Nucleophilic Participation in the Solvolyses of (Arylthio)methyl Chlorides and Derivatives: Application of Simple and Extended Forms of the Grunwald-Winstein Equations

Author(s): Dennis N. Kevill, Young Hoon Park, Byoung-Chun Park, Malcolm J. D'Souza.

Journal Name: Current Organic Chemistry

Volume 16 , Issue 12 , 2012

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Abstract:

The specific rates of solvolysis of chloromethyl phenyl sulfide [(phenylthio)methyl chloride] and its p-chloro-derivative have been determined at 0.0 oC in a wide range of hydroxylic solvents, including several containing a fluroalcohol. Treatment in terms of a two-term Grunwald-Winstein equation, incorporating terms based on solvent ionizing power (YCl) and solvent nucleophilicity (NT) suggest a mechanism similar to that for the solvolyses of tert-butyl chloride, involving in the rate-determining step a nucleophilic solvation of the incipient carbocation in an ionization process. A previous suggestion, that a third-term governed by the aromatic ring parameter (I) is required, is shown both for the new and for the previously studied related substrates to be an artifact, resulting from an appreciable degree of multicollinearity between I values and a linear combination of NT and YCl values.

Keywords: Solvolysis, Grunwald-Winstein, ionization, chloromethyl phenyl sulfide, 2-chloro-2-(methylthio)acetophenone, 2-chloro-2-(phenylthio)acetophenone , 2-chloro-2-(4-methoxyphenylthio)acetophenone, 2-chloro-2-(methylthio)acetone, Chloromethyl p-chlorophenyl sulfide

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Article Details

VOLUME: 16
ISSUE: 12
Year: 2012
Page: [1502 - 1511]
Pages: 10
DOI: 10.2174/138527212800672592
Price: $58

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