Bromine → 3-Bromo-4-fluorobenzaldehyde

Participants

Reaction Conditions

Reaction Steps

Powdered aluminium trichloride (226 g) was suspended in dry dichloromethane (250 cm3) and the suspension was cooled to 0° C. 4-Fluorobenzaldehyde (124 g) was added to the stirred suspension, the temperature of the mixture being maintained below 10° C. during the addition. Stirring of the dark reaction mixture was continued at 0° C. for 15 minutes and bromine (176g) was then added in a single addition. The mixture was then heated at the reflux temperature for a total of 14 hours, the mixture being stood overnight at the ambient temperature twice within this heating period. At this point, analysis by GLC suggested only 78% bromination. Further bromine (5 cm3) was added and heating at the reflux temperature continued for a further 2 hours, but little change was observed on GLC analysis. The mixture was cooled to the ambient temperature and poured into ice (1 kg). After the ice had melted, the aqueous layer was separated and extracted with dichloromethane. The combined organic layers were washed with sodium metabisulphite solution, to remove unreacted bromine, and brine and then dried over anhydrous magnesium sulphate. Evaporation of the solvent under reduced pressure gave a red oil which was purified by distillation using a 15 cm Vigreux column. The title compound (84 g) was collected as the major fraction, boiling at 144° C./28 mmHg.

Provenance & Evidence