SummaryThe reactions of 2exo-and 2endo-norbornyl bromide ( l e and 2e, respectively) in 90% ethanol with a large excess of potassium hydroxide, and of 2exo-norbornyl p-toluenesulfonate (1 g) with excess sodium thiophenolate in methyl cellosolve, have been studied. They obey the first order rate law and are zero order with respect to the base-nucleophile. However, the ratio of 1,2-and 1,3-elimi n~r i o n to exo-substitution products depends strongly on the base-nucleophile conci'n I I'LLtion. Ion pair intermediates are indicated. The extreme inertness of 2-norbornyl derivatives in displacement reactions is due to severe steric hindrance of rearside nucleophilic attack, a feature they have in common with other bi-and tricyclic molecules bearing nucleofugal groups adjacent to one or two bridgehead atoms.The literature contains surprisingly little evidence for bimolecular nucleophilic displacement reactions at C (2) of 2exo-and 2endo-norbornane derivatives') 1 and 2, respectively, when R represents a nucleofugal group. Claims that such reactions occur are based mainly on the formation of inverted products by reaction with strong nucleophiles under non-solvolytic conditions. Thus, 2exo-and Zendo-norbornyl p-bromobenzenesulfonate (1 a and 2 a, respec-I )
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