Diethyl Malonate → Diethyl 2-[(4-nitrophenyl)methyl]propanedioate

Participants

Reaction Steps

Diethyl malonate (7.41 g, 46.3 mmol) was added to a slurry of NaH (60% oil dispersion, 2.04 g, 50.9 mmol) in THF (200 ml) and stirred for 15 min, before adding a solution of 4-nitrobenzyl bromide (10.0 g, 46.3 mmol) in THF (100 ml) by cannula. The reaction was stirred for 3 h at room temperature then quenched by the addition of water (100 ml). The aqueous layer was separated and extracted with Et2O (200 ml). The combined organic layers were washed with brine (200 ml), dried (MgSO4) and the solvent evaporated in vacuo to give an off-white solid. Trituration with Et2O/hexane (1:5, 100 ml), removal of the solid by filtration and concentration of the filtrate in vacuo gave an oil which was purified by chromatography (SiO2;EtOAc/hexane 1:3) to give the title compound as an oil (9.4 g), containing about 20% diethyl malonate. δH (CDCl3) 8.15 (2H, d, J 8.8 Hz, Ar—H), 7.39 (2H, d, J 8.7 Hz, Ar—H), 4.25-4.11 (4H, m, CH2CH3), 3.67 (1H, t, J 7.8 Hz, CHCH2Ar), 3.32 (2H, d, J 7.8 Hz, CHCH2Ar) and 1.23 (6H, t, J 7.2 Hz, CH2CH3).

Provenance & Evidence