Water → HCID 86719566, compound

Temperature

70 °C

To a solution of methyl 2-bromo-5-chloro-3-nitrobenzoate (4.0 g, 14 mmol) in methanol (130 ml) at room temperature was added ammonium chloride (7.13 g, 136 mmol) followed by deionized water (65 ml). The mixture was heated to 70° C. in air before the addition of iron (4.55 g, 81.5 mmol). The reaction was stirred at 70° C. for 3 hours, allowed to cool to room temperature and filtered through Kieselgel. The filter pad was washed with MeOH (65 ml) and the filtrate concentrated under reduced pressure. The residue was dissolved in saturated NaHCO3 (50 ml) and EtOAc (100 ml). The phases were separated and the organic phase was washed with saturated NaHCO3(aq) (3×50 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 7:3 Heptane:EtOAc) to give 1.92 g (48%) of the title compound as a colourless oil. LC-MS 92%, m/z=268.8/265.8/267.6, 1H NMR (500 MHz, Chloroform-d) δ 7.08 (1H, d, J=2.36 Hz), 6.86 (1H, d, J=2.36 Hz), 4.34-4.49 (2H, m), 3.93 (3H, s).

1. temperatureto cool to room temperature
2. filtrationfiltered through Kieselgel
3. washThe filter pad was washed with MeOH (65 ml)
4. concentrationthe filtrate concentrated under reduced pressure
5. dissolutionThe residue was dissolved in saturated NaHCO3 (50 ml)
6. customThe phases were separated
7. washthe organic phase was washed with saturated NaHCO3(aq) (3×50 ml)
8. dry with materialbefore being dried over MgSO4
9. filtrationfiltered
10. concentrationconcentrated under reduced pressure
11. customThe residue was purified by FCC (50 g silica, Isolute cartridge, gradient of eluents; 95:5 Heptane:EtOAc to 7:3 Heptane:EtOAc)

ORD record

ord-89b36552108f409bb5093fc542fd773f

Source dataset

uspto-grants-2016_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09376422B2