Reactivity of acetanilides in the alkaline hydrolysis reaction: theory vs. experiment

Abstract

The rate constants (at 25°C) for the alkaline hydrolysis of a series of seven acetanilide derivatives were determined experimentally. The series included the parent compound acetanilide and the following para-substituents: CH₃, OCH₃, NH₂, CHO, COCH₃ and NO₂. The obtained kinetic data were then correlated with the following theoretically estimated reactivity indices: Mulliken and NBO atomic charges, the Parr electrophilicity index (ω), and the electrostatic potential at the carbon and nitrogen atoms of the reaction center (V _C, V _N). Very good correlation between the logarithm of the rate constant, ln k, and the ω values was established. Excellent correlations between V _C and V _N and ln k were found. The data obtained show that the model-independent electrostatic potential at the nuclei provides a reliable quantitative approach for describing the reactivity of organic compounds.

Keywords:

• alkaline hydrolysis
• amides
• anilides
• kinetics
• reactivity indices

Acknowledgements

Professor Wesley D. Allen is thanked for comments on the manuscript. This research was supported by the National Science Fund of Bulgaria (grant VU X-04/05).