Water → Methyl 3-amino-5-chloro-2-ethylbenzoate

Participants

Reaction Conditions

Reaction Steps

To a solution of methyl 5-chloro-2-ethyl-3-nitrobenzoate (6.18 g, 25.4 mmol) in methanol (250 ml) at room temperature was added ammonium chloride (13.3 g, 253 mmol) followed by deionized water (125 ml). The mixture was heated to 70° C. before the addition of iron (8.50 g, 152 mmol). The reaction turned to a dark color over the 2.5 hours it was stirred at 70° C. This mixture was allowed to cool to room temperature and was filtered through Kieselgel. The filter pad was washed with MeOH (250 ml) and the filtrate concentrated under reduced pressure. The residue was dissolved in saturated NaHCO3(aq) (50 ml) and EtOAc (150 ml). The phases were separated and the organic phase was washed with saturated NaHCO3(aq) (2×50 ml) before being dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by FCC (50 g silica, Isolute cartridge, gradient of eluents; 95:5 Heptane:EtOAc to 75:25 Heptane:EtOAc) to give 2.42 g of crude methyl 3-amino-5-chloro-2-ethylbenzoate as a yellow oil. The material was taken through the next step without further purification. LC-MS 31%, m/z=295.0, 1H NMR (500 MHz, Chloroform-d) δ ppm 7.17 (d, J=2.1 Hz, 1H), 6.79 (d, J=2.1 Hz, 1H), 3.87 (s, 3H), 3.86-3.81 (m, 2H), 2.74 (q, J=7.5 Hz, 2H), 1.20 (t, J=7.5 Hz, 3H).

Provenance & Evidence