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http://dx.doi.org/10.5012/bkcs.2014.35.8.2263

The Grunwald-Winstein Relationship in the Solvolysis of β-Substituted Chloroformate Ester Derivatives: The Solvolysis of 2-Phenylethyl and 2,2-Diphenylethyl Chloroformates  

Park, Kyoung-Ho (Department of Chemistry and Applied Chemistry, Hanyang University)
Yang, Gi-Hoon (Department of Chemistry and Applied Chemistry, Hanyang University)
Kyong, Jin Burm (Department of Chemistry and Applied Chemistry, Hanyang University)
Publication Information
Bulletin of the Korean Chemical Society / v.35, no.8, 2014 , pp. 2263-2270 More about this Journal
Abstract
Solvolysis rate constants of 2-phenylethyl-(2-$PhCH_2CH_2OCOCl$, 1) and 2,2-diphenylethyl chloroformate (2,2-$Ph_2CHCH_2OCOCl$, 2), together with the previously studied solvolyses of ${\alpha}$- and ${\beta}$-substituted chloroformate ester derivatives, are reported in pure and binary solvents at $40.0^{\circ}C$. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) of the solvolytic reactions are analyzed using the Grunwald-Winstein equation. The kinetic solvent isotope effects (KSIEs) in methanol and activation parameter values in various solvents are investigated for 1 and 2. These results support well the bimolecular pathway with same aspects. Furthermore, the small negative values of the entropies of activation of solvolysis of 1 and 2 in the highly ionizing aqueous fluoroalcohols are consistent with the ionization character of the rate-determining step, and the KSIE values of 1.78 and 2.10 in methanol-d indicate that one molecule of solvent acts as a nucleophile and the other acts as a general-base catalyst. It is found that the ${\beta}$-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.
Keywords
2-Phenylethyl chloroformate; 2,2-Diphenylethyl chloroformate; Grunwald-Winstein equation; Solvolysis; Linear free energy relationship;
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