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http://dx.doi.org/10.5012/bkcs.2012.33.12.4117

Rate and Product Studies on the Solvolyses of Allyl Chloroformate  

Koh, Han Joong (Department of Science Education, Jeonju National University of Education)
Kang, Suk Jin (Department of Science Education, Jeonju National University of Education)
Publication Information
Bulletin of the Korean Chemical Society / v.33, no.12, 2012 , pp. 4117-4121 More about this Journal
Abstract
The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.
Keywords
Allyl chloroformate; Extended grunwald-winstein equation; $S_N2$ mechanism; Solvent kinetic isotope effect; Product selectivity;
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