3,5-Diaminopyridine (DAP) and 3,5-dimethoxycarbonylaminopyridine (DMAP) were synthesized from 3,5-dimethylpyridine via a three-step reaction(oxidation,ammoniation and Hofmann degradation) with the yields of 70% (for DAP) and 72% (for DMAP). This procedure possesses advantages of mild conditions,easy operation,high yield and environmentally-friendly. A number of influencing factors for each step were investigated and discussed. The intermediates and target compounds structures were characterized by ¹H NMR,MS/MS,IR and elemental analysis.