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The importance of the ortho effect in the solvolyses of 2,6‐difluorobenzoyl chloride
Author(s) -
Park KyoungHo,
Kevill Dennis N.
Publication year - 2012
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.1906
Subject(s) - chemistry , steric effects , chloride , dissociation (chemistry) , ionization , medicinal chemistry , electronic effect , fluorine , ion , computational chemistry , photochemistry , organic chemistry
The ortho effect of the chloro substituents in 2,6‐dichlorobenzoyl chloride sufficiently hindered attack on the acyl carbon such that an ionization mechanism was observed over the full range of solvents studied. We now compare this behavior with that of 2,6‐difluorobenzoyl chloride. The smaller fluoro substituents allow the dominant pathway to be addition–elimination (association–dissociation) in all solvents except those rich in fluoroalcohol, where ionization is dominant. Ranges of operation for both mechanisms had previously been observed for the parent benzoyl chloride but with a wider ionization range than for the 2,6‐difluoro derivative. This indicates that, relative to the parent, the electronic destabilizing influence of the fluorines on acyl cation formation outweighs the steric retardation to attack because of the presence of the two ortho ‐fluorine atoms. An extended (two‐term) Grunwald–Winstein equation treatment of the solvolyses of 2,6‐difluorobenzoyl chloride is reported. Copyright © 2011 John Wiley & Sons, Ltd.