An ether solution of methyl lithium (109 mmol, 1.09 M, 100 mL) was added dropwise to an ether (100 mL) solution of 5-bromopyrimidine (17.3 g, 109 mmol) at room temperature. The resulting reaction mixture was stirred at room temperature for 1 hour. Upon completion of the reaction, water (1.96 mL, 109 mmol) and a solution of tetrahydrofuran (150 mL) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (24.7 g, 109 mmol) were added to the reaction mixture, and stirring was continued for 16 hours at room temperature. Upon completion of the reaction, water and ethyl acetate were added for extraction and the organic layer was separated. The organic layer was washed with 1 M aqueous sodium hydroxide, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate=1/1) to afford the target product 5-bromo-4-methylpyrimidine (2.9 g, 15% yield). Product properties: yellow oil. 1H-NMR (CDCl3) δ: 2.65 (s, 3H), 8.72 (s, 1H), 8.98 (s, 1H).
