Reaction of (E)-O-Arylbenzaldoximes with Sodium Methoxide in Methanol. Effect of Leaving Group upon Nitrile-Forming Transition State

Bong Rae Cho; Jinhee Jung; Eun Kyung Ahn

doi:10.1021/ja00035a040

Reaction of (E)-O-Arylbenzaldoximes with Sodium Methoxide in Methanol. Effect of Leaving Group upon Nitrile-Forming Transition State

Bong Rae Cho^*
, Jinhee Jung
, Eun Kyung Ahn

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

Reactions of (E)-O-arylbenzaldoximes 1-3 with MeONa-MeOH have been studied kinetically. The reactions proceed via competing E2 and S_NAr reactions, in which the first step is rate-determining. Although the reactions were strongly influenced by the electronic effect of the β-and O-aryl substituents, they were insensitive to the steric effect of the O-aryl group, except that the SNAr reaction was retarded by the CF₃ group of 2. For eliminations from 1-3 promoted by MeONa-MeOH, the k_H/k_D value increased and the Hammett ρ value decreased with better leaving groups. From these results, the effect of leaving group variation upon the nitrile-forming transition state is assessed.

Original language	English
Pages (from-to)	3425-3429
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	114
Issue number	9
DOIs	https://doi.org/10.1021/ja00035a040
Publication status	Published - 1992 Apr 1

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Reaction of (E)-O-Arylbenzaldoximes with Sodium Methoxide in Methanol. Effect of Leaving Group upon Nitrile-Forming Transition State",

abstract = "Reactions of (E)-O-arylbenzaldoximes 1-3 with MeONa-MeOH have been studied kinetically. The reactions proceed via competing E2 and SNAr reactions, in which the first step is rate-determining. Although the reactions were strongly influenced by the electronic effect of the β-and O-aryl substituents, they were insensitive to the steric effect of the O-aryl group, except that the SNAr reaction was retarded by the CF3 group of 2. For eliminations from 1-3 promoted by MeONa-MeOH, the kH/kD value increased and the Hammett ρ value decreased with better leaving groups. From these results, the effect of leaving group variation upon the nitrile-forming transition state is assessed.",

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T1 - Reaction of (E)-O-Arylbenzaldoximes with Sodium Methoxide in Methanol. Effect of Leaving Group upon Nitrile-Forming Transition State

AU - Cho, Bong Rae

AU - Jung, Jinhee

AU - Ahn, Eun Kyung

PY - 1992/4/1

Y1 - 1992/4/1

N2 - Reactions of (E)-O-arylbenzaldoximes 1-3 with MeONa-MeOH have been studied kinetically. The reactions proceed via competing E2 and SNAr reactions, in which the first step is rate-determining. Although the reactions were strongly influenced by the electronic effect of the β-and O-aryl substituents, they were insensitive to the steric effect of the O-aryl group, except that the SNAr reaction was retarded by the CF3 group of 2. For eliminations from 1-3 promoted by MeONa-MeOH, the kH/kD value increased and the Hammett ρ value decreased with better leaving groups. From these results, the effect of leaving group variation upon the nitrile-forming transition state is assessed.

AB - Reactions of (E)-O-arylbenzaldoximes 1-3 with MeONa-MeOH have been studied kinetically. The reactions proceed via competing E2 and SNAr reactions, in which the first step is rate-determining. Although the reactions were strongly influenced by the electronic effect of the β-and O-aryl substituents, they were insensitive to the steric effect of the O-aryl group, except that the SNAr reaction was retarded by the CF3 group of 2. For eliminations from 1-3 promoted by MeONa-MeOH, the kH/kD value increased and the Hammett ρ value decreased with better leaving groups. From these results, the effect of leaving group variation upon the nitrile-forming transition state is assessed.

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Reaction of (E)-O-Arylbenzaldoximes with Sodium Methoxide in Methanol. Effect of Leaving Group upon Nitrile-Forming Transition State

Abstract

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