Sulphur monoxide, extrusion

Sulphuranes - see also Dialkoxysulphuranes, Oxysulphuranes as intermediates 406 Sulphur bonding 484-493 Sulphur-containing groups, stereoelectronic effects of 584-594 Sulphur dioxide addition to 215-217 extrusion of 137, 140, 141, 158, 163, 397-402, 801, 805, 962, 1098 Sulphur monoxide, extrusion of 397-402 Sulphur trioxide, reactions of 217, 218 Sultenes, as intermediates 743 Sultines 679, 943 as photolytic products 881, 882... 

When heated in toluene, both types of compound form pyrazoles by extrusion of sulphur or sulphur monoxide (equation 158)187. 

The hetero[10]annulenone 2,5-diphenyl-3-thiabicyclo[4.4.1]undeca-l,5,7,9-tetraen-4-one (149) was prepared together with the isomers (150) and (151) by photoelimination of sulphur monoxide from the sulphoxide (152). Extrusion... 

Thiaziridines have been postulated as reactive intermediates in the photochemical rearrangement of thiazoles, isothiazoles, -and 4-aryl-l,3,2-oxathiazolium S-oxide," and in the conversion of oxaziridines into imines and elemental sulphur on treatment with thiourea, potassium thiocyanate, or potassium ethyl xanthate. Irradiation of a mixture of 7V-sulphinyl-aniline and diphenyldiazomethane gave iV-diphenylmethyleneaniline, which was probably formed by extrusion of sulphur monoxide from 2,3,3-triphenyl-thiaziridine 1-oxide formed as an intermediate. ... 

The extrusion of sulphur dioxide from a sulphene to give a carbene has been postulated previously, but never authenticated. Flash pyrolysis of a-(toluene-p-sulphonyl)phenyldiazomethane gave i7-tolyl phenyl ketone (15%) and 2-methylfluorene (5%). The former could arise from phenyl-p-tolylsulphene by loss of sulphur monoxide and the latter by loss of sulphur dioxide to give the carbene, which rearranges to the fluorene. Sulphene is postulated as an intermediate in the formation of carbonyl sulphide by the solid-state photolysis of dimethyl sulphone and by various other high-energy processes. 

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