Classical carbonium ions. Part 9. Rates of solvolysis of nitroaryl ethers in aqueous ethanol

Abstract

1-Adamantyl 2,4-dinitrophenolate and t-butyl 2,4-dinitrophenolate undergo solvolysis reactions in aqueous ethanol at rates which accurately fit the Winstein–Grunwald equation, the low m values indicating that solvation of the leaving group distinguishes weakly between water and ethanol. 1-Adamantyl picrate behaves similarly, but secondary picrates react both by alkyl–oxygen heterolysis and by bimolecular aromatic substitution. This fact limits the use of picrate as a leaving group in mechanistic work in such solvents.