Some Aspects of the Chemistry of Sulphur Halides and Oxyhalides

Abstract

The reactions between thionyl chloride and ketones containing
at least one alpha proton, have been shown to give a variety of
products depending upon the applied conditions and the structure
of the adjacent groups. This work partly deals with the reactions
of thionyl chloride with 1,3-diketones which afforded sulphides
and o-chlorides. Typically, dimedone gave di-2-hydroxy-4,4-dimethyl-
~6-oxocyclohex-1-enyl sulphide and 2-chloro-5,5-dimethylcyclohexane-
-1,3-dione,whereas 1,1-dibenzoyl ethane gave a mixture of products
containing an α-sulphinyl chloride, which upon treatment with
ethanol gave a disulphide, a trisulphide, or a thiosulphinate
according to the conditions employed.

A number of possible intermediates were investigated in
an attempt to establish the conditions and structural requirements
necessary for the formation of the above products.

A novel synthesis of β-ketosulphinyl chlorides was developed
which afforded excellent yields in a simple one stage process.
Certain of the chemical and spectral properties of this new class
of compounds were examined in an effort to elucidate the role
of sulphinyl chlorides as intermediates in the reaction of 1,3-
-diketones with thionyl chloride.

Ethyl isopropyl ketone afforded a 3~thietanone upon treatment
with thionyl chloride, a reaction which possibly involved a sulphinyl
chloride intermediate.

Lastly a number of partly saturated cyclic compounds suitably
activated by carbonyl groups, were shown to be readily oxidised
by thionyl chloride to give aromatic systems.

Date of Award	1973
Original language	English