Manufacture of Colouring Matter from Substituted Fluorescöines.
Year: 1896

page_text: Date of Application, 10th Feb., 1896
Complete Specification Left, 10th Nov., 1896-Accepted, 12th Dec., 1896
ONAL
[Communicated from abroad by THE FARBWERKE, vormals MEISTER LUCIUS
AND BRUNING, of Hoechst a/ Main, in the Empire of Germany, Chemical
Manufacturers.]
Manufacture of Colouring Matter from Substituted Fluorescöines.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
As first stated by Bayer (Ann. d. Chem. 183) bromcoeruleïne is obtained by
strongly heating tetrabromfluoresceine with concentrated sulphuric acid.
According to his process, however, as he admits, a raw product is obtained,
containing only very little bromcoerulëïne and this only after a troublesome
purification; thus the manufacture of bromcoeruleïne on a large scale, according to
Bayer's system, has not hitherto been practicable.
My foreign correspondents have discovered, that substituted fluoresceïnes may
be transformed into colouring matter of the nature of coeruleine with a good yield,
if, instead of ordinary concentrated sulphuric acid, containing 5 to 8 per cent. of
water, monohydrated or fuming sulphuric acid is employed.
The quantity of anhydride contained in the fuming sulphuric acid may vary
greatly the temperature necessary and the length of time required depending upon
the strength of the acid employed.
EXAMPLE:-
1) 1 kilo. of tetrabromfluoresceine is added to 5 kilos. of fuming sulphuric acid
containing 20 per cent. SO and the mixture is kept at a temperature of 125° C.,
till a test portion mixed with excess of aqueous alkali and a solution of common
salt no longer gives a coloured filtrate.
By adding 40 kilos. of sulphuric acid of 66° Bé. and 100 kilos. of 60° Bé., the
excess of fuming sulphuric acid is decomposed and the colouring matter is
precipitated by means of ice and water.
After washing out the almost black paste thus obtained, it can at once be used
for dyeing purposes. It is not soluble in water, soluble with great difficulty in
alcohol and in sulphuric acid with a dark cherry-red colour; it is soluble. with a
bluish green colour in alkalies and alkaline carbonates. Common salt precipitates
the sodium salt from these solutions; it dyes chrome mordanted wool a strong
bluish-green and is very fast to light, air and fulling.
My correspondents have also discovered, that the product obtained by means of
the above process undergoes a further change by treating it with sulphuric acid
containing water. The colouring matter, thus obtained, dyes more vividly and
with a more greenish tint.

page_text: sulphuric acid, and precipitated by the addition of water, then filtered, washed out
and used as colouring paste. In order to manufacture this greenish product, it is
expedient to combine processes 1 and 2 in the following manner :-
EXAMPLE:-
3) 1 part by weight of tetrabromfluoresceine together with 5 parts by weight of
fuming sulphuric acid are heated to 125° C., until, according to Example 2), no
further colouring matter, soluble red in alkali, can be traced; then, by adding a
little water or sulphuric acid containing water, the excess of anhydride is destroyed
and, after a lapse of 3 hours, the product is heated to 150° C. Having precipitated
with water, the colouring matter separates as explained in 2).
For the manufacture of coeruleine like colouring matters from tetrabrom-
fluoresceine, as described above, the following bodies are also suitable :-
1). Di-substituted bromfluoresceine.
2). The fluoresceines substituted with iodine instead of bromine (di-iodo a tetra-
iodofluoresceine).
3) The substitution products of bromine and iodine of the di-chlorfluoresceïne
from di-chlorphthalic acid and resorcinol (tetrabrom and tetraiodo-di-chlor-
#uoresceine).
4) The substitution products of bromine and iodine of the tetrachlor fluoresceine
from tetrachlorphthalic acid and resorcinol (tetrabromtetrachlorfluoresceine and
tetraiodotetrachlorfluoresceïne).
Dated this 10th day of February 1896.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Colouring Matter from Substituted Fluorescëines.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, 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:-
As first stated by Bayer (Ann. d. Chem. 183) bromcoerulëine is obtained by
strongly heating tetrabromfluoresceine with concentrated sulphuric acid.
According to his process, however, as he admits, a raw product is obtained,
containing only very little bromcoeruleine and this only after a troublesome
purification; thus the manufacture of bromcoerulëine on a large scale, according to
Bayer's system, has not hitherto been practicable.
My foreign correspondents have discovered that substituted fluoresceines may be
transformed into colouring matter of the nature of coerulëine with a good yield,
if, instead of ordinary concentrated sulphuric acid, containing 5 to 8 per cent. of
water, monohydrated or fuming sulphuric acid is employed.
The quantity of anhydride contained in the fuming sulphuric acid may vary
greatly, the temperature necessary and the length of time required depending upon
the strength of the acid employed.
EXANDLE

