SOLVOLYSIS OF BICYCLO[2.2.0]HEXANE-1-METHYL P-NITROBENZOATE

Bicyclo[2.2.0]hexane-l-methanol (10) was synthesized in a five-step reaction sequence from the Diels-Alder adduct of 5,5-dimethoxytetrachlorocyclopentadiene and ethylene via 1,4-dichloro-7,7-dimethoxybicyclo-[2.2.1 ]heptane (5), the related 7-ketone 6, 4-chlorobicyclo[2.2.0]hexane-l-carboxylic acid (7), and 4-chlorobicyclo-[2.2.0]hexane-l-methanol (9). The p-nitrobenzoate ester of 10 underwent solvolysis in 60% aqueous acetone at 99.5 and 116.8° to yield 81 % of 1-norbornyl p-nitrobenzoate (13) and 19% 1-norbornanol (14). The rate of the reaction is 7 X 106 faster than the extrapolated rate for the corresponding neopentyl derivative. A correlation between rate and strain release is presented as evidence for anchimeric assistance in this type of rearrangement. © 1968, American Chemical Society. All rights reserved.