta amidophenols or their alkyl-ethers, with or
without the employment of condensing apparatus at a-temperature of 150°--200°.
The method employed is as follows....
1.) Acid rhodamines from the sulphophthalic acids and meta .ethyl amido
phenol.
CO
26 kg. (about 52 lbs.) of anhydrous sulpho phthalate of soda C,H,CO
SO,Na
and 174 (about 35 lbs.) of ethyl amidophenol are heated in a closed vessel or
kettle for 8 hours at a temperature of 170-175°. The "melt" is dissolved in
water the solution acidulated with a little hydrochloric acid, and the colouring
matter is then precipitated with common salt. To purify the colouring matter it is
dissolved in water, the solution filtered precipitated with common salt, the
precipitate is then separated from the liquid by filtration and dried.
The colouring matter is in this way obtained in the form of a brownish red
powder which is easily soluble in water.
The colour of the aqueous solution is not effected either by acids or alkalies and
it possesses the same fluorescence and shade as the corresponding basic rhodamine;
but it has this advantage, that while the aqueous solution of the latter when made
alkaline with soda may be extracted by ether, the acid rhodamine cannot be
extracted from aqueous solution by this means.

page_text: 2.) Acid rhodamine from the sulphophthalic acids and meta dimethylamido-
COOH
27 kg. of acid sulpho phthalate of soda CH3COOH
SO,Na
16.5 kg. meta dimethylamido phenotol
100 kg. hydrochloric acid 33%
30 kg. chloride of zinc
are heated as described above in an iron kettle. On moistening with water the
mass becomes gradually firm and displays a deep metallic copper coloured lustre.
It is dissolved in water brought to the boiling point and the zinc precipitated with
soda. The colouring matter solution is then separated by filtration from the zinc
carbonate the solution acidulated and precipitated by common salt. The colouring
matter is purified as in example 1.
it dyes the shade of tetra methylrhodamine.
3.) Acid rhodamine from sulphophthalic acid and meta dimethylamidophenotol.
24 kg. sulphophthalic acid
16.5 kg. meta dimethyl amido phenotol
25 kg. chloride of zinc
are heated as described above. For further treatment the "melt" is heated as in
example 1).
The dye-stuff dissolves easily in water and imparts the same beautiful shade as
tetra methyl rhodamine.
SO,H
4.) 23 kg. anhydrous sulphophthalic acid C.H3CO
CO
0
20.3 kg. meta phenylamidophenol C.H.NHC¸H,
OH
are heated in an iron kettle
for 4 hours at a temperature of 170-175° after which the "melt" is dissolved in
dilute solution of soda and the colouring matter precipitated by addition of acid.
The colouring matter is purified by dissolving the thus separated precipitate in
soda and re-precipitating. It is then stirred up with water neutralized with soda,
and the solution evaporated to dryness. In this manner the soda salt of the
colouring matter is obtained as a deep blue-black copper lustrous mass easily
soluble in water and dyeing wool or silk direct with a red shade.
The various examples given may serve to characterize the different methods of
carrying out the process of preparing the colouring matters.
The remaining colouring matters may be prepared in a similar manner.
Dated this 19th day of August 1890.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
I, Dr. WILHELM MAJERT of 10 Madi-Strasze Berlin in the Empire of Germany,
Chemist, 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 rhodamines (meta amidophenolphthaleins) derived from the meta amido-
phenols which are at present known are mainly employed for dyeing wool and silk.
As is the case with the acid derivatives of alkyl-rosaniline (Fuchsin) acid rhodamines
are prepared with difficulty.

