Hydrogen Peroxide → Methyl 4-bromopicolinate

Participants

Reaction Steps

A solution of 4-bromopyridine hydrochloride (595 mg, 3.06 mmol) in DCM (20 mL) is washed with aqueous NaHCO3 (2×20 mL), dried (MgSO4) and filtered. The filtrate is made up to 45 mL by the addition of more DCM, then water (3 mL) is added, followed by iron(II) sulphate heptahydrate (8.51 g, 30.6 mmol) and conc. H2SO4 (0.95 mL, 9.18 mmol). In a separate flask, methyl pyruvate (4.15 mL, 46 mmol) is treated with hydrogen peroxide (3.5 mL, 30.6 mmol, 30% solution in water) at −10° C., then this solution is added to the DCM/water mixture at −10° C. with vigorous stirring. After 15 minutes, the reaction is diluted with iced water (100 mL) and extracted into DCM (4×20 mL). The combined DCM phases are dried (MgSO4) and removed in vacuo. The title compound is obtained after sequential column chromatography (gradient elution—10-40% EtOAc in heptane with 0.5% triethylamine, then repeating with 0-20% EtOAc in heptane with 0.5% triethylamine).

Provenance & Evidence