The Manufacture or Production of a Colouring Matter or Dye Stuff from Phenol-phthalein.
Year: 1889

page_text: Date of Application, 26th Feb., 1889
Complete Specification Left, 15th Nov., 1889-Accepted, 18th Jan., 1890
PROVISIONAL SPECIFICATION.
The Manufacture or Production of a Colouring Matter or Dye Stuff
from Phenol-phthalein.
We, CHARLES DREYFUS of Clayton Manchester, in the County of Lancaster
Chemist and HENRY BULL and JOHN HALL both of Clayton aforesaid Chemists do
hereby declare the nature of this Invention to be as follows :-
The object of this Invention is to obtain from phenol-phthalein a new colouring
matter or dye-stuff. According to this Invention we dissolve phenol-phthalein in
Sulphuric acid and we afterwards add nitric acid. The following is a more precise
description of the process which will we believe be found best in practice. We
dissolve one hundred parts by weight of phenol-phthalein in five hundred parts by
weight of sulphuric acid (at 168° Twaddle) on the water bath and under moderate
heat. We allow the solution to cool down say to 20° Centigrade and then we add
seventy parts by weight of nitric acid of a specific gravity of 146. The completion
of the re-action is indicated when a sample dissolved in dilute caustic soda solution
shews the yellow colour of the new nitro-derivative instead of the red colour of the
phenol-phthalein. The product of the re-action is poured into three thousand parts
by weight of water and the precipitated nitro-derivative is filtered off and dried. If
recrystallized repeatedly in a mixture of phenol and alcohol it gives a yellow
crystalline powder which is nearly insoluble in water but which dissolves in an
alkaline solution when it gives a deep yellow colour. It is believed that the new
derivative is a di- or tri-nitro derivative of the phenol-phthalein.
We may use glacial acetic acid in place of sulphuric acid and a nitrate instead of
the nitric acid but we generally prefer to use Sulphuric and nitric acids. The new
nitro-derivative we can transform into its alkaline salts by means well known to
chemists. The salts are soluble in water and dye in a neutral bath animal fibres a
deep and good yellow colour.
DL: ocal
1
1000
COMPLETE SPECIFICATION..
The Manufacture or Production of a Colouring Matter or Dye Stuff
from Phenol-phthalein.
We CHARLES DREYFUS of Clayton near Manchester in the County of Lancaster
Chemist and HENRY BULL and JOHN HALL of the same place Chemists 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 object of this Invention is to obtain from phenol-phthalein a new colouring
matter or dye-stuff. According to the said Invention we dissolve phenol-phthalein in
sulphuric acid and we afterwards add nitric acid. We may use glacial acetic acid in
whole or in part in place of sulphuric acid and we may use a nitrate in place of the
nitric acid.
In order that this Invention and the best ways with which we are acquainted for
carrying it out in practice may be well understood we will describe it more particu-
larly with reference to the following methods of performing the said Invention.

