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.)
The free acid is mixed with resorcin in the proportion of 1 part acid
to 1.2 parts resorcin, or a slight excess over two molecules of the
latter to one of the former. The mixture is placed in a deep vessel,
a test tube or beaker, which is placed in a sulphuric acid bath, a
thermometer being suspended in the mixture. The bath is heated and at
about 100° the resorcin melts and the acid slowly dissolves in the
liquid. No action appears to take place till the temperature reaches
175° where water begins to be given off and the liquid slowly assumes
a darker color. White crystals of resorcin collect on the sides of
the vessel. After the heating has been continued for about seven
hours at 178°-185° the liquid has a clear deep red color but shows no
signs of becoming viscous. At length lustrous yellow crystalline
plates appear in the liquid and soon the whole mass becomes a thick
nearly solid yellow paste. Continuous heating at the same temperature
causes no further apparent change. This mass, which on cooling is
made up of yellow crystals imbedded in a red vitreous matrix, is then
dissolved in hot water forming a clear red solution or at most one
containing but a small quantity of a brown flocculent precipitate.
This solution is filtered if necessary and evaporated to a small
volume from which the substance separates on cooling in reddish
yellow radial crystals. These are filtered and washed with ether
till the washings are perfectly colorless. The substance on repeated
crystallization from water has a pale straw yellow color and when
deposited slowly forms transparent crystal blocks from 2·6 mm long,
arranged in radial groups.
A considerable amount of resorcin is lost by sublimation during
the reaction especially if the operation is carried on in a beaker
so that some excess should be added. But even when the resorcin
is present in excess at the end of the reaction some free acid is
always left which may be obtained from the mother liquid in the
characteristic colorless orthorhombic crystals.
The water of crystallization and sulphur were determined in the
new compound. In estimating the water, the substance was heated to
106°-123° for about ten hours till it attained a constant weight.
On standing in the air it quickly regains its original weight. When
heated to 130°-140° for some time it turns slightly reddish and loses
over 10% of its weight which is not regained by standing in the air.
Estimation No. I. was made by fusion with KOH and KNO_{3}. Nos. II
and III were made by Mr. Mindileff by Morse’s method, oxidizing with
KMnO_{4} in KOH solution.
·3882 gr. heated to 106°-123° lost ·0302 gr. = 8·5%
Calculation for 2H_{2}O - C_{19}H_{12}O_{6}S+2H_{2}O = 8·9% water.
I. ·2007 gr sub. gave ·1286 gr BaSO_{4} = 8·77% S.
II. gr ” ” ” gr ” = 7·91” ”
III. gr ” ” ” gr ” = 7·89” ”
Calculation for C_{19}H_{12}O_{6}S+2H_{2}O = 7·92% S.
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