SYNTHESIS AND REACTIONS OF S,S-DIPHENYL-N -NITROSULFILIMINE

Reaction of S,S-diphenyl-N-tosylsulfilimine with mixed acid of cone. H 2SO4 and cone. HNO3 gave S,S-diphenyl-N-nitrosulfilimine in 57% yield. Pyrolysis of this N-nitrosulfilimine gave the corresponding sulfide ( 30%) and sulfoxide (31%). Alkaline and acidic hydrolysis gave the corr esponding sulfoxide in high yields. Reactions with Grignard reagents a nd organolithium reagents and reductions with phenylmethanethiol, LiAl H4, and NaBH4 afforded the products which were considered to be formed through nucleophilic substitutions on the sulfur atom. Many of these reactions showed that N-nitrosulfilimines are more subject to the subs titution than other N-substituted sulfilimines. Thermal analysis (TG-D TA/DTG, TG-Mass) of the N-nitrosulfilimine and reactions with acyl chl orides, triphenylphosphine, and oxidation with MCPBA, hydrogen peroxid e and sodium hypochlorite were also examined. Results of ab initio cal culation (RMP2/6-31G) of the model compounds (H(2)SNX) suggest that t he S-N bond of the N-nitrosulfilimine is the longest of the N-substitu ted sulfilimines to consist with the above character of N-nitrosulfili mines.