Some Aspects of the Chemistry of Sulphur Halides and Oxyhalides


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.

Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Additional Information: Copyright © Symeonides, 1973. K.C. Symeonides asserts their moral right to be identified as the author of this thesis. This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with its author and that no quotation from the thesis and no information derived from it may be published without appropriate permission or acknowledgement. If you have discovered material in Aston Publications Explorer which is unlawful e.g. breaches copyright, (either yours or that of a third party) or any other law, including but not limited to those relating to patent, trademark, confidentiality, data protection, obscenity, defamation, libel, then please read our Takedown Policy and contact the service immediately.
Institution: Aston University
Uncontrolled Keywords: Chemistry,sulphur halides,oxyhalides
Last Modified: 08 Dec 2023 08:03
Date Deposited: 11 Jan 2011 13:51
Completed Date: 1973
Authors: Symeonides, Kyriakos C.

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