BROMINATION OF EXO-TRICYCLO[3.2.1.0(2,4)]OCTANE AND ENDO-TRICYCLO[3.2.1.0(2,4)]OCTANE

被引：5

作者：

BURRITT, A ^{[1
]}

COXON, JM ^{[1
]}

STEEL, PJ ^{[1
]}

WHITTINGTON, BI ^{[1
]}

机构：

[1] UNIV CANTERBURY,DEPT CHEM,CHRISTCHURCH 1,NEW ZEALAND

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 09期

关键词：

D O I：

10.1021/jo00114a034

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reaction of exo-tricyclo[3.2.1.0(2,4)]octane with bromine in CCl4 or methanol proceeds, at least in part, by way of a classical ion to give 1,3-addition products. Electrophilic attack by bromine occurs with inversion at the corner to the C2C4 bond and nucleophilic attack by both inversion and retention. In methanol the initial cation species is sufficiently short lived that it does not relax to the classical cation, and nucleophilic attack with inversion competes with skeletal rearrangement. Reaction of endo-tricyclo[3.2. 1.0(2,4)]octane with bromine in CCl4 gives 1,3-addition and an addition rearrangement product which are formed with inversion at the site of both electrophile and nucleophile attack. A further dibromide product is observed, the formation of which is suppressed in methanol. In methanol nucleophilic attack occurs with inversion to give a mixture of 1,3-addition and rearrangement products.

引用

页码：2812 / 2819

页数：8

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