2-Chloro-4-aminopyridine (0.642 g, 5 mmol), zinc cyanide (0.323 g, 2.75 mmol) and tetrakis(triphenylphosphine)palladium (0.288 g, 0.025 mmol) were mixed in 5 mL N,N-dimethylformamide (DMF). The reaction mixture was heated at 145°C for 20 hours. After completion of the reaction, it was cooled to room temperature and subsequently partitioned between ethyl acetate and water. The aqueous layer was extracted with additional ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by fast column chromatography on silica gel, using 9:1 hexane/ethyl acetate as eluent to give 0.29 g (20% yield) of 4-aminopyridine-2-carbonitrile. Mass spectrum (DCI) m/e 120 (M + H)+; 1H NMR (300 MHz, DMSO-D6) δ 8.08 (d, J = 5.76 Hz, 1H), 6.94 (d, J = 2.34 Hz, 1H), 6.68 (dd, J = 5.76,2.37 Hz, 1H), 6.59 (s, 2H).
