Acetic Acid → 2-(Bromomethyl)-4-fluoro-1-nitrobenzene

Participants

Reaction Steps

5-Fluoro-2-nitrotoluene (9.3 g, 60 mmol), 1,3-dibromo-5,5-dimethylhydantoin (20 g, 70 mmol), and 1,1′-azobis(cyclohexanecarbonitrile) (VAZO 88, 600 mg, 2.5 mmol) were combined in C6H5Cl (600 ml) and stirred. Acetic acid (300 ul, 5.24 mmol) was added to the solution and the solution was stirred at 40° C. for 96 h. The crude reaction mixture was washed three times with hot NaHCO3 solution (200 ml, 80° C.), dried over magnesium sulfate, filtered and the solvent removed. The resulting crude red-orange solid was filtered through silica to yield a mixture that was about 1:1 brominated product and unbrominated starting material. The material was carried onto the next step without further purification. Pure material could be obtained from flash chromatography on silica (6:1 hexanes/EtOAc) to give a brown oil (3.84 g, 27%).

Provenance & Evidence