Br[C:2]1[CH:6]=[CH:5][S:4][C:3]=1[CH2:7][C:8]#[N:9].[CH:10](OCC)=O.[O-]CC.[Na+].C(O)C.Cl.[NH2:23][C:24]1[CH:32]=[CH:31][C:27]([C:28]([OH:30])=[O:29])=[C:26]([OH:33])[CH:25]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].Cl>CS(C)=O.[Cu]I.C(O)CO.O>[C:8]([C:7]1[C:3]2[S:4][CH:5]=[CH:6][C:2]=2[N:23]([C:24]2[CH:32]=[CH:31][C:27]([C:28]([OH:30])=[O:29])=[C:26]([OH:33])[CH:25]=2)[CH:10]=1)#[N:9]To a solution of 2-(3-bromothiophen-2-yl)acetonitrile (1.0 g) and ethyl formate (3.7 g) in dimethyl sulfoxide (5.0 mL) was added sodium ethoxide (20% solution in ethanol, 3.1 mL), and the mixture was stirred at room temperature for 3 hours. 2.5 mol/L hydrochloric acid ethanol solution (3.6 mL) and 4-amino-2-hydroxybenzoic acid (0.9 g) were added to reaction solution. The mixture was stirred at 50° C. for 5 hours. To the reaction solution was added water. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 50° C. for 3 hours. The obtained residue was purified by column chromatography on silica gel (eluent: dichloromethane/methanol=87/13−78/22) to give the condensate (0.91 g). To a solution of this condensate (0.91 g) in dimethyl sulfoxide (4.5 mL) were added copper(I) iodide (47 mg), ethylene glycol (0.3 g) and tripotassium phosphate (1.1 g), and the mixture was stirred at 80° C. for 5 hours. After cooling to 50° C., to the mixture was added 2 mol/L hydrochloric acid (8.7 mL) and the mixture was stirred at room temperature for 1 hour. The precipitated solid was collected by filtration, washed with mixed solution of water and dimethyl sulfoxide, 1 mol/L hydrochloric acid and water, and dried under reduced pressure at 50° C. to give the title compound (0.45 g).
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