Classical carbonium ions. Part 10. Selectivity in the solvolytic products from 1-adamantyl derivatives in aqueous ethanol

Abstract

The relative proportions of adamantan-1-ol and its ethyl ether obtained when 1-adamantyl bromide, picrate, 2,4-dinitrophenolate, and toluene-p-sulphonate undergo solvolysis at 100 °C in aqueous ethanol were measured at four solvent compositions. Differences between the four substrates were observed, implying ion-pair involvement, and variations with solvent composition which are attributed to differences in the ability of the various ion-pairs to select a molecule of water or of ethanol in forming a solvent-separated ion-pair.