Methyl 2-(4-bromo-2-nitrophenyl)acetate

Synthesis

GENERAL STEPS: To a stirred solution of 1,3-dimethyl 2-(4-bromo-2-nitrophenyl) malonate (20 g, 60.2 mmol) in dimethyl sulfoxide (DMSO, 200 mL) was added lithium chloride (5.11 g, 2 eq.) followed by water (1.1 mL, 1 eq.). The reaction mixture was stirred at 100°C for 2 days and then continued at room temperature for 4 days. Upon completion of the reaction, the mixture was poured into water and extracted with ethyl acetate (2 x 200 mL). The organic phases were combined, washed with saturated brine (2 x 200 mL) and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by Combi-Flash column chromatography (eluent: ethyl acetate/hexane) to afford methyl 2-(4-bromo-2-nitrophenyl)acetate (12 g, 73% yield) as a light yellow solid.1H NMR (400 MHz, DMSO-d6) δ 8.30 (d, J = 2.1 Hz, 1H), 7.98 (dd, J = 8.2, 2.1 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 4.08 (s, 2H), 3.63 (s, 3H).LCMS-ESI (POS), m/z, [M + H]+: measured values 274.0 and 276.0.

References

[1] Synthesis, 1993, # 1, p. 51 - 53
[2] Journal of the American Chemical Society, 2013, vol. 135, # 2, p. 620 - 623
[3] Patent: WO2009/158011, 2009, A1. Location in patent: Page/Page column 59-60
[4] Patent: WO2009/85040, 2009, A1. Location in patent: Page/Page column 25-26
[5] Patent: US6350747, 2002, B1. Location in patent: Page column 48