GENERAL STEPS: Diethyl malonate (3.84 mL, 25.3 mmol) was slowly added dropwise to a suspension of sodium hydride (1.01 g, 60% oil suspension, 25.3 mmol) in DMF (15 mL) at 0 °C and stirred for 30 min until gas escape ceased. Subsequently, 3-bromo-4-chloro-5-nitropyridine (3.00 g, 12.6 mmol) was slowly added and the resulting dark reddish brown solution was stirred for 1 hour at room temperature. Upon completion of the reaction, it was carefully quenched with water and the pH was adjusted to 1 with 1 N HCl. The aqueous phase was extracted with EtOAc (2 x 150 mL), the organic phases were combined and washed with deionized water (100 mL) and saturated saline, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was dissolved in 4N HCl (50 mL) and refluxed for 16 hours. The reaction mixture was cooled in an ice bath and neutralized with 50% NaOH solution to pH 7. The aqueous phase was again extracted with EtOAc (3 x 100 mL), the organic phases were combined and washed with saturated saline, dried over MgSO4, filtered and concentrated under reduced pressure to afford the target product 3-bromo-4-methyl-5-nitropyridine (94a, 1.90 g, 70% yield) as a yellow solid. The product was characterized by 1H NMR (300 MHz, CDCl3): δ 8.94 (s, 1H), 8.97 (s, 1H), 2.65 (s, 3H).
