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Substituent effects on the kinetic solvent isotope effect in solvolyses of arenesulphonyl chlorides
Author(s) -
Koo In Sun,
Lee Ikchoon,
Oh Jieun,
Yang Kiyull,
Bentley T. W.
Publication year - 1993
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.610060405
Subject(s) - chemistry , kinetic isotope effect , hammett equation , substituent , methanol , solvent , kinetic energy , solvent effects , computational chemistry , solvolysis , medicinal chemistry , inorganic chemistry , organic chemistry , kinetics , hydrolysis , reaction rate constant , deuterium , physics , quantum mechanics
The Hammett type plot of kinetic solvent isotope effect (KSIE = k SOH/ k SOD), log(KSIE) vs σ, can be a useful mechanistic tool for solvoltic reactions. The slopes of such straight line plots for para ‐substituted benzenesulphonyl chlorides in methanol (0·15), water (0·05) and methanol–water (0·05) are interpreted in terms of different reaction channels (general base‐catalysed and S N 2), in contrast to simple Hammett plots, log k SOH (or log k SOD) vs σ, invariably exhibiting non‐linear concave curves.