Base-catalysed hydrolysis of γ-lactones: reactivity–structure correlations for 3-(aryl- and alkylmethylene)-(Z)-1(3H)-isobenzofuranones

✍ Scribed by Keith Bowden; Kanwaljit Agnihotri; Richard J. Ranson; Alexander Perjéssy; Pavol Hrnĉiar; Ivan Prokeŝ; Walter M. Fabian

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 131 KB
• Volume: 10
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199711)10:11<841::aid-pca950>3.0.co;2-6

✦ Synopsis

Rate coefficients were measured for the base-catalysed hydrolysis of a series of ␥-lactones, i.e. 39 substituted 3-(aryl-and alkylmethylene)-(Z)-1(3H)-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-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.