C(=O)([O-])[O-].[Na+].[Na+].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([CH:14]([C:22]#[N:23])[C:15](=[O:21])C(OCC)=O)=[CH:10][CH:9]=1.C=O>O.C(Cl)Cl>[OH:21][CH2:15][CH:14]([C:11]1[CH:10]=[CH:9][C:8]([Cl:7])=[CH:13][CH:12]=1)[C:22]#[N:23]Sodium carbonate (204 mg, 1.9 mmol) dissolved in water (1.2 mL) was added dropwise over 10 min to a vigorously stirred mixture of the above ethyl 3-(4-chlorophenyl)-3-cyano-2-oxopropanoate (400 mg 1.59 mmol), 37% HCHO (131 μL 1.75 mmol) and methylene chloride (2 mL). After an additional 2 min, the mixture was diluted with ˜one mL each of water and methylene chloride and phase separated. Acidification of the aqueous phase and filtration of the precipitated solid recovered 68 mg (17%) of the starting material. The organic phase was washed twice with water, dried and stripped to give a colorless oil. Flash chromatography on 10 g of silica gel eluting with 5-50% ethyl acetate in hexane recovered 43 mg of a higher Rf product assumed to be 4-chloroatroponitrile, and 210 mg (75%) of the desired alcohol, Rf 0.09 (silica gel, ethyl acetate:hexane=1:4).
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