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.)
Before passing on to the methods used for converting the sulphinide
into free acid another method should be described by which
the former was obtained in larger quantities and much more easily
than by the one above described.
Beckurts and Otto (Ber. XI. 2061) found that by treatment of toluene
with sulphuryl hydroxy-chloride or chlorsulphonic acid, ClSO_{2}OH,
both o- and p- and as they supposed also m-toluene sulphonchlorides
were formed together with the corresponding sulphonic acid.
Claesson and Wallin (Ber. XII. p. 1848) repeated the work reaching
practically the same results and finally Noyes (Am. Ch. Jour. Vol.
VIII. p. 176) employed the reaction as a convenient method for
obtaining toluene o-sulphon-chloride.
Chlorsulphonic acid is made by passing dry HCl over solid sulphuric
acid so long as it continues to be absorbed. Since no solid sulphuric
acid was at hand, ordinary fuming Nordhausen acid was taken and
from one of two equal portions the SO_{3} was driven over into
the other. HCl was passed into the latter and the resulting
chlorsulphonic acid distilled off at about 156°.
This was placed in a flask, provided with a drop funnel and exit
tube, in portions of 150 gr. and to each portion 60 gr. of toluene
was added, very slowly, with constant shaking, the temperature
being kept near 10°. The action is violent and if any toluene is
allowed to collect on the surface of the liquid it is apt to produce
disastrous results. Large quantities of HCl are given off and the
liquid in the flask assumes a brown color. When all the toluene has
been added, it is poured into a large quantity of ice water, when
the sulphon-chlorides separate out, the ortho- as a heavy oil and
the para- as a white crystalline solid. After allowing to stand some
time in order that as much of the para-chloride might crystallize as
possible the ortho- was drawn off and subjected to a freezing
temperature for several hours. By this means more of the p-chloride
was removed and the operation was replicated as long as any crystals
continued to form, generally two or three times. In this way the
greater part of the para- may be removed, though some still remains
dissolved in the liquid chloride, which cannot be removed by repeated
freezings.
The chloride thus obtained was treated with strong aqueous ammonia.
The conversion to the sulphamide does not take place so readily as
in case of the pure o-chloride obtained from the sulphonic acid and
phosphorus pentachloride.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account