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Kinetics of the reaction of phenyl picrates with phenoxide ions in water. Concerted or stepwise?
Author(s) -
Crampton Michael R.,
Robotham Ian A.
Publication year - 2013
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.3172
Subject(s) - chemistry , nucleophile , adduct , kinetics , reaction rate constant , medicinal chemistry , ion , concerted reaction , leaving group , computational chemistry , catalysis , organic chemistry , physics , quantum mechanics
A kinetic study is reported of the exchange reactions of substituted phenoxide ions with some ring‐substituted 2,4,6‐trinitrophenyl ethers in water. The βrønsted diagrams formed by plotting log k , where k is the second‐order rate constant for reaction, versus p K a show a distinct change in slope when Δp K a = 0 (Δp K a being the difference in p K a values of the leaving group and nucleophile). This is consistent with a two‐step process involving a discrete σ‐adduct intermediate rather than a concerted process. From the measured β values for forward and reverse processes, the overall effective charge map has been constructed. Copyright © 2013 John Wiley & Sons, Ltd.