On the mechanism of the N,N-dimethyl amination of Grignard reagents: a kinetic study

Erdik E., Uelhue S. A.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, vol.20, no.9, pp.671-676, 2007 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 20 Issue: 9
  • Publication Date: 2007
  • Doi Number: 10.1002/poc.1229
  • Journal Name: JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.671-676
  • Keywords: grignard reagents, aryl carbanions, electrophilic amination, C-N coupling, N,N-dimethyl O-(mesitylenesulfonyl)hydroxylanine, Hammett plot, activation parameter, CATALYZED ELECTROPHILIC AMINATION, AB-INITIO, DISPLACEMENTS, DIARYLAMINES, ARYLAMINES, GEOMETRY
  • Ankara University Affiliated: No

Abstract

A direct kinetic study is reported for the electrophilic amination of substituted phenylmagnesium bromides with N,N-dimethyl O-(mesitylenesulfonyl)hydroxylamine in THF. Rate data, Hammett relationship, and activation entropy are consistent with a S(N)2 displacement involving the attack of carbanions to sp(3)N in the amination reagent (AR). Copyright (C) 2007 John Wiley & Sons, Ltd.