Phosphoric Amides. 5. Acid-Catalyzed Hydrolysis of Dimethyl N-(Alkylphenyl)phosphoramidates

Article abstract of DOI:10.1021/jo00138a002

Studies of the acid-catalyzed hydrolysis of dimethyl N-(alkylphenyl)phosphoramidates demonstrate that the LFER between observed rates and basicities of the leaving amines is different for meta/para- and for ortho- substituted derivatives (slopes of log_obsd vs. pK_a are 0.4 and 0.9, respectively).Since the ΔS(excit) values and KSIE determined are approximately constant irrespective of the position of an alkyl group, the observed change in the slope of the rate/basicity plot is discussed in terms of the steric effects on solvation rather than as an indication of the change in reaction mechanism.