Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[OH:12].C(=O)([O-])[O-].[Na+].[Na+].[CH3:19][NH:20]C>C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].[Fe-3](C#N)(C#N)(C#N)(C#N)(C#N)C#N.[K+].[K+].[K+]>[C:19]([C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[OH:12])#[N:20]To a solution of methyl 4-bromo-3-hydroxybenzoate (1.01 g, 4.4 mmol) in 7 ml of dimethylamine was added Pd(OAc)2 (15 mg, 0.5 mol %), sodium carbonate (0.47 g, 4.4 mmol) and potassium ferricyanide (0.41 g, 0.97 mmol). The mixture was heated to 120° C. and stirred at this temperature for 4 hours and at RT for 18 hours. The reaction mixture was diluted with 30 ml of ethyl acetate and the resulting slurry was filtered through Celite. The filtrate was washed with water (2×15 ml) and 5% aqueous ammonium hydroxide (1×15 ml). The organic layer was dried over sodium sulfate, filtered and concentrated to provide methyl 4-cyano-3-hydroxybenzoate (0.26 g, 33.5% yield) (S. Weissman, D. Zewge, C. Chen; J. Org. Chem. 2005, 70, 1508-1510). 1H NMR (400 MHz, CD3OD): 7.65 (d, 1H), 7.56-7.54 (m, 2H), 3.91 (s, 3H). MS (EI) for C9H7NO3: 178 (MH+).
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