Reaction of S,S-diaryl-S-fluorothiazynes6) with cyclic secondary amines gave novel thiazynes, the corresponding S-aminothiazynes in good yields. Spectroscopic studies, measurement of pKa values, pyrolysis and alkylation reactions of the aminothiazynes were carried out.

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.

The reaction of fluorodiphenyl-l 6 -sulfanenitrile with primary alkyl-or aryl-amines in the presence of acid catalysts or tertiary amines gave N-monosubstituted S,S-diphenylsulfodiimides effectively.

ÁClO 4 À , consists of two crystallographically independent cations and anions. In the salt, protonation occurs at the nitrile N atom attached to the S atom of the corresponding 6 -sulfanenitrile. The structures of the two independent cations are almost the same and the configuration around the S atom is a slightly distorted tetrahedral geometry, with two S-N bonds and two S-C bonds. The S-N(pyrrolidine) and S N bond lengths are 1.6216 (18) and 1.503 (2) Å , respectively, for one cation, and 1.6236 (19) and 1.502 (2) Å , respectively, for the other. The dihedral angles between the two phenyl rings in the cations are 76.61 (9) and 76.42 (9) . There are N-HÁ Á ÁO hydrogen bonds, which link the cation and the anion. The cation-anion pairs are further linked by C-HÁ Á ÁO and C-HÁ Á ÁN hydrogen bonds, forming a three-dimensional network.

1993sulfoxides, sulfones, sulfenes and derivatives sulfoxides, sulfones, sulfenes and derivatives (benzene compounds) Q 0600 -177Preparation and Reactivities of S,S-Diaryl-S-aminothiazynes, Ar2S(NR2)( N).-Reaction of the S,S-diaryl-S-fluorothiazynes (I) with the cyclic secondary amines (II) produces the title compounds (III). The diphenylsulfilimine (IV) and the tetrahydropyridine (V) are obtained by thermal treatment of (IIIc). Alkylation of (IIIc) with methyl iodide (VI) gives the N-methylated sulfonediiminium iodide (VII). -(YOSHIMURA, T.; TAKATA, E.; MIYAKE, T.; SHIMASAKI, C.; HASEGAWA, K.; TSUKURIMICHI, E.; Chem. Lett. (1992) 11, 2213-2216 Dep. Chem. Bichem. Eng., Fac. Eng., Toyama Univ., Gofuku, Toyama 930, Japan; EN)