ALPHA-AMINONITRILE HYDRATION IN THE PRESE NCE OF HYDROGEN-PEROXIDE INAQUEOUS BASIC-MEDIUM

alpha-Aminonitriles are hydrated into alpha-aminoamides in the presenc e 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 conditi ons, the amine function of alpha-aminonitrile is competitively oxidize d via a peroxyimidic acid by an intramolecular process. In the case of 2-aminopropanenitrile, this reaction leads to pyruvamide oxime. Furth ermore, the study of structure-reactivity relationships in the hydrati on of aliphatic and aromatic monofunctional nitriles and alpha-aminoni triles showed that the reactivity of the substrates towards hydroperoz ide anion, which mostly depends on inductive effects of the substituen ts, is sufficiently enhanced to allow hydration of tertiary alpha-amin onitriles with low steric hindrance and regioselective hydration of di ssymmetric alpha-aminodinitriles.