[OH:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].P(S)(OCC)(OCC)=[S:11].C([O-])(O)=O.[Na+].C(=O)=O.[Na+].[Cl-]>C(Cl)Cl.CCOCC.O>[OH:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4](=[S:11])[NH2:5]A stirred solution of 2-hydroxybenzonitrile (23.8 g, 200 mmol), (EtO)2P(S)SH (33.6 mL, 200 mmol) and water (40 mL) was heated at 80° C. for 12 hr under nitrogen. The mixture was cooled down to 0°-10° C., diluted with CH2Cl2 (200 mL)/Et2O (400 mL), then cautiously treated with saturated aq. NaHCO3 (60 mL), and followed by adding solid NaHCO3 in small portions until CO2 evolution ceased. Half-saturated aq. NaCl (40 mL) was added to the mixture. The organic layer was separated, washed with brine (100 mL), dried over MgSO4, and filtered. After concentration in vacuo, the residue was chromatographed on silica gel (gradient EtOAc/CH2Cl2 :0-5%) to give 3a (16.7 g, 55%) as a pinkish solid, which had the same 1HNMR data as reported in the literature (Yousif, N. M. Tetrahedron 1989, 45, 4599).
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