Pyridine → 3-Bromo-6-methylquinoline

Temperature

80 °C

6-Methylquinoline (1.9906 g, 13.903 mmol) was dissolved in 20 mL of carbon tetrachloride. Bromine (0.72 mL, 14 mmol) was added dropwise to the reaction solution and the suspension was heated to reflux (80° C.). Pyridine (1.15 mL, 13.9 mmol) was added while reaction was heating to 80° C. and the reaction was allowed to stir at reflux for 1.5 hours. The reaction was cooled to room temperature and diluted with dichloromethane. The reaction was washed with water and the organic was dried over sodium sulfate, filtered and concentrated to give a thick brown oil that solidified upon standing. The crude solid was purified on an 80 g silica gel ISCO column eluting with a very slow gradient: 0% to 15% to 20% ethyl acetate in heptanes to give the desired 3-bromo-6-methylquinoline. 1H NMR (400 MHz, CDCl3) δ ppm 2.52 (s, 3 H) 7.47 (s, 1 H) 7.54 (dd, J=8.59, 1.95 Hz, 1 H) 7.95 (d, J=8.59 Hz, 1 H) 8.19 (d, J=2.15 Hz, 1 H) 8.81 (d, J=2.34 Hz, 1 H). GCMS=221 at 2.93 minutes.

1. temperaturethe suspension was heated
2. temperaturewas heating to 80° C.
3. temperatureat reflux for 1.5 hours
4. temperatureThe reaction was cooled to room temperature
5. washThe reaction was washed with water
6. dry with materialthe organic was dried over sodium sulfate
7. filtrationfiltered
8. concentrationconcentrated
9. customto give a thick brown oil that
10. customThe crude solid was purified on an 80 g silica gel ISCO column
11. washeluting with a very slow gradient

ORD record

ord-0e29751061a643dd970bed43c9332591

Source dataset

uspto-grants-2015_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09139538B2