2，6-Diamino-3，5-dinitropyridine (ANPy) and 2，6-diamino-3，5-dinitropyridine-1-oxide (ANPyO) was reacted with aqueous ammonia and KMnO₄ under different conditions. Substitutions in the 4 position to the nitro group were obtained with high yields: 2，4，6-triamino-3，5-dinitropyridine (81.5%) and 2，4，6-triamino-3，5-dinitropyridine-1-oxide (85.4%). The effects of solvent type，concentration of the aqueous ammonia on the yields of target compounds were studied. The different results between 2，6-diamino-3，5-dinitropyridine (and 2，6-diamino-3，5-dinitropyridine-1-oxide) and 3-nitropyridien were analyzed. Structures of 2，4，6-triamino-3，5-dinitropyridine and 2，4，6-triamino-3，5-dinitropyridine-1-oxide were characterized by 1H NMR，IR and MS.