Issue 0, 1973

Free-radical reactions of halogenated bridged polycyclic compounds. Part XV. The reaction of methyl-lithium with some chlorine-substituted norbornenes and norbornadienes

Abstract

The reaction of methyl-lithium with chlorine-substituted norbornenes and norbornadienes not containing C-5 or C-6 substituents results in the replacement of a bridge chlorine atom by a methyl group. The methyl group prefers to enter a position anti to a double bond, and product formation can be accommodated in terms of the formation of C-7 radical pairs. If a C-5 endo-halogen atom is also present, reaction products are different as typified by the formation, in the proportions 20 : 1, of 3,4,5,6-tetrachloro-7-methyltricyclo[4,1,0,03,7]hept-4-ene and 1,2,3,5-tetrachloro-4,6-dimethylnorborna-2,5-diene as products from 5-endo-bromo-1,2,3,4,7,7-hexachloronorborn-2-ene. The formation of the tricyclic product is explicable in terms of C-5 and C-7 radical pairs, but diene formation is more complex, and is best accounted for by initial formation and combination of a C-7 radical pair, followed by the formation ands ubsequent rearrangement of a methyl-substituted C-5 radical. Tricyclic and diene products result from other compounds having halogen substituents at both C-5 and C-7. A choice between reaction paths is finely balanced, and depends on both the position and the reactivity of the various halogen substituents.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 1, 1973, 83-91

Free-radical reactions of halogenated bridged polycyclic compounds. Part XV. The reaction of methyl-lithium with some chlorine-substituted norbornenes and norbornadienes

R. Alexander and D. I. Davies, J. Chem. Soc., Perkin Trans. 1, 1973, 83 DOI: 10.1039/P19730000083

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