Carbonyl Hydration of the Diethyl and Dimethyl Phosphate Derivatives of Acetone: Equilibrium Constants, Polar Substituent Constants of the -CH2OP(O)(OR)2 Groups, and Use of the Marcus Equation to Clarify the Mechanism of Alkaline Hydrolysis

Abstract

This study provides an examination of the equilibrium constants and thermodynamic quantities for hydration of the diethyl and dimethyl phosphate derivatives of acetone in D2O. Notably, our results offer direct evidence for the hydration of the carbonyl group in the ketol phosphate utilizing Marcus theory to gain insight into microscopic rate constants associated with hydrolysis. Additionally, hydration constants are employed with linear free-energy relationships to obtain polar substituent constants for the (RO)2P(O)OCH2 - groups and equilibrium constants for hydroxide addition to the ketol phosphates. By elucidating the thermodynamic, kinetic, and microscopic rate constants, a deeper understanding of the alkaline ketol hydrolysis has been studied.