Chemistry of <i>N</i>-Thiosulfinylanilines. I. Reactions of Sterically Hindered Anilines with Sulfur Chlorides. Preparation of <i>N</i>-Thiosulfinylanilines

Abstract

Abstract Reaction of 2,4-di-t-butyl-6-methylaniline (3) with disulfur dichloride afforded 2,4-di-t-butyl-6-methyl-N-thiosulfinylaniline (4) as a stable compound in 80% yield. Reaction of 2,4,6-tri-t-butylaniline (1) with disulfur dichloride gave in 70% yield 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene, which in solution, exists as a tautomeric mixture with 2,4,6-tri-t-butyl-N-thiosulnnylaniline (2b) as a minor component. In the reactions with 2,4-di-t-butyl-6-isopropyl- or 2,4,6-trimethylaniline, N-thiosulfinylanilines obtained were unstable at ambient temperature. Aniline 1 reacted with sulfur dichloride to give 2 and the corresponding sulfur diimide and N-sulfinylaniline. The reaction of 4 with the dichloride afforded 4 and the corresponding sulfur diimide.