The synthesis and properties of some novel 5-amino-1,4,2-dithiazolium salts and the X-ray molecular structure of 5-morpholino-3-(4-nitrophenyl)-1,4,2-dithiazolium fluoroborate

Abstract

Reaction of dithiocarbamate salts, either with α-bromo iminium salts followed by oxidative bromination, or simply with α-chloro oxime O-sulphonates, leads to novel 5-amino-1,4,2-dithiazolium salts. Reaction of the salts with sodium borohydride, or with active methylene compounds in the presence of base, gives products analogous to those from 1,3-dithiolium salts, although the former reduction products fail to eliminate the 5-amino group on treatment with acid. The crystal structure of 5-morpholino-3-(4-nitrophenyl)-1,4,2-dithiazolium fluoroborate is reported. This, and n.m.r. evidence, indicates that most of the positive charge resides on the exocyclic nitrogen atom.