General procedure for the synthesis of 2-methoxy-6-(methylamino)pyridine from 2-chloro-6-methoxypyridine and monomethylamine: 2-chloro-6-methoxypyridine (12.0 g, 85.6 mmol) was mixed with 40% aqueous methanamine (24 mL) in a sealed tube and reacted for 7 hr at 170 °C. After completion of the reaction, it was cooled to room temperature and the reaction mixture was diluted with 50 mL of water and subsequently extracted with dichloromethane (3 x 50 mL). The organic layers were combined, washed sequentially with 100 mL of water and 100 mL of brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (100-200 mesh, eluent 0 to 5% dichloromethane solution in methanol) to afford 6-methoxy-N-methylpyridin-2-amine (2.7 g, 31% yield) as a light yellow oil.1H NMR (400 MHz, CDCl3) δ 7.37 (t, J = 8.0 Hz, 1H), 6.04 (d, J = 8.0 Hz, 1H), 5.94 (d, J = 7.8 Hz, 1H), 4.39 (br. s, 1H), 3.86 (s, 3H), 2.90 (s, 3H).
