Methylamine → HCID 118092892, compound

To a flask with 2-fluoro-5-nitrobenzaldehyde (2 g, 11.83 mmol) in MeOH (60 mL) was added methylamine (33% in EtOH, 2.94 mL, 23.65 mmol). The reaction mixture was stirred at rt for 2 h, cooled to 0° C. Sodium borohydride (0.895 g, 23.65 mmol) was added and the mixture was stirred at rt for 1 h. Solvent was removed and the residue was suspended in THF (60.0 mL) and water (30.0 mL). The mixture was treated with sodium bicarbonate (2.98 g, 35.5 mmol), cooled to 0° C., and then CBZ-Cl (2.195 mL, 15.37 mmol) was added dropwise. The mixture was stirred rt overnight. The solvent was removed and the residue was dissolved in EtOAc. The organic layer was washed with water, brine, dried over sodium sulfate and concentrated in vacuo. The crude product was purified by flash chromatography to give 13A (3.6 g, 11.31 mmol, 96% yield) as a yellow oil. MS (ESI) (m/z): 341 (M+Na)+. 1H NMR (400 MHz, chloroform-d) δ ppm 8.04-8.28 (m, 2H) 7.28-7.50 (m, 5H) 7.21 (t, J=8.34 Hz, 1H) 5.19 (d, J=8.84 Hz, 2H) 4.51-4.68 (m, 2H) 3.01 (br. s., 3H).

1. temperaturecooled to 0° C
2. stirringthe mixture was stirred at rt for 1 h
3. customSolvent was removed
4. temperaturecooled to 0° C.
5. stirringThe mixture was stirred rt overnight
6. customThe solvent was removed
7. dissolutionthe residue was dissolved in EtOAc
8. washThe organic layer was washed with water, brine
9. dry with materialdried over sodium sulfate
10. concentrationconcentrated in vacuo
11. customThe crude product was purified by flash chromatography

ORD record

ord-da3cc21510b243c48b7d7052576f2262

Source dataset

uspto-grants-2015_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09174974B2