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Correlation of the rates of solvolysis of benzoyl chloride and derivatives using extended forms of the Grunwald–Winstein equation
Author(s) -
Kevill Dennis N.,
D'Souza Malcolm J.
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.569
Subject(s) - solvolysis , chemistry , substituent , benzoyl chloride , carbocation , nucleophile , chloride , medicinal chemistry , derivative (finance) , solvation , computational chemistry , ring (chemistry) , nitration , organic chemistry , ion , hydrolysis , catalysis , financial economics , economics
Available specific rates of solvolysis at 25 °C of benzoyl chloride and four para ‐substituted derivatives for which both N T and Y Cl 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.