page_text: moderate heat, say a temperature of 50° Centigrade. We allow the solution to cool
down (say to 20° Centigrade) and then we add seventy parts by weight of Nitric
acid of a specific gravity of 1'46. The completion of the re-action is indicated when
a sample dissolved in dilute caustic soda solution shows the yellow colour of the new
nitro-derivative instead of the red colour of the Phenol-phthalein. The product of
the re-action is poured into three thousand parts by weight of water and the pre-
cipitated nitro derivative is filtered off and dried.
If re-crystallized repeatedly from a mixture of phenol and alcohol or from acetic
acid it gives a yellow crystalline powder having the melting point 2444°, which is
nearly insoluble in water but which dissolves in an alkaline solution, when it gives a
deep yellow colour and is a tetranitro derivative of the phenol phthalein. This new
derivative we can transform into its alkaline salts by means well known to chemists.
The salts are soluble in water and dye in a neutral bath animal fibres a deep and good
yellow colour.
METHOD II.
-
100 parts by weight of phenolphthalein are dissolved cold in 500 parts by weight
sulphuric Acid at 168 Twaddel, then cooled down to from 10° to +10° Centigrade
& a mixture of 60 parts by weight of nitric acid of a specific gravity of 144 and
60 parts by weight of Sulphuric acid at 168 Twaddel are run slowly into it, while it
is constantly stirred the temperature may not rise above 10° Centigrade; when all
the acid mixture has been run in, the stirring is continued a few hours longer and
then the same quantity of the aforesaid acid mixture is run in stirring all the while
and cooling to a temperature of 20 to 30° Centigrade; after standing say about
2 hours, the product of the re-action is run into 3,000 parts by weight of cold water
and the nitro product separates as a fine powder which is filtered and washed.
The dry product is an amorphous white or slightly yellow powder, which has
usually a melting point of 120° to 140° Centigrade; if it be extracted in a Soxhlet
apparatus for some hours with 3 times its weight of glacial acetic acid there remains
a residue representing about 65% of the total substance used the melting point of
which residue is between 230° and 244° Centigrade. Out of the solution a small
quantity of the same substance is deposited, so that the total weight represents about
75 per cent. of the original substance used.
After distilling off the glacial acetic acid the remaining 25% is obtained in the
form of a sticky mass the half of which is soluble and the other half insoluble in
water. These two substances give alkaline salts of a dirty yellow colour.
If the residue of the extraction be repeatedly crystallized from its acetic solution,
the melting point of the substance rises to 2441 Centigrade, this substance is a
tetranitrophenolphthalein. The analysis has shewn 10.89 per cent. of nitrogen
for C. 20. H. 10. N. 4. O. 12 the calculation gives 11-2 per cent. of nitrogen.
This substance is slightly soluble only in the usual solvents; a saturated solution of
it in glacial acetic acid contains at a temperature of -15° to 20° Centigrade 1.06 per
cent. The alkaline salts are very soluble. The barium salt is a yellow amorphous
body slightly soluble in cold water and more soluble in hot water. The Calcium Salt
is a yellow body more soluble than the Barium Salt. The Zinc and Silver Salts are
soluble in hot water and in Ammonia. The Lead Salt is only slightly soluble, it
dissolves in Caustic Soda but not in Ammonia.
By treating tetranitrophenolphthalein with a solution of Sulphide of Sodium the
colour passes from red brown to black and finally to a pure blue this solution when
acidified becomes red, an Alkali brings the blue colour back again. By leaving this
blue solution in contact with air it becomes red.
METHOD III.
We dissolve 100 parts phenol phthalein in 1000 parts of Glacial Acetic Acid and
run into it slowly whilst agitating a mixture of 70 parts nitric acid of a specific
gravity of 1-48 and 210 parts Sulphuric Acid at 168 Twaddel. After a short time a
nitro compound of phenol phthalain canarates which is filtered

page_text: By recrystallising in glacial acetic acid a dinitrophenolphthalein is obtained of a
melting point at 196° Centigrade. The analysis shows 6.91 per cent. Nitrogen, the
theory requires 6.86 per cent.
If one part of the crude or recrystallised product is dissolved in 5 parts of
Concentrated Sulphuric Acid and if it be treated a few hours at a temperature of
from 20 to 30° Centigrade with 0-6 parts of nitric acid of the same concentration as
above a tetranitro derivative is obtained which is separated as in Method No. II.
If a mixture of 100 parts phenolphthalein and 500 parts Sulphuric Acid (at
168 Twaddel) be heated in the Water Bath at a temperature of 90-100° Centigrade
for about two hours a Sulphoacid of phenolphthalein is formed which is soluble in
water.
This mixture is cooled to-10 to +10° Centigrade and to it is added gradually
and whilst stirring 120 parts of a mixture of equal parts of nitric acid of a specific
gravity of 141 and Sulphuric Acid at 168 Twaddel.
When the whole mixture is introduced into the Apparatus the mixing is continued
for 4 hours longer at the ordinary temperature and we add again slowly 120 parts of
the Acid mixture as above letting the temperature rise to from 30 to 40° Centigrade
the mixing is continued for say another 4 hours and then the mass is poured into
water which precipitates the nitro product which is filtered washed and dried. This
product is insoluble in water, it is easily soluble in Alkalies, the solution being yellow.
The Alkaline Salts dye Animal fibres whereas the intermediate nitro sulphuric acid
obtained is easily soluble in water and its Alkaline Salts dye Animal fibres only to a
very inferior degree.
In Method II the quantities given can be varied, it is important however to use
at least 4 molecules of nitric acid and also not to let the temperature rise too high
during the first period of the nitrification, though at a higher temperature for example
at 50° Centigrade the tetranitro product is still formed but this product prepared at a
higher temperature is not so pure.
In Method III the nitrification can be made in the acetic solution without using
sulphuric acid or a part only of the proportion given.
Having now particularly described and ascertained the nature of our said Inven-
tion and in what manner the same is to be performed we declare that what we
claim is:-
First The manufacture of a colouring matter or dye stuff from phenol-phthalein
by treating it with sulphuric acid or with glacial acetic acid or with both and with
nitric acid or a nitrate.
Second-The manufacture of colouring matters or dye stuffs from phenol phthalein
by proceeding in the manners herein before described under Examples I II III
and IV.
Third As new articles of manufacture the colouring matters or dye stuffs such as
are prepared from phenol-phthalein in the manners hereinbefore described.
Dated this 15th
L1000
CHARLES DREYFUS.
JOHN HALL.
HENRY BULL.
By J. H. Johnson & Co.,
Agents.