Nucleophilic Addition of Hydroxylamine, Methoxylamine, and Hydrazine to Malononitrileoxime

The chemistry of malononitrileoxime, HONC(CN)2, with respect to nucleophilic addition to ammonia, methylamine, hydroxylamine, methoxylamine, and hydrazine is reported. Whereas the poorly nucleophilic ammonia and methylamine do not react, hydroxylamine, methoxylamine, and hydrazine add to the nitrile groups of the oxime, yielding the corresponding amidoximes and amidrazones. Depending on the stoichiometry of the reactions, hydroxylamine and hydrazine add to one or both of the nitrile groups; methoxylamine adds to only one of the nitrile groups. Three of the products, namely, cyanoacetamidoxime (1), 3-amino-2,3-hydroxyiminopropionitrile monohydrate (2·H2O), and 3,5-diaminopyrazolone-4-oxime monohydrochloride monohydrate (6·HCl·H2O), are characterized by single-crystal X-ray diffraction data. All of the products exhibit exothermic decomposition properties with heats of decomposition in the range of 500−1500 kJ mol-1.