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

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Reactions of (E)-Oarylbenzaldoximes 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.

Original languageEnglish
Pages (from-to)3420-3425
Number of pages6
JournalJournal of the American Chemical Society
Volume114
Issue number9
Publication statusPublished - 1992 Dec 1

Fingerprint

Nitriles
Methanol
Sodium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Reaction of (E)-o-arylbenzaldoximes with sodium methoxide in methanol. Effect of leaving group upon nitrile-forming transition state. / Cho, Bong-Rae; Jung, Jinhee; Ahn, Eun Kyung.

In: Journal of the American Chemical Society, Vol. 114, No. 9, 01.12.1992, p. 3420-3425.

Research output: Contribution to journalArticle

@article{8ef0486c560e4840a20099e1e1e4c248,
title = "Reaction of (E)-o-arylbenzaldoximes with sodium methoxide in methanol. Effect of leaving group upon nitrile-forming transition state",
abstract = "Reactions of (E)-Oarylbenzaldoximes 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.",
author = "Bong-Rae Cho and Jinhee Jung and Ahn, {Eun Kyung}",
year = "1992",
month = "12",
day = "1",
language = "English",
volume = "114",
pages = "3420--3425",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

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 - 1992/12/1

Y1 - 1992/12/1

N2 - Reactions of (E)-Oarylbenzaldoximes 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)-Oarylbenzaldoximes 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.

UR - http://www.scopus.com/inward/record.url?scp=11944249816&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=11944249816&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:11944249816

VL - 114

SP - 3420

EP - 3425

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 9

ER -