First Preparation and Reactions of S,S-Diaryl-S-fluorothiazynes, Ar2SF(N)

Abstract

S,S-Diaryl-S-fluorothiazynes, Ar2SF(≡N), were prepared by the reaction of S,S-diaryl-N-bromosulfilimines with tetrabutylammonium fluoride. The thiazyne structure was assigned by the spectral data, physical properties, and is consistent with reactions with sodium alkoxides and primary amines. The thiazyne prepared previously by Clifford et al. is doubtful.

S,S-Diphenyl-S-pyrrolidinoiminosulfonium perchlorate

“…However, iminosulfonium salts bearing two carbons and one amino ligand are also very rare. Furthermore, we reported that the reaction of S,S-diaryl-data reports S-fluorosulfanenitrile with cyclic secondary amines afforded the corresponding aminosulfanenitriles (Yoshimura, Kita et al, 1992;, though the corresponding pyrrolidinosulfanenitrile was an impure oily material and thus its identification remained ambiguous. The crystal structure of the title compound, which is now successfully resolved, is a precursor of the sulfanenitrile.…”

Application of alkoxy‐λ6‐sulfanenitriles as strong alkylating reagents

“…In recent years, we have prepared a series of organic 6 -sulfanenitriles [4,5], and have reported the X-ray structural analysis of some 6 -sulfanenitriles [4c,4d,5]. In our previous paper [5], it was reported that alkoxy- 6 -sulfanenitriles [5] exceptionally undergo a facile Ei reaction, although 6 -sulfanenitriles are tetracoordinated hexavalent sulfur compounds like sulfones and sulfoximides.…”

N-Bromo-S-(4-nitrophenyl)-S-phenylsulfimide

“…-sulfanenitriles by the reaction of S,S-diaryl-N-bromosulfimides with tetrabutylammonium fluoride (Yoshimura et al, 1992) and also by the reaction of S,Sdiarylsulfimides using Selectfluor TM , an electrophilic fluorinating reagent, where the reaction proceeds via S,S-diaryl-N-fluorosulfimides as intermediates which undergo 1,2-migration of the F atom (Fujii et al, 2003). We have also performed DFT calculations using a model compound, S,S-dimethyl-N-fluorosulfimide, which showed that the syn conformer of N-fluorosulfimide is more stable than the anti one.…”