Arylsulphonyl radicals

Arylsulphonyl radicals 879 Arylthiomethyl sulphoxides, reactions of 331 / -Arylthiovinyl sulphoxides, synthesis of 345 Aryl unsaturated alkyl sulphones, mass spectra of 137-143... 

Recently, the e.s.r. spectra of some arylsulphonyl radicals, ArS02, have been reported (McMillan and Waters, 1966) these unstable radicals were generated in a flow system by oxidation of the sulphinic acids with ceric ion. Similar radicals have been generated in the solid state by y-irradiation of sulphones (Ayscough et al., 1966). 

Thermal decomposition of diazomethyl aryl sulphones gives numerous products, some derived from the sulphonylcarbene [e.g. 1,2,3-tris-(arylsulphonyl)cyclopropanes] and others from the arylsulphonyl radical (disulphides, thiolsulphonates, and arylsulphonylmethanesulphonates). Conversion of N-nitrosocarbamates ArSOzCHRNCNOlCOjEt into a-diazoalkyl sulphones is rendered more difficult if R is a space-demanding grouping. ... 

Photolysis (2537 A) of A-arylsulphonyldimethyl sulphoximines in aromatic hydrocarbon solvents did not produce arylsulphonyl nitrenes instead, aryl radicals were generated which arylated the solvent 43>. 

Tributylstannane-induced reactions of l-arylsulphonyl-2-iodomethyl-piperidines (4) yield products which include substituted piperidines (5) via radical substitution on the aromatic ring and thiazine S -dioxides (6) by... 

Mass Spectra. The mass spectra of aromatic sulphines, aryl arylthio sulphines, aryl arylsulphinyl sulphines and aryl arylsulphonyl sulphines have been interpreted. In all cases the occurrence of a rearrangement involving the intermediacy of an oxathiiran could be established. The loss of a sulphydryl radical from the molecular ion appeared to be a characteristic process by the electron-induced fragmentation of thioamides, and this was in some cases taken as evidence for pronounced enethiolization of the molecular ion. The fragmentation... 

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