A Study On The Electrophilic Amination of Phenyllithuim And Phenylmagnesium Bromide

The electrophilic amination of phenyllithium and phenyl Grignard reagents with O-methylhydroxylamine (I) has been reinvestigated. The effects of the solvent, the reaction temperature and the PhLi / I stoichiometry on the amination yield have been discussed and a mechanism involving the formation of mono-and dilithio deriva- tives of I as intermadiates, has been proposed. The conditions for the amination of an organolithium or Grignard reagent are optimized to be as follows: An ethereal solution of I is added in a 3:1 organolithium / I mole ratio to an ethereal solution of organo lithum at -15°. The use of O-mesitylenesulfonlhyroxlamine as an amino transfer reagent and the examination of organocopper reagents to aminate with I are found to decrease the amination yield. This survey has revealed that I remains as a convenient reagent for the amination of organolithium and Grignard reagent