Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
The rates of the solvolysis of 3-R-4-homoadamantyl methanesulphonates (mesylates) (3) were determined in 80% aqueous ethanol. The relative first-order rate constants at 25 °C were 1·0 (R = H), 2·29 (R = Ph), 3·26 (R = p-anisyl), 73·6 (R = Me) and 209 (R = Et). The methanolysis of 3 gave rearranged methyl ethers and rearranged olefins as major products together with small amounts (0·9-3·4%) of unrearranged products. The order of the accelerating effect suggests that the transition states involve significant σ-participation, despite the fact that 3 (R = H) solvolyses via a classical ion intermediate. The logarithms of the solvolysis rate constants of 3 showed linear correlations with those of 1-R-2-adamantyl tosylates (1) and 1-R-exo-2-norbornyl tosylates (2), indicating that the linear free-energy relationship between the β-substituent effects on the solvolysis rate is not a definite measure to distinguish between classical and non-classical intermediates.
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