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

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 retent...

Full description

Saved in:
Bibliographic Details
Published inJournal of organic chemistry Vol. 60; no. 9; pp. 2812 - 2819
Main Authors BURRITT, A, COXON, JM, STEEL, PJ, WHITTINGTON, BI
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 05.05.1995
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
CYCLOPROPANE
MERCURIC IONS
CORNER ATTACK
DERIVATIVES
CATION
Online AccessGet full text

Cover

More Information
Summary: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.
ISSN:0022-3263
DOI:10.1021/jo00114a034