N-bromobutanimide → 4-(Bromomethyl)-3-chlorobenzonitrile

To a stirred solution of 3-chloro-4-methylbenzonitrile (5 g, 25.4 mmol) in carbon tetrachloride (CCl4; 50 mL) under an argon atmosphere was added NBS (5.16 g, 29 mmol), and the mixture was degassed for 30 min To this was added azobisisobutyronitrile (AIBN; 0.3 g, 1.8 mmol), and the resultant reaction mixture was heated at reflux for 4 h. The reaction mixture was cooled to ambient temperature, washed with water, and extracted with CH2Cl2. The combined CH2Cl2 layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane) to afford the title compound as a white solid (4.8 g, 68%): mp 87-88° C.; 1H NMR (400 MHz, CDCl3) δ 7.71 (s, 1H), 7.59 (s, 2H), 4.60 (s, 2H); ESIMS m/z 229.77 ([M+H]+); IR (thin film) 2235, 752, 621 cm−1.

1. customthe mixture was degassed for 30 min To
2. customthe resultant reaction mixture
3. temperaturewas heated
4. temperatureat reflux for 4 h
5. washwashed with water
6. extractionextracted with CH2Cl2
7. washThe combined CH2Cl2 layer was washed with brine
8. dry with materialdried over Na2SO4
9. concentrationconcentrated under reduced pressure
10. customThe crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane)

ORD record

ord-495608a6803541a98bcf7277fb8be5d5

Source dataset

uspto-grants-2015_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09211281B2