Résumé
alpha-Aminonitriles are hydrated into alpha-aminoamides in the presence of hydrogen peroxide in sodic or ammoniacal basic medium. While the hydration mechanism is close to the mechanism described previously in the case of aromatic nitriles, we showed that, in weakly basic conditions, the amine function of alpha-aminonitrile is competitively oxidized via a peroxyimidic acid by an intramolecular process. In the case of 2-aminopropanenitrile, this reaction leads to pyruvamide oxime. Furthermore, the study of structure-reactivity relationships in the hydration of aliphatic and aromatic monofunctional nitriles and alpha-aminonitriles showed that the reactivity of the substrates towards hydroperozide anion, which mostly depends on inductive effects of the substituents, is sufficiently enhanced to allow hydration of tertiary alpha-aminonitriles with low steric hindrance and regioselective hydration of dissymmetric alpha-aminodinitriles.