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

温度

70 °C

To a solution of methyl 5-chloro-2-methoxy-3-nitrobenzoate (1.21 g, 4.93 mmol) in methanol (50 ml) at room temperature was added ammonium chloride (2.59 g, 49.2 mmol) followed by deionized water (25 ml). The mixture was heated to 70° C. before the addition of iron (1.65 g, 29.6 mmol). The reaction turned to a dark color over the 2 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 (50 ml) and the filtrate concentrated under reduced pressure. The residue was dissolved in deionized water (25 ml) and EtOAc (25 ml). The phases were separated and the aqueous phase was extracted with EtOAc (2×25 ml). The combined organic extracts were washed with brine (25 ml), dried over MgSO4, filtered and concentrated under reduced pressure to give 892 mg (67%) of the title compound as a viscous brown oil. This material was used without further purification. LC-MS 89%, 1.75 min (3 minute LC-MS method), m/z=216.3/218.0, 1H NMR (500 MHz, Chloroform-d) δ ppm 7.16 (1H, d, J=2.52 Hz), 6.87 (1H, d, J=2.52 Hz), 4.03 (2H, br. s.), 3.89-3.94 (3H, m), 3.84 (3H, s).

1. customturned to a dark color over the 2 hours it
2. temperatureto cool to room temperature
3. filtrationwas filtered through Kieselgel
4. washThe filter pad was washed with MeOH (50 ml)
5. concentrationthe filtrate concentrated under reduced pressure
6. dissolutionThe residue was dissolved in deionized water (25 ml)
7. customThe phases were separated
8. extractionthe aqueous phase was extracted with EtOAc (2×25 ml)
9. washThe combined organic extracts were washed with brine (25 ml)
10. dry with materialdried over MgSO4
11. filtrationfiltered
12. concentrationconcentrated under reduced pressure

ORDレコード

ord-1767b6c35d58410c9379f78f70656ab6

出典データセット

uspto-grants-2016_06

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US09376422B2