Hydrolysis of Mustard Derivatives. Failure of the Raber-Harris Probe in Predicting Nucleophilic Assistance

摘要

It is shown that a well known method for characterizing nucleophilic assistance fails for mustard derivatives. It is suggested that mustard derivatives are showing a different susceptibility to solvent electrophilicity than models on which the method is based. This work, having documented for the first time failure of currently acceptable methods of correlation of medium effects, requires the reevaluation of current theory of medium effects in displacement reactions. (Author)