Methyl 4-cyano-2-methyl-5-nitrobenzoate → Methyl 5-amino-4-cyano-2-methylbenzoate

Participants

Reaction Conditions

Reaction Steps

To a solution of methyl 4-cyano-2-methyl-5-nitrobenzoate (14.8 g, 0.0672 mol) in acetic acid (250 mL) was added iron powder (22.5 g, 0.40 mol). The reaction mixture was heated to 45° C. and stirred for 1 h, at which time it was cooled to room temperature. The reaction mixture was filtered through a bed of celite, and the filter cake rinsed with ethyl acetate. The volume of the filtrate was reduced by half and then partitioned between water and ethyl acetate. The organic layer was washed with 10% lithium chloride followed by saturated aqueous sodium bicarbonate. The organic layer was further washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was triturated with hexanes to afford methyl 5-amino-4-cyano-2-methylbenzoate (11.7 g, 91%) as a bright yellow powder. 1H NMR (400 MHz, CDCl3): 7.28 (s, 1H), 7.26 (s, 1H), 4.35 (br s, 2H), 3.89 (s, 3H), 2.43 (s, 3H). MS (EI) for C10H10N2O2: 191 (MH+).

Provenance & Evidence