page_text: By adding 40 kilos. of sulphuric acid of 66° Bé. and 100 kilos. of 60° Bé., the
excess of fuming sulphuric acid is decomposed and the colouring matter is.
precipitated by means of ice and water.
After washing out the almost black paste thus obtained, it can at once be used
for dyeing purposes. It is not soluble in water, soluble with great difficulty in
alcohol but easily in sulphuric acid with a dark cherry-red colour; it is soluble
with a bluish green colour in alkalies and alkaline carbonates. Common salt.
precipitates the alkali salt from these solutions; it dyes chrome mordanted wool a
strong bluish-green and is very fast to air and fulling.
My correspondents have also discovered, that the product obtained by means.
of the above process undergoes a further change by treating it with sulphuric acid
containing water. The colouring matter, thus obtained, dyes more vividly and with.
a more greenish tint
By adding 40 kilos. of sulphuric acid of 66° Bé. and 100 kilos. of 60° Bé., the
excess of fuming sulphuric acid is decomposed and the colouring matter is.
precipitated by means of ice and water.
After washing out the almost black paste thus obtained, it can at once be used
for dyeing purposes. It is not. soluble in water, soluble with great difficulty in
alcohol but easily in sulphuric acid with a dark cherry-red colour; it is soluble
with a bluish green colour in alkalies and alkaline carbonates. Common salt.
precipitates the alkali salt from these solutions; it dyes chrome mordanted wool a
strong bluish-green and is very fast to air and fulling.
My correspondents have also discovered, that the product obtained by means.
of the above process undergoes a further change by treating it with sulphuric acid
containing water. The colouring matter, thus obtained, dyes more vividly and with.
a more greenish tint
EXAMPLE:-
2) 1 part by weight of the dried colouring matter, as prepared according to
Example 1 is heated to 130° C. for 3 to 4 hours, together with 10 parts by weight
of ordinary concentrated sulphuric acid, and precipitated by the addition of water,.
then filtered, washed out and used as colouring paste.
In order to manufacture this greenish product, it is expedient to combine.
processes 1 and 2 in the following manner :-
EXAMPLE
3) 1 part by weight of tetrabromfluorescëine together with 5 parts by weight of
fuming sulphuric acid are heated to 125° C., until, according to Example 2) no.
further colouring matter, soluble red in alkali, can be traced; then, by adding a
little water or sulphuric acid containing water, the excess of anhydride is destroyed
and, after a lapse of 3 to 4 hours, the product is heated to 130° C. Having
precipitated with water, the colouring matter separates as explained in 2).
For the manufacture of coeruleine like colouring matters from tetrabrom-
fluorescëine, as described above, the following bodies are also suitable :-
1) Di-substituted bromfluorescëine.
2) The fluoresceines substituted with iodine instead of bromine (di-iodo a tetra--
iodofluoresceine).
3) The substitution products of bromine and iodine of the di-chlorfluorescöine
from di-chlorphthalic acid and resorcinol (tetrabrom and tetraiodo-di-chlorfluor-
escëine).
4) The substitution products of bromine and iodine of the tetrachlor fluoresceine
from tetrachlorphthalic acid and resorcinol (tetrabromtetrachlorfluoresceine and
tetraiodotetrachlorfluorescëine).
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 :-
1. The herein described manufacture of colouring matters from substituted
fluoresceines by heating the fluoresceines with monohydrated or fuming sulphuric
acid.
2. The modified manufacture subjecting the products thus obtained to further
heating with sulphuric acid containing water.
3. The colouring matters manufactured as above set forth.
Dated this 10th day of November 1896
ABEL & IMRAY,
Agents for the Applicant..