Correlation of the rates of solvolyses of cinnamyl chloride

In Sun Koo; Sun Kyoung An; Kiyull Yang; Ikchoon Lee; T. William Bentley

doi:10.1002/poc.550

journal article Oct 09, 2002

Correlation of the rates of solvolyses of cinnamyl chloride

In Sun Koo Sun Kyoung An Kiyull Yang Ikchoon Lee T. William Bentley

Journal of Physical Organic Chemistry Vol. 15 No. 11 pp. 758-764 · Wiley

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Abstract

AbstractSolvolytic rate constants (k) at 25 °C are reported for solvolyses of cinnamyl chloride (1) in binary mixtures of water with acetone, ethanol, methanol, methanol‐d and 2,2,2‐trifluoroethanol (TFE), and also in TFE–ethanol mixtures; product selectivities (S) are reported for aqueous ethanol and methanol: S = [ether product]/[alcohol product] × [water]/[alcohol solvent]. A good correlation observed between log k and the parameter YCl (solvent ionizing power) is improved only slightly by additional parameters (N for solvent nucleophilicity and/or I, an aromatic ring parameter). Rate ratios in solvents of the same YCl value but different nucleophilicities provide measures of the minimum extent of nucleophilic solvent assistance, and the value of 1.48 for [k40EW/k97TFE]
Y (EW = ethanol–water) is consistent with an essentially SN1 reaction mechanism. A linear relationship between 1/S and molar ratio of solvent was derived theoretically and validated experimentally for solvolyses of the above substrate from water up to 75% alcohol–water. The dependence of S on solvent composition and the absence of rate depression in the presence of added chloride anions are explained by product formation via a contact ion pair. Copyright © 2002 John Wiley & Sons, Ltd.

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Details

Published: Oct 09, 2002
Vol/Issue: 15(11)
Pages: 758-764
License: View

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Cite This Article

In Sun Koo, Sun Kyoung An, Kiyull Yang, et al. (2002). Correlation of the rates of solvolyses of cinnamyl chloride. Journal of Physical Organic Chemistry, 15(11), 758-764. https://doi.org/10.1002/poc.550

Correlation of the rates of solvolyses of cinnamyl chloride

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