Migration sulphide groups

The use of 2,6-dimethoxyphenyl as the aryl group of the cyclopropyl sulphide provides electronic acceleration for the migration of the cyclopropyl bond and steric bulk which reduces the nucleophilicity of the thiol. Consequently, the cleanliness and the yield of the reaction are improved ... 

Irradiation of sulphonium salts (308) in acetonitrile solution has been shown to lead to lateral-nuclear rearrangement and the gg formation of l-(methylthio)-2-substituted alkylnaphthalenes (309). The quantum yield of product formation varies between 0.24 and 0.1 but bond cleavage to yield 1-naphthyl methyl sulphide also occurs and MeCONH-CHg-R is a by-product of the migrating group and the solvent. The steric crowding in r.tris(trimethylsilyl )methyl] benzene (310) is considered to be the origin of its photolability and on irradiation it efficiently yields (311), (312), and five... 

Rate constants, for ion-molecule reactions 348, 349 Rearrangement—see also Cyclization and Group migrations of N-alkylaminodiaryl sulphides 689... 

Certain a-hydroxyalkylthioketals eliminate benzenethiol under treatment with a sulphonic acid to provide a regiospecific approach to a-phenylthioketones (Scheme 31), On the other hand, j8-hydroxyalkyl phenyl sulphides eliminate water, with migration of the PhS group, to yield allyl sulphides. ... 

Thermolysis of allyl 2-thienyl sulphide (224) yields a mixture of the thiol (225), the diallyl compound (226), and the bicyclic heterocycles (227) and (228)." In the base-induced Truce-Smiles rearrangement of 5-mesitylenesulphonyl-2-methylthiophen (229) to yield (230), the thienyl group migrates with a change in... 

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