Dimethyl Sulfide → 4-Hydroxy-3-methylbenzonitrile

To a solution of 4-bromo-3-methylbenzonitrile (7.07 g, 36.1 mmol) in 225 mL of THF at -78° C. is added a 1.7 M solution of tert-butyl lithium (45.6 mL, 77.6 mmol) in pentane. After 5 minutes, CuBr.SMe2 (15.9 g, 77.6 mmol) is added. The resulting solution is stirred for 10 minutes, then O2 is slowly bubbled through the reaction mixture for 30 minutes. After this time, the solution is allowed to warm to ambient temperatures. The solution is stirred for 16 hours. The solution is then poured into 100 mL of H2O. The solution is diluted with EtOAc. The layers are separated. The organic layer is washed with saturated (NH4)2SO4 solution. The organic layer is then extracted with 10 N NaOH. The collected aqueous basic layers are acidified to pH=6 with 6N HCl. The solution is then extracted with EtOAc. The combined organic layers are dried over MgSO4, filtered and concentrated. The title compound is obtained as a solid.

1. customO2 is slowly bubbled through the reaction mixture for 30 minutes
2. temperatureto warm to ambient temperatures
3. stirringThe solution is stirred for 16 hours
4. additionThe solution is then poured into 100 mL of H2O
5. additionThe solution is diluted with EtOAc
6. customThe layers are separated
7. washThe organic layer is washed with saturated (NH4)2SO4 solution
8. extractionThe organic layer is then extracted with 10 N NaOH
9. extractionThe solution is then extracted with EtOAc
10. dry with materialThe combined organic layers are dried over MgSO4
11. filtrationfiltered
12. concentrationconcentrated

ORD record

ord-7442773e2bb9450ba42edecb02221994

Source dataset

uspto-grants-1999_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05958918