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Correlation of the rates of solvolysis of 2‐furancarbonyl chloride and three naphthoyl chlorides
Author(s) -
D'Souza Malcolm J.,
Boggs Mary E.,
Kevill Dennis N.
Publication year - 2006
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.1010
Subject(s) - chemistry , solvolysis , nucleophile , steric effects , chloride , medicinal chemistry , solvation , organic chemistry , solvent , hydrolysis , catalysis
The correlations of the specific rates of solvolysis of the title compounds using extended forms of the Grunwald–Winstein equation are consistent with the overall picture which is emerging for acyl chloride solvolyses, with competing addition–elimination (with rate‐determining addition) and ionization (assisted by nucleophilic solvation) pathways. Except in the more ionizing solvents of low nucleophilicity, 2‐furancarbonyl chloride follows the addition–elimination pathway, in contrast to 2‐thiophenecarbonyl chloride. Except in solvents of highest nucleophilicity and low ionizing power, the solvolyses of the naphthoyl chlorides (1‐naphthoyl, 2‐naphthoyl and 6‐methyl‐2‐naphthoyl) all favor the ionization pathway. In the correlation of the 1‐naphthoyl chloride solvolyses, there is a slight improvement when a term governed by the sensitivity to changes in the aromatic ring parameter ( hI ) is incorporated; this can be associated with a rather minor steric hindrance involving the peri ‐hydrogen. Copyright © 2006 John Wiley & Sons, Ltd.