The oxidative addition of disulphides to alkenes
The oxidative addition of disulphides to alkenes
Vicinally substituted sulphur-nitrogen compounds are important as natural products and synthetic targets. Their chemistry is surveyed and synthetic routes to this vicinal substitution pattern are reviewed. The electrochemical oxidation of disulphides in the presence of alkenes in acetonitrile gives acetamidosulphides directly. Acetamido sulphides were prepared from the oxidation of diphenyl, dibenzyl and dipyridyl disulphides in the presence of a range of alkenes, including ethene, on platinum and carbon anodes. The effect of added water and/or acid on the reaction systems was investigated. The synthetic and mechanistic aspects of the use of lead (IV) as a reagent for the trifluoroacetoxysulphenylation of alkenes in dichloromethane-trifluoroacetic acid were investigated. Manganese (111), copper (II) and iron (III) were also investigated as reagents for this process and the use of manganese (III) was generalised. Trifluoroacetoxysuiphenylation of alkenes with simple disulphides was found to occur both in dichioromethane-trifluoroacetic acid and with small concentrations of metal salts. Oxidation in the presence of low concentrations of copper (II) was investigated and products derived from the basic disulphides di(2-aminophenyl) and 2,2'dipyridyl disulphide were prepared where other chemical systems failed to give reaction. The trifluoroacetoxysulphides thus prepared may be transformed to acetamidosulphides by a modified Ritter reaction. The chemistry of these products, including the cleavage of benzyl acetamidosulphides to acetamidothiols by sodium in liquid ammonia, is briefly described.
University of Southampton
1983
Owton, William Martin
(1983)
The oxidative addition of disulphides to alkenes.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Vicinally substituted sulphur-nitrogen compounds are important as natural products and synthetic targets. Their chemistry is surveyed and synthetic routes to this vicinal substitution pattern are reviewed. The electrochemical oxidation of disulphides in the presence of alkenes in acetonitrile gives acetamidosulphides directly. Acetamido sulphides were prepared from the oxidation of diphenyl, dibenzyl and dipyridyl disulphides in the presence of a range of alkenes, including ethene, on platinum and carbon anodes. The effect of added water and/or acid on the reaction systems was investigated. The synthetic and mechanistic aspects of the use of lead (IV) as a reagent for the trifluoroacetoxysulphenylation of alkenes in dichloromethane-trifluoroacetic acid were investigated. Manganese (111), copper (II) and iron (III) were also investigated as reagents for this process and the use of manganese (III) was generalised. Trifluoroacetoxysuiphenylation of alkenes with simple disulphides was found to occur both in dichioromethane-trifluoroacetic acid and with small concentrations of metal salts. Oxidation in the presence of low concentrations of copper (II) was investigated and products derived from the basic disulphides di(2-aminophenyl) and 2,2'dipyridyl disulphide were prepared where other chemical systems failed to give reaction. The trifluoroacetoxysulphides thus prepared may be transformed to acetamidosulphides by a modified Ritter reaction. The chemistry of these products, including the cleavage of benzyl acetamidosulphides to acetamidothiols by sodium in liquid ammonia, is briefly described.
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Published date: 1983
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Local EPrints ID: 460170
URI: http://eprints.soton.ac.uk/id/eprint/460170
PURE UUID: 8506cbc5-6952-49c9-abd0-fe9b73970f10
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Date deposited: 04 Jul 2022 18:06
Last modified: 04 Jul 2022 18:06
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Author:
William Martin Owton
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