The alkaline hydrolysis of a series of aryl phosphorodiamidates has been studied in aqueous ethanol and aqueous DMSO mixtures. Although the reactions do not show any saturation kinetics with respect to the hydroxide ion, the low solvent isotope effect, the highly negative Bronsted β value, the large Hammett ρ for the leaving aryloxy group and the decrease in rate with increase in the proportion of DMSO in the solvent mixtures indicate that the hydrolysis proceeds by an elimination-addition pathway. Comparison of rate data with other hydrolytic E1CB reactions show that the title reaction belongs to the (E1CB)R category.
Volume 134, 2022
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