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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 35, Number 8
BKCSDE 35(8)
August 20, 2014 

The Grunwald-Winstein Relationship in the Solvolysis of β-Substituted Chloroformate Ester Derivatives: The Solvolysis of 2-Phenylethyl and 2,2-Diphenylethyl Chloroformates
Kyoung-Ho Park, Gi-Hoon Yang, Jin Burm Kyong*
2-Phenylethyl chloroformate, 2,2-Diphenylethyl chloroformate, Grunwald-Winstein equation, Solvolysis, Linear free energy relationship
Solvolysis rate constants of 2-phenylethyl-(2-PhCH2CH2OCOCl, 1) and 2,2-diphenylethyl chloroformate (2,2- Ph2CHCH2OCOCl, 2), together with the previously studied solvolyses of α- and β-substituted chloroformate ester derivatives, are reported in pure and binary solvents at 40.0 oC. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity (NT) and solvent ionizing power (YCl) 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 β-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.
2263 - 2270
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