SOLVOLYSIS-DECOMPOSITION OF N-1-ADAMANTYL-N-P-TOLYLCARBAMOYL CHLORIDEIN HYDROXYLIC SOLVENTS

In hydroxylic solvents, N-1-adamantyl-N-p-tolylcarbamoyl chloride unde rgoes a facile rate-determing ionization with very little assistance f rom nucleophilic solvation (very low sensitivity to changes in solvent nucleophillcity). In the relatively nucleophilic aqueous ethanol or a queous acetone, the cation formed reacts directly with the solvent. In fluoroalcohols, the low nucleophilicity of the solvent allows an effe ctive competition from a pathway involving disproportionation to the 1 -adamantyl cation and p-tolyl isocyanate, followed by reaction of the new cation either with solvent or with the chloride ion formed in the initial ionization, Grunwald-Winstein plots against Y-Cl values show f or different binary solvent systems a marked dispersion, which can be considerably reduced by incorporation into the analyses of a term gove rned by the aromatic ring parameter. (I). (C) 1997 by John Wiley & Son s, Ltd.