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

• Published in: Bulletin of the Korean Chemical Society Vol. 33; no. 11; pp. 3657 - 3664
• Main Authors: Park, Kyoung-Ho, Lee, Yelin, Lee, Yong-Woo, Kyong, Jin Burm, Kevill, Dennis N
• Format: Journal Article
• Language: Korean
• Published: 2012
• Subjects: Grunwald-Winstein equation; Solvent isotope effect; 1-Adamantylmethyl haloformates; Leaving group effect
• ISSN: 0253-2964; 1229-5949

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.