Origin of" hetero effect" on nitrogen inversion. Comparison of hydroxylamines and aminoxide anions

CL Perrin, JD Thoburn, S Elsheimer

Index: Perrin, Charles L.; Thoburn, John D.; Elsheimer, Seth Journal of Organic Chemistry, 1991 , vol. 56, # 25 p. 7034 - 7038

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Citation Number: 23

Abstract

Rate constants for nitrogen inversion in N-benzyl-N-methylhydroxylamine, NJV- diethylhydroxylamine, 1-hydroxy-2, 2, 4, 4-tetramethylpyrrolidine, their conjugate bases, and their 0-acetyl derivativea in dimethylformamide-d, were determined based on the'H NMR coalescence temperatures. Relative to-OH, the-0- substituent ought to either raise the barrier to inversion owing to stronger lone-pair repulsions or lower the barrier owing to weaker u- ...