• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3657-3664
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• 2012

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.