[Cl:1][C:2]1[C:7]([C:8]([OH:10])=[O:9])=[C:6]([SH:11])[CH:5]=[CH:4][CH:3]=1.[H-].[Na+].[CH3:14][O:15][C:16]1[CH:21]=[C:20]([O:22][CH3:23])[N:19]=[C:18](S(C)(=O)=O)[N:17]=1.[Cl-].[Na+].Cl>CN(C)C=O.C(OCC)(=O)C.O>[Cl:1][C:2]1[C:7]([C:8]([OH:10])=[O:9])=[C:6]([S:11][C:18]2[N:19]=[C:20]([O:22][CH3:23])[CH:21]=[C:16]([O:15][CH3:14])[N:17]=2)[CH:5]=[CH:4][CH:3]=1
A solution of 1.4 grams (0.007 mole) of 6-chloro-2-mercaptobenzoic acid in 50 mL of dimethylformamide was stirred, and 0.6 gram (0.01 mole) of 60% sodium hydride in mineral oil was added in two portions during a 3 minute period. After this time the reaction mixture was stirred for 30 minutes, and 1.6 grams (0.007 mole) of 4,6-dimethoxy-2-methylsulfonylpyrimidine (prepared as in Example 1, Steps A-C) was added. Upon completion of addition, the reaction mixture was stirred for about 60 hours. After this time the reaction mixture was poured into 150 mL of an aqueous solution saturated with sodium chloride. Water, 50 mL, was added, and the mixture was extracted with three 70 mL portions of ethyl acetate. The combined extracts were evaporated under reduced pressure, leaving no residue. The aqueous layer was cooled and acidified to pH 2 with aqueous 3N hydrochloric acid. The mixture was reextracted with three 70 mL portions of ethyl acetate. The combined extracts were washed with four 50 mL portions of an aqueous solution saturated with sodium chloride. The organic layer was concentrated under reduced pressure to a residue. The residue was subjected to two purifications by column chromatography on silica gel. Elution for the first purification was accomplished using 10% methanol in methylene chloride, and with 33% acetone in methylene chloride for the second purification. The yield of 6-chloro-2-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid was 0.3 gram. The nmr spectrum was consistent with the proposed structure.
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