Reactions of formamidinium salts with organolithium reagents

Abstract

Reaction of tetramethylchloroformamidinium chloride (1) with methyllithium gave vinylidenebisdimethylamine (3) in good yield. Extension of this reaction to higher alkyllithiums was unsuccessful. Reactions of 1 with íerí-butyllithium and phenyllithium proceeded by radical processes. The mechanisms of these reactions, which probably involve substit uted bis (dimethylamino )methyl radicals and possibly bis (dimethylamino) carbene, are discussed.In connection with our study of the chemistry of alkyhdenebisdialkylamines (enediamines) we have been interested in developing new synthetic routes to these compounds. Two such routes have previously been(1) H.

A Convenient Synthesis and Some Characteristic Reactions of Novel Propiolamidinium Salts

“…In this context, it must be remembered that the reaction of phenyl lithium and higher alkyl lithium compounds with this chloroformamidinium salt also did not take the expected addition/substitution pathway, but instead gave products derived from radical intermediates. 7 Coupling of the chloroformamidinium salt with terminal alkynes under Sonogashira conditions was also unsuccessful.…”