Predicting Reactivities of Phenyl N-methylcarbamates in their Alkaline Hydrolysis

Abstract

The quality of predictions of reactivity coming from alternative theoretical approaches as related to the experimental values is examined for the hydrolysis of phenyl N-methylcarbamates. We have combined literature kinetic data for phenyl N-phenylcarbamates with our own kinetic data and have correlated them all with theoretically estimated reactivity indices: i.e. Hirshfeld and NBO atomic charges, the Parr electrophilicity index (Ω), and the electrostatic potential at the carbon and oxygen atoms of the reaction centre (VC, VO). The results show that the best correlation coefficients are obtained with the electrostatic potentials VO and VC and the electrophilicity index Ω. The variations of electronic structure in the phenolate ions (leaving groups) were also analysed. The results obtained illustrate the accuracy of theoretical description of local properties as provided by the electrostatic potential at the nuclei.