[S:1]1[CH:5]=[CH:4][C:3]2[CH:6]([NH:10][C:11](=[O:13])[CH3:12])[CH2:7][CH2:8][CH2:9][C:2]1=2.C(O)(=[O:16])C.C(C(C)=O)C(C)C>O.[Cl-].[Na+]>[O:16]=[C:9]1[C:2]2[S:1][CH:5]=[CH:4][C:3]=2[CH:6]([NH:10][C:11](=[O:13])[CH3:12])[CH2:7][CH2:8]1A mixture of N-(4,5,6,7-tetrahydrobenzo[b]thien-4-yl)-acetamide (2.0 g; 10.25 m mole), cobaltous acetate (0.49 g; 2.77 m mole), cobaltous bromide tetrahydrate (0.635 g; 2.18 m mole), water (0.4 ml), acetic acid (5.0 ml) and methyl isobutyl ketone (35.0 ml) in suitable flask fitted with a reflux condenser, a gas dispersion tube and a thermometer is stirred vigorously. Air is introduced through the dispersion tube into the turbid blue solution at room temperature for 45 minutes, and then the mixture is heated. After 25 minutes, the solution turns greenish blue (temperature: 45° C.) and in 15 minutes green (temperature: 55° C.). The reaction is run overnight with periodic additions of methyl isobutyl ketone. The greyish green reaction mixture containing some suspended dark gray solid is then diluted with water (40.0 ml) and saturated with sodium chloride. The upper organic phase is separated and the aqueous phase extracted with chloroform (2×100 ml). The organic phase and the chloroform extracts are combined, washed with brine (50 ml) and water (25 ml), respectively. The water wash is counter-extracted with chloroform (50 ml) and the chloroform extract added to the above organic phase. The combined organic phase is evaporated in vacuo to afford a gum, which contains the desired compound. The latter is hydrolyzed without further purification and the resultant amine hydrochloride is converted to 4,5,6,7-tetrahydro-7-oxobenzo[b]thien-4-ylurea.
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