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http://dx.doi.org/10.5012/bkcs.2012.33.11.3657

Rate and Product Studies of 1-Adamantylmethyl Haloformates Under Solvolytic Conditions  

Park, Kyoung-Ho (Department of Chemistry and Applied Chemistry, Hanyang University)
Lee, Yelin (Department of Chemistry and Applied Chemistry, Hanyang University)
Lee, Yong-Woo (Department of Chemistry and Applied Chemistry, Hanyang University)
Kyong, Jin Burm (Department of Chemistry and Applied Chemistry, Hanyang University)
Kevill, Dennis N. (Department of Chemistry and Biochemistry, Northern Illinois University)
Publication Information
Bulletin of the Korean Chemical Society / v.33, no.11, 2012 , pp. 3657-3664 More about this Journal
Abstract
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.
Keywords
1-Adamantylmethyl haloformates; Grunwald-Winstein equation; Leaving group effect; Solvent isotope effect;
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