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Vidwans, D. B. (1959) The reaction of olefins with sulphur monochloride. Doctoral thesis, Northern Polytechnic.
Reactions of olefines with sulphur monochloride have been known for a long time. A survey of the available literature revealed that no details are known as regards the kinetics of the mechanism in such a reaction. The work described in this thesis was undertaken so as to elucidate the mechanism of the reaction of sulphur monochloride with cyclohexene and to establish the chemical constitution of the reaction product. The work is restricted to studies of the reaction between cyclohexene and sulphur monochloride.
A brief survey of the relevant literature is presented in Part I, together with the necessary discussion. Part II describes the preparation and characterisation of the reaction product from cyclohexene and sulphur monochloride. Based on the results of chemical analysis, molecular weight, ultra-violet and infra-red examination, a structure has been proposed and the structure is further confirmed by an independent synthesis. The various methods of studying the kinetics of the reaction are summarised in Part III and the validity of the dilatometric technique has been clearly brought out by comparison with Spekker absorptiometric and infra-red methods. Dilatometric studies are then extended to investigate the reaction in further details. The kinetic order both with respect to cyclohexene and sulphur monochloride is studied at two different temperatures and the Arrhenius parameters are evaluated. The effect of various additives - dichloro dicyclohexyl disulphide, benzoquinone, cetyl pyridinium chloride, tetra-n-butyl ammonium chloride, hydrogen chloride and ferric chloride - on the reaction rate has been investigated in the search for mechanistic information. The polar nature of the mechanism is indicated as a result of strong accelerative effect by polar solvents. The general conclusions are then summarised and finally a mechanism of the reaction is proposed in Part VI. Detailed experimental results and infra-red spectra are given in the experimental part, together with a bibliography at the end.
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