Reactions of N-Chlorobenzylmethylamines with Secondary Amines in Acetonitrile. Effect of Base Strength upon the Imine-Forming Transition State

Bong Rae Cho, Sung Keon Namgoong, Richard A. Bartsch

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Reactions of N-chlorobenzylmethylamines 1 with R2NH in MeCN have been investigated kinetically. Eliminations from 1 were quantitative and regiospecific, producing only benzylidenemethylamines. For the elimination reaction of 1 with Bu2NH, kH/kD = 8.8, p = 0.96, ΔH* = 7.6 kcal/mol, and ΔS#= -45.1 eu were determined. The transition state structure is assessed as being highly symmetrical with similar extents of Cβ-H and Nα-C1 bond cleavage, little carbanionic character, and significant π bond formation. The kH/kD and p values first increase and then decrease with enhancing amine base strength. Comparison of these results with those for related olefin-forming eliminations provides insight into the transition state differences between imine- and olefin-forming eliminations.

Original languageEnglish
Pages (from-to)1320-1324
Number of pages5
JournalJournal of Organic Chemistry
Volume51
Issue number8
DOIs
Publication statusPublished - 1986 Jan 1

ASJC Scopus subject areas

  • Organic Chemistry

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