Nucleophilic addition of hydroxylamine, methoxylamine, and hydrazine to malononitrileoxime

The chemistry of malononitrileoxime, HONC(CN)(2), with respect to nucleophi lic addition to ammonia, methylamine, hydroxylamine, methoxylamine, and hyd razine is reported. Whereas the poorly nucleophilic ammonia and methylamine do not react, hydroxylamine, methoxylamine, and hydrazine add to the nitri le groups of the oxime, yielding the corresponding amidoximes and amidrazon es. Depending on the stoichiometry of the reactions, hydroxylamine and hydr azine add to one or both of the nitrile groups; methoxylamine adds to only one of the nitrile groups. Three of the products, namely, cyanoacetamidoxim e (1), 3-amino-2,3-hydroxyiminopropionitrile monohydrate (2 . H2O), and 3,5 -diaminopyrazolone-4-oxime.monohydrochloride monohydrate (6 . HCl . H2O), a re characterized by single-crystal X-ray diffraction data. All of the produ cts exhibit exothermic decomposition properties with heats of decomposition in the range of 500-1500 kJ mol(-1).