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.)
Some experiments previously performed by Remsen and Palmer (A.G.)
indicated the possibility of the formation of a fluorescent substance
by the action of ortho-sulpho-benzoic acid on resorcin but they did
not succeed in obtaining any definite crystallized compound from the
reaction.
The chief obstacle to be overcome in the work is the difficulty in
obtaining the o-sulpho-benzoic acid and a large proportion of the
work here described was applied in that direction.
Ortho-sulpho-benzoic acid: Methods for its preparation.
1. From toluene and H_{2}SO_{4}.
A method employed by Remsen and Fahlberg (Am. Ch. Jour. Vol. 1.
p __ ) for getting the sulphonic acid group in the ortho position to
methyl was; (a) treat toluene with fuming H_{2}SO_{4} forming thus
ortho- and para- toluene sulphonic acids, (b) make the calcium salt
of the sulphonic acids thus formed and from this the potassium
salt. (c) treat this mixture of potassium toluene sulphonates
with phosphorous penta-chloride forming the corresponding
sulphonchlorides. One of these (para) being a solid and the other
(ortho) an oily liquid a nearly complete separation could be
effected. The difficulty with this method is however that the larger
part of the product is the para and only a comparatively small
proportion of the ortho compound is formed.
2. From p-nitro-toluene and H_{2}SO_{4}.
A second method employed consists in starting with p-nitro-toluene.
This when treated with H_{2}SO_{4} forms toluene p-nitro o-sulphonic
acid. If now a method could be obtained for removing the nitro group
the desired result would be attained.
The attempt was made by Remsen and Palmer (A.G.) to accomplish this
by (a) reducing the nitro compound to the amide, (b) making the diazo
compound and (c) boiling this with absolute alcohol. According to
generally accepted views this should effect the removal of the diazo
group and its replacement by hydrogen.
Experiments however showed that the replacement was made not by
hydrogen but by the ethoxy group -OC_{2}H_{5}. This method was
therefore impracticable.
A modification of this method was suggested by an observation of
Baeyer and Liebermann that if phenyl hydrazine be boiled with a
dilute solution of copper sulphate the hydrazine group is replaced
by hydrogen and benzene thus formed. Hence it was believed that if
the hydrazine compound should be made from diazo compound mentioned
above, the corresponding hydrocarbon, i.e. toluene o-sulphonic acid
could be obtained. The results of experiments showed that this
afforded a practicable method of preparing toluene ortho-sulphonic
acid.
After experimenting with various modifications of the method the
following was found to be the best adapted to the purpose.
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