Acetonitrile → 3-(6-Bromopyridin-2-yl)-3-oxopropanenitrile

To a suspension of sodium hydride (0.6 g, 60% in oil, 15.7 mmol) in anhydrous THF (70 mL) was added dropwise anhydrous acetonitrile (1.02 mL, 19.6 mmol). The mixture was stirred for about 30 min at rt and then ethyl 6-bromopyridine-2-carboxylate (3.00 g, 13.0 mmol, Apollo Scientific) was added. Subsequently, the resulting mixture was heated under reflux, for about 2 h. After cooling to rt, the volatiles were removed in vacuo and to the residue was added saturated aqueous ammonium chloride (150 mL) and ethyl acetate (600 mL). The resulting layers were separated, and the aqueous layer was extracted with ethyl acetate (2×125 mL). The combined organic layers were washed with water (2×100 mL), dried (MgSO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:3) to give crude 3-(6-bromo-2-pyridyl)-3-oxo-propanenitrile (1.71 g, 7.6 mmol, 58%), as a pale yellow solid: 1H-NMR (CDCl3, Bruker 400 MHz) δ 4.38 (2 H, s); 7.74-7.84 (2 H, m); 8.08 (1 H, dd, J=2 Hz, 6.5 Hz).