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 H2O, 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
2. customthe resultant reaction mixture
3. temperaturewas heated
4. temperatureat reflux for 4 h
5. washwashed with H2O
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-3ec4cac749d74401b144c320eba33575

Source dataset

uspto-grants-2015_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09212163B2