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Free energy relationships and intramolecular general acid catalysis
Author(s) -
Greig Ian R.,
Kirby Anthony J.
Publication year - 2004
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.766
Subject(s) - chemistry , intramolecular force , salicylic acid , reactivity (psychology) , aqueous solution , hydrogen bond , hydrolysis , catalysis , computational chemistry , photochemistry , phenols , transition state , organic chemistry , combinatorial chemistry , molecule , medicine , biochemistry , alternative medicine , pathology
Variations in reactivity of substituted salicylic acid derivatives are appraised in the light of the work of Jencks on transition‐state structures, variations in transition‐state structure and variations in reaction mechanism. The transition states for the intramolecular general acid‐catalysed hydrolyses of a variety of compounds derived from salicylic acid are shown to be closely related to those for the corresponding spontaneous hydrolysis reactions of compounds derived from substituted phenols. Free energy relationships are used to estimate the potential benefits of improving intramolecular hydrogen bond geometry in an aqueous environment. Copyright © 2004 John Wiley & Sons, Ltd.