page_text: Acid rhodamines of first class industrial importance, and of a quality fully equal
to that of the basic rhodamines may be prepared by condensing the two sulpho-
phthalic acids together with the meta amido phenol and its alkyl derivatives, and
with the ethers of the meta amidophenols and their alkyl derivatives.
The products of the two sulpho-phthalic acids and their ethers differ from one
another so little as regards shade and other industrial qualities, that no difference is
technically made between them but a mixture of both of them is usually made
use of.
The dye stuffs obtained from the sulphophthalic acids possess great industrial
value especially,
1. meta ethylamido phenol
2. meta dimethylamidophenol
3. meta diethylamido phenol
4. meta methy ethylamido phenol
5. meta phenylamido phenol
6. meta orthotolylamido phenol
7. meta paratolylamidophenol
8. meta xylylamidophenol
9. meta naphthylamido phenol
and the ethers of the above named bodies.
The rhodamines are prepared by allowing the secondary acid salts of the sulpho-
phthalic acids or their anhydrides or the free (uncombined) sulphophthalic acids or
their anhydrides to act upon the meta amidophenols or their alkyl-ethers, with or
without the employment of condensing apparatus at a temperature of about
150°-200°.
The method employed is as follows:-
1.) Acid rhodamines from the sulphophthalic acids and meta ethyl amido phenol.
CO
26 kgs. (about 52 lbs.) of anhydrous sulphophthalate of soda C.H.CO
SO,Na
and 17.4 (about 35 lbs.) of ethylamido phenol, are heated in a closed vessel or
kettle for 8 hours at a temperature of 170-175°. The "melt" is dissolved in
water, the solution acidulated with a little hydrochloric acid, and the colouring
matter is then precipitated with common salt. To purify the colouring matter it is
dissolved in water, the solution filtered and precipitated with common salt, the
precipitate is then separated from the liquid by filtration and dried. The colouring
matter is in this way obtained in the form of a brownish red powder which is easily
soluble in water.
The colour of the equeous solution is not affected either by acids or alkalies, and
it possesses the same fluorescence and shade as the corresponding basic rhodamine;
but it has this advantage, that while the aqueous solution of the latter when made
alkaline with soda may be extracted by ether the acid rhodamine cannot be extracted
from aqueous solution by this means.
2.) Acid rhodamine from the sulphophthalic acids and meta dimethylamido-
phenetol.
COOH

page_text: 3.) Acid rhodamine from sulphophthalic acid and meta dimethylamidophenetol.
24 kgs. sulphophthalic acid
16.5 kgs. meta dimethylamidophenetol
25 kgs. chloride of zinc,
are heated as described above. For further treatment the "melt" is heated as in
example 1). The dye-stuff dissolves easily in water and imparts the same beautiful
shade as tetramethyl rhodamine.
SO,H
4.) 23 kgs. anhydrous sulphophthalic acid CH3CO
CO/
0
OH
20-3 kgs. meta phenylamidophenol C.H.NHC.H
are heated in an iron kettle for 4 hours at a temperature of 170-175° after which
the "melt" is dissolved in dilute solution of soda, and the colouring matter
precipitated by addition of acid. The colouring matter is purified by dissolving
the precipitate thus separated in soda and reprecipitating, it is then stirred up with
water neutralized with soda, and the solution evaporated to dryness. In this manner
the soda salt of the colouring matter is obtained as a deep blue black mass having
a copper lustre easily soluble in water, and dyeing wool or silk direct into a red
shade.
The various examples given may serve to characterize the different methods of
carrying out the process of preparing the colouring matters.
The remaining colouring matters may be prepared in a similar manner.
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:
-
A method of preparing the acid rhodamines which consist in heating at a fixed
temperature, (1) a or B anhydrous sulphophthalic acid or a mixture of the same.
(2) a or 3 sulphophthalic acids or a mixture of the same. (3) The secondary acid
salt of a or ẞ sulphophthalic acid or a mixture of the same. (4) The anhydrous
forms of the secondary acid salts of a or 3 sulphophthalic acids or a mixture thereof
with (1) meta ethyl amido phenol (2) meta dimethyl amido phenol (3) meta diethyl
amido phenol (4) meta methylethyl amido phenol (5) meta phenylamido phenol
(6) meta orthotolylamidophenol (7) meta paratolylamidophenol (8) meta xylyl-
amidophenol (9) meta a naphthylamidophenol or with the ethers of the above
named bodies or with the salts of the above named derivatives of the meta amido-
phenol, with or without the employment of means of condensation.
Dated this 16th day of May 1891.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.