Benzyl Alcohol → 5-Benzyloxy-4-chloro-2-nitro-phenylamine

Temperature

80 °C

Benzyl alcohol (12.5 mL, 0.121 mol), 4,5-dichloro-2-nitro-phenylamine (5.00 g, 24.2 mmol), cesium carbonate (15.7 g, 48.3 mmol), and DMA (110 mL) were combined in a sealable pressure vessel. The vessel was purged with dry nitrogen, sealed, and heated at 80° C. for 17 h. The reaction mixture was poured into brine (400 mL) and cooled to 0° C. The resulting precipitate was collected and dissolved in EtOAc (400 mL). The organic layer was washed with water (50 mL) and brine (50 mL). The organic layers were combined, dried, filtered, and concentrated under reduced pressure. The residue was purified (FCC) (1-50% EtOAc/hexanes, dryloaded) to yield the titled compound (2.47 g, 37% yield). MS (ESI/CI): mass calcd. for C13H11ClN2O3, 278.1; m/z found, 279.2 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.20 (s, 1H), 7.50-7.30 (m, 5H), 6.23 (s, 1H), 6.19 (br s, 2H), 5.16 (s, 2H).

1. customThe vessel was purged with dry nitrogen
2. customsealed
3. additionThe reaction mixture was poured into brine (400 mL)
4. temperaturecooled to 0° C
5. customThe resulting precipitate was collected
6. dissolutiondissolved in EtOAc (400 mL)
7. washThe organic layer was washed with water (50 mL) and brine (50 mL)
8. customdried
9. filtrationfiltered
10. concentrationconcentrated under reduced pressure
11. customThe residue was purified (FCC) (1-50% EtOAc/hexanes, dryloaded)

ORD record

ord-b82feda7324f424fa5e8532cf038f28b

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09073923B2