methyl 4-sulfanylbutanoate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under an argon atmosphere, 2-fluorobenzaldehyde (3 g) was dissolved in 9 ml of dimethylformamide and potassium carbonate (5.01 g) was added. Methyl 4-mercaptobutyrate (4.5 ml) was added at room temperature and-was stirred at room temperature for 14 hours. After the addition of 50 ml of ethyl acetate, the mixture was washed with 30 ml of water twice, 3 ml of a 1N hydrochloric acid, and 30 ml of water three times. After drying with anhydrous sodium sulfate, the mixture was concentrated. The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification. The resulting effective fractions were concentrated to yield methyl 4-(2-formylphenylthio)butyrate (5.45 g, Yield 95%). the mixture was washed with 30 ml of water twice After drying with anhydrous sodium sulfate the mixture was concentrated The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification The resulting effective fractions were concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a cooled mixture of 4-tert-butyl-2-(5-formylbenzofuran-2-yl)thiazole (0.713 g), N,N-dimethyl-3-mercaptopropionamide (0.37 g) and methyl 4-mercaptobutyrate (0.37 g) in acetonitrile (15 ml), boron trifluoride etherate (1.38 ml) was added dropwise at 0° C. After being stored in refrigerator for 18 hours, the resulting mixture was poured into ice-water, adjusted to pH 7 with aqueous sodium hydrogen carbonate solution and extracted with diethyl ether. The organic layer was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to give a mixture containing 3 compounds. The mixture was subjected to column chromatography on silica gel and eluted with toluene, successively a mixture of toluene and ethyl acetate (20:1 to 3:1) and at last a mixture of chloroform and methanol (10:1). The fractions eluted with toluene were concentrated under reduced pressure to give an oil of 4-tert-butyl-2-{5-[bis-(3-methoxycarbonylpropylthio)methyl]benzofuran-2-yl}thiazole (0.3 g). was added dropwise at 0° C extracted with diethyl ether The organic layer was washed with brine dried over magnesium sulfate concentrated under reduced pressure to give a mixture containing 3 compounds eluted with toluene successively a mixture of toluene and ethyl acetate (20:1 to 3:1) at last a mixture of chloroform and methanol (10:1) The fractions eluted with toluene were concentrated under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under an argon atmosphere, 2-fluorobenzaldehyde (3 g) was dissolved in 9 ml of dimethylformamide and potassium carbonate (5.01 g) was added. Methyl 4-mercaptobutyrate (4.5 ml) was added at room temperature and-was stirred at room temperature for 14 hours. After the addition of 50 ml of ethyl acetate, the mixture was washed with 30 ml of water twice, 3 ml of a 1N hydrochloric acid, and 30 ml of water three times. After drying with anhydrous sodium sulfate, the mixture was concentrated. The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification. The resulting effective fractions were concentrated to yield methyl 4-(2-formylphenylthio)butyrate (5.45 g, Yield 95%). the mixture was washed with 30 ml of water twice After drying with anhydrous sodium sulfate the mixture was concentrated The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification The resulting effective fractions were concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under an argon atmosphere, 2-fluorobenzaldehyde (3 g) was dissolved in 9 ml of dimethylformamide and potassium carbonate (5.01 g) was added. Methyl 4-mercaptