Diethyl Malonate → Diethyl 2-(5-bromo-3-nitropyridin-2-yl)malonate

Participants

Reaction Steps

Sodium hydride (60% in mineral oil, 1.28 g, 0.032 mol) was suspended in DMF (25 ml) and diethyl malonate (4.0 ml, 26 mmol) was added via syringe slowly over 20 minutes, and more DMF (5 ml) was added as a rinse. The reaction stirred at room temperature for 20 minutes, and then 5-bromo-2-chloro-3-nitropyridine (3.2 g, 14 mmol) was added as a solution in DMF. The reaction was placed in a preheated oil bath (40° C.) and stirred under nitrogen for 1 hour. The reaction was cooled to room temperature, quenched with water (50 ml) and allowed to stand at room temperature overnight. The aqueous phase was extracted with Et2O (3×100 ml, 50 ml), then EtOAC (100 ml) and Et2O (50 ml, 2×100 ml). The organic extracts were combined, dried over magnesium sulfate, filtered, and concentrated, and taken to the next step. MS (ESI pos. ion) m/z: 361 (MH+, 79Br), 363 (MH+, 81Br). Calculated exact mass for C12H13BrN2O6: 360 (79Br), 362 (81Br).

Provenance & Evidence