On Sulphonfluoresceïn and Some of Its Derivatives — John Shaqi
On Sulphonfluoresceïn and Some of Its DerivativesHayes, C. W. (Charles Willard)
Science
On Sulphonfluoresceïn and Some of Its Derivatives
Hayes, C. W. (Charles Willard)
Sulfonefluorescein; Thesis (Ph. D.)
Attempts were made to prepare the calcium salt but without success.
The S-fluoresceïn was boiled several hours with very finely powdered
calcite, and some salt was formed as shown by the CO_{2} evolved
but on evaporating the solution and recrystallizing the substance
deposited it was found to be the unchanged S-fluoresceïn. Some Ca.
salt was in the mother liquors but its extreme solubility prevented a
separation being made.
Acetyl derivative of S.fluoresceïn.
S.fluoresceïn was boiled with an excess of acetic anhydride for about
three hours. The solution became quite dark and when evaporated on
the water bath left a black tarry residue. This was treated with
water which dissolved a part leaving a dark flocculent precipitate.
The solution was boiled with animal charcoal and evaporated nearly
to dryness. On cooling there separated a light yellow flocculent
precipitate very soluble in hot water and but slightly less so in
cold. This was dissolved in a small quantity of alcohol from which
it separated on evaporation in small radial crystals having a light
lavender color & satiny luster. They also have a peculiar odor
resembling slippery elm which is not removed by recrystallization.
They show a tendency to decompose, becoming yellow on exposure to
the air. The substance does not melt or change in appearance under
245°. With alkalis it gives a slight greenish fluorescence. From the
method of its formation this was taken to be an acetyl derivative
of S.fluoresceïn but whether the mono-or di-acetyl could not be
determined without analysis for which the substance did not suffice.
Bromine substitution products of S-fluoresceïn.
It was especially interesting to see what influence the SO_{2} group
would exert upon the introduction of Bromine into the compound. In
the case of fluoresceïn four Bromine atoms enter easily and special
precautions are necessary to obtain a product containing a smaller
number. The case however is different with S.fluoresceïn.
The latter was dissolved in glacial acetic acid in which it is
soluble with some difficulty and to the solution was added a 20%
solution of bromine in acetic acid, in sufficient quantity to make
eight atoms of bromine to one molecule of S.fluoresceïn. This
solution was evaporated on the water bath and while still having a
considerable volume, small, red, sharply defined crystals began to
separate. The solution was evaporated to a small volume and allowed
to cool but nothing further separated. These crystals are difficultly
soluble in water, alcohol and ether. The alkaline solution shows a
green fluorescence and slight red color by transmitted light. These
crystals were dissolved in a large quantity of alcohol which on
evaporation gradually deposited very small yellow crystals, which
were dried in the air and taken for analysis. The Br. was determined
by Carius method.
I. ·2345 gr sub. gave ·1718 gr AgBr = 31·17% Br.
II. ·2786 gr ” ” ·1815 gr ” = 27·72% Br.
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