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Title: Radical reactions of sulfur compounds
Author: da Silva Correia, C. M. M.
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1967
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The reactions of sulphonyl halides with olefins have been reviewed, with other processes of producing free sulphonyl radicals. Reactions of polynuclear aromatic hydrocarbons and quinones with free radicals have also been presented. The decomposition of p-toluene sulphonyl iodide was investigated. The sulphonyl iodide decomposed very slowly when refluxed in carbon tetrachloride for eight hours but in the presence of metals, e.g. silver and copper powders, the decomposition was achieved in less than three hours. The products of this decomposition were p-toluenesulphonic anhydride and p-tolyl-p-toluenethiosulphonate. Copper salts of p-toluenesulphonic acid seem to be formed. The expected dimer, p-tolyldisulphone could not be isolated. Free radicals were used instead of metals to decide whether the sulphonic anhydride was formed by a homolytic or heterolytic reaction. It was expected that the free radicals would combine with the iodine atoms yielding sulphonyl radicals. The reaction mixtures were complex but the formation of p-toluenesulphonic anhydride could still be detected. The dimer, p-tolyldisulphone was also isolated but only in 3-18% yield. Azobis-isobutyronitrile and azobis(1-cyano-l-cyclohexyl) were used as sources of free radicals. The other products of reaction were of the type R-I, R-R and R'-SO2Tol (R = 2-cyano-2-propyl and 1-cyano-l-cyclohexyl; R' = 2-cyano-2-propyl). Decomposition of the sulphonyl iodide under u.v. light gave also p-toluenesulphonic anhydride.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available