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Base‐catalysed hydrolysis of γ‐lactones: reactivity–structure correlations for 3‐(aryl‐ and alkylmethylene)‐( Z )‐1(3 H )‐isobenzofuranones
Author(s) -
Bowden Keith,
Agnihotri Kanwaljit,
Ranson Richard J.,
Perjéssy Alexander,
Hrnĉiar Pavol,
Prokeŝ Ivan,
Fabian Walter M.
Publication year - 1997
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/(sici)1099-1395(199711)10:11<841::aid-pca950>3.0.co;2-6
Subject(s) - chemistry , substituent , reactivity (psychology) , hydrolysis , aryl , base (topology) , reaction rate constant , medicinal chemistry , aqueous solution , alkaline hydrolysis , computational chemistry , organic chemistry , stereochemistry , kinetics , alkyl , medicine , mathematical analysis , alternative medicine , mathematics , physics , pathology , quantum mechanics
Rate coefficients were measured for the base‐catalysed hydrolysis of a series of γ‐lactones, i.e. 39 substituted 3‐(aryl‐ and alkylmethylene)‐( Z )‐1(3 H )‐isobenzofuranones (3‐aryl‐ and alkylmethylenephthalides) in 70% (v/v) aqueous dioxane at 30·0 °C. A Hammett reaction constant for the 3‐ or 4‐substituted phenyl series is ca 1·5, whereas those for the 2‐substituted phenyl and 4‐substituted 1‐naphthyl series, using para ‐σ values, are ca 1·0 and 1·9. These results are related to an electrostatic field effect model. A very successful correlation between the rates of alkaline hydrolysis of all 39 phthalides and the carbonyl stretching frequencies in chloroform was found. Substituent effects in widely different environments give linearly related effects on both reactivity and physical properties. Computational studies using the semi‐empirical AM1 method correctly modelled both the details of the mechanistic pathway and the substituent effects. © 1997 John Wiley & Sons, Ltd.