Sodium Carbonate → Methyl 3-cyano-4-hydroxybenzoate

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Reaction Steps

A mixture of methyl 3-bromo-4-hydroxybenzoate (Journal of Organic Chemistry (1997), 62(13), 4504-4506; 3.47 g, 15.0 mmol), potassium ferrocyanide trihydrate (1.394 g, 3.30 mmol), palladium acetate (0.034 g, 0.150 mmol), 1,1-bis(diphenylphosphino)ferrocene (0.166 g, 0.300 mmol), and sodium carbonate (1.590 g, 15.00 mmol) in dry N,N-dimethylacetamide (DMA) (30 ml) was degassed by evacuation and refilling with nitrogen, and the mixture was heated under nitrogen at 125° for 18 h. More potassium ferrocyanide trihydrate (700 mg), palladium acetate (34 mg) and 1,1′-bis(diphenylphosphino)ferrocene (166 mg) were added, and stirring was continued under nitrogen at 130° for 21.5 h. More sodium carbonate (1.59 g), palladium acetate (0.034 g, 0.150 mmol) and 1,1′-bis(diphenylphosphino)ferrocene (0.166 g, 0.300 mmol) was added, and heating was continued at 130° with stirring under nitrogen for 4 h. The solvent was evaporated in vacuo and the residue treated with glacial acetic acid (3 ml) and partitioned between water (100 ml) and ethyl acetate (100 ml). The layers separated poorly, hence the mixture was filtered through Celite filter aid, and the aqueous layer was further extracted with ethyl acetate (70 ml). The combined organic layers were washed with saturated aqueous sodium chloride, dried (MgSO4) and evaporated in vacuo to give a black solid which was purified by flash chromatography on silica, eluting with 0-50% ethyl acetate-cyclohexane. The appropriate fractions were combined and evaporated in vacuo to give the title compound as a yellow solid (1.01 g)

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