Research Article

Correlation of the rates of solvolysis of benzoyl chloride and derivatives using extended forms of the Grunwald–Winstein equation†

  1. Dennis N. Kevill1,*,
  2. Malcolm J. D'Souza2

Article first published online: 21 NOV 2002

DOI: 10.1002/poc.569

Issue

Journal of Physical Organic Chemistry

Journal of Physical Organic Chemistry

Special Issue: CLAFQO Special Issue

Volume 15, Issue 12, pages 881–888, December 2002

Additional Information

How to Cite

Kevill, D. N. and D'Souza, M. J. (2002), Correlation of the rates of solvolysis of benzoyl chloride and derivatives using extended forms of the Grunwald–Winstein equation. J. Phys. Org. Chem., 15: 881–888. doi: 10.1002/poc.569

Author Information

  1. 1

    Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA

  2. 2

    Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA

*Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA

  1. †

    Presented, in part, at the Sixth Latin American Conference on Physical Organic Chemistry, Isla de Margarita, Venezuela, December 2–7, 2001. This paper is dedicated to Professor Shinjiro Kobayashi in recognition of his many contributions to physical organic chemistry.

Publication History

  1. Issue published online: 21 NOV 2002
  2. Article first published online: 21 NOV 2002
  3. Manuscript Accepted: 14 AUG 2002
  4. Manuscript Revised: 11 JUL 2002
  5. Manuscript Received: 13 APR 2002

Funded by

  • NIH–NCRR. Grant Number: 1 P290 RR 16472-01

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Keywords:

  • Grunwald–Winstein equation;
  • solvolysis;
  • solvent nucleophilicity;
  • solvent ionizing power;
  • aromatic ring parameter

Abstract

Available specific rates of solvolysis at 25 °C of benzoyl chloride and four para-substituted derivatives for which both NT and YCl values are tabulated were analyzed using the extended (two-term) Grunwald–Winstein equation. The ionization pathway with appreciable nucleophilic solvation of the incipient carbocation observed for the p-methoxy derivative is accompanied by increasingly important regions of dominant operation of an addition–elimination pathway as the Hammett σ value for the substituent increases. Accordingly, for the p-nitro derivative only the 97% HFIP data point deviates from the addition–elimination correlation. Correlations of the specific rates of solvolysis of 2,6-dimethylbenzoyl chloride are improved by incorporation of a term governed by the aromatic ring parameter (I). Copyright © 2002 John Wiley & Sons, Ltd.

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