Hydrochloric Acid → (2-Amino-3-chlorophenyl)amine

To solution of 3-chloro-2-nitroaniline (10.00 g, 57.95 mmol), 3 N aq. HCl (96.58 mL, 289.7 mmol), and ethyl alcohol (148.6 mL, 57.95 mmol) was added Tin(II) chloride dihydrate (65.96 g, 289.7 mmol) and the mixture was heated under reflux with stirring. After 3 h, the mixture was cooled to room temperature and concentrated under reduced pressure to give a brown syrup. The mixture was cautiously treated with an excess of 10 M KOH (115.9 mL, 1159 mmol, 20 eqv.). The mixture was diluted with EtOAc (200 mL), filtered through Celite™ pad, and washed the pad well with EtOAc (100 mL×2). The filtrate was extracted with EtOAc (100 mL×2). The combined organic layers were washed with water (100 mL×1), dried over MgSO4, filtered, and concentrated under reduced pressure to give 3-chlorobenzene-1,2-diamine as a red oil: 1H NMR (400 MHz, DMSO-d6) δ ppm 6.43-6.53 (2H, m), 6.38 (1H, t, J=7.8 Hz), 4.80 (2H, s), 4.60 (2H, s); LC-MS (ESI) m/z 142.9 [M+H]+. The crude product was carried on crude without purification for the next step.

1. temperaturethe mixture was heated
2. temperatureunder reflux
3. concentrationconcentrated under reduced pressure
4. customto give a brown syrup
5. filtrationfiltered through Celite™ pad
6. washwashed the pad well with EtOAc (100 mL×2)
7. extractionThe filtrate was extracted with EtOAc (100 mL×2)
8. washThe combined organic layers were washed with water (100 mL×1)
9. dry with materialdried over MgSO4
10. filtrationfiltered
11. concentrationconcentrated under reduced pressure

ORDレコード

ord-f645749d9c844698aa11db37c6bfa133

出典データセット

uspto-grants-2012_06

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08193199B2