PART I: THE REDUCTIVE CLEAVAGE OF ALKYL PHENYL SULFONES. PART II: THE TRUCE-SMILES REARRANGEMENT OF ARYL ALKYL SULFONES. PART III: THE GAMMA-ELIMINATION OF ARYL 3-CHLOROPROPYL SULFIDES. PART IV: METALATION VS. HALOGEN-METAL EXCHANGE IN BROMOARYL SULFONES. PART V: THE OXIDATIVE CLEAVAGE OF TRIS-(P-TOLYLMERCAPTO)ETHENE TO BIS-(P-TOLYLSULFONYL)METHANE (RADICAL ANION, FREE CARBANION)
Abstract
Reductive cleavage of alkyl phenyl sulfones follows a pathway which can involve fission of either the alkyl-sulfur or aryl-sulfur bond. The direction of cleavage, which is dependent on both the nature of the alkyl group and on solvent (among other factors), has been rationalized on the basis of relatively low-lying (sigma)('* )orbitals. Lithiation of appropriate methylaryl alkyl sulfones is followed by migration of the alkyl group from sulfur to the benzylic carbon. Product studies, relative reactivities and crossover experiments have led to the conclusion that this reaction occurs via a radical-radical anion chain process. The (gamma)-elimination of 3-chloropropyl sulfides induced by alkali metal amides was found to proceed most likely via initial proton abstraction by amide followed by internal displacement of chloride. The reactions of benzyne with cyclic sulfides was also studied. Bromoaryl sulfones were found to react with n-butyllithium via predominant halogen-metal exchange or metalation. The direction of reaction is largely determined by solvent. Tris-(p-tolylthio)ethene reacts with hydrogen peroxide in acetic acid to give bis-(p-tolylsulfonyl)methane, not tris-(p-tolylsulfonyl)ethene as previously reported.
Degree
Ph.D.
Subject Area
Organic chemistry
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