Sulphonyl halides sulphenes from

Sulphonyl Halides and Sulphenes.—It is becoming clear that reactions of alkanesulphonyl chlorides in the presence of a tertiary amine are likely to give poor yields of simple sulphonation products, due to the formation of sulphenes (RCHaSOgCl RCH=SOa) and artefacts resulting from them. Electron-withdrawing groups in the substituent facilitate sulphene... 

The most common route to sulphenes, the elimination of hydrogen halide from a sulphonyl halide, has been the subject of a recent mechanistic and kinetic study which led to the conclusion that this reaction most probably proceeds by an El mechanism. Tsuge and Iwanami used this reaction for the generation of benzoylsulphene (130) from benzoylmethane-sulphonyl chloride. The reaction of (130) with a series of anils (131) was found to be somewhat dependent on the presence or absence of triethylamine and very dependent on the nature of R in (131). For R = alkyl, the (4 -I- 2) cycloadduct (132) is the predominant or only product, whereas for R = aryl the (2 + 2) cycloadduct (133) is the reaction product. Similar results were obtained for the reaction of (130) with carbodi-imides. The reaction of (130) with aryl cinnamylideneamines gave Diels-Alder adducts (134). ... 

The reactions of sulphimides studied recently concern the kinetics of the reaction between PhSH and JV-toluene-p-sulphonyl-sulphimides - to give PhSSPh, or RSPh (other differences exist between the results from these two studies) the formation of vinyl sulphides by treatment of JV-toluene-p-sulphonyl aryl ethyl sulphimides with Bu OK [TsN=S(Et)Ar -> CHg= CHSAr] the halide-ion-induced Stevens-type rearrangement to the sulphen-amide [TsN=SRAr -> RN(Ts)SAr] and the S-substitution or Pummerer rearrangement products from iV-toluene-/j-sulphonyl-sulphimides by cleavage with NaOH or NaOMe in MeOH. °... 

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