Acid-catalyzed rearrangement of ethynylcycloheptatriene to phenylallene

被引：14

作者：

Kitagawa, T ^{[1
]}

Kamada, J ^{[1
]}

Minegishi, S ^{[1
]}

Takeuchi, K ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Engn, Dept Energy & Hydrocarbon Chem, Sakyo Ku, Kyoto 6068501, Japan

来源：

ORGANIC LETTERS | 2000年 / 2卷 / 19期

关键词：

D O I：

10.1021/ol006328e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

GRAPHICS 7-Ethynylcycloheptatriene (1) cleanly isomerizes to phenylallene in the presence of acid. A mechanism involving the protonation of ethynylnorcaradiene, which is in equilibrium with 1, followed by the cleavage of a three-membered ring to give an arenium ion, is proposed. The rearrangement is accelerated by a factor of 370 by introducing tert-butyl groups on C-2 and C-5, indicating the importance of the equilibrium concentration of the norcaradiene form as a rate-controlling factor.

引用

页码：3011 / 3013

页数：3

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