Methyl 2-[(3-chloropropyl)amino]-4-methoxy-3-nitrobenzoate → Methyl 3-amino-2-[(3-chloropropyl)amino]-4-methoxybenzoate

Temperature

80 °C

A mixture of methyl 2-[(3-chloropropyl)amino]-4-methoxy-3-nitrobenzoate (1.61 g, 5.23 mmol) and iron (1.46 g, 26.1 mmol) in acetic acid (32 mL) was stirred at 80° C. for 3 hr. Iron (0.58 g, 10.4 mmol) was added to the reaction mixture at room temperature and the mixture was stirred at 80° C. for 1 hr. To the reaction mixture was added iron (0.88 g, 15.8 mmol) at room temperature and the mixture was stirred at 80° C. for 1 hr. The solid was removed by filtration and the filter cake was washed with tetrahydrofuran. The filtrate was concentrated in vacuo. Water was added to the residue and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel eluting with a 10-50% ethyl acetate/n-hexane gradient mixture to give the title compound (967.5 mg, 3.55 mmol, 68%) as a yellow amorphous.

1. stirringthe mixture was stirred at 80° C. for 1 hr
2. stirringthe mixture was stirred at 80° C. for 1 hr
3. customThe solid was removed by filtration
4. washthe filter cake was washed with tetrahydrofuran
5. concentrationThe filtrate was concentrated in vacuo
6. additionWater was added to the residue
7. extractionthe mixture was extracted with ethyl acetate
8. washThe organic layer was washed with aqueous sodium hydrogen carbonate and brine
9. dry with materialdried over anhydrous magnesium sulfate
10. concentrationconcentrated in vacuo
11. customThe residue was purified by flash column chromatography on silica gel eluting with a 10-50% ethyl acetate/n-hexane gradient mixture

ORD record

ord-9978a0a5a90f46e7a572865cf6d81479

Source dataset

uspto-grants-2014_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08785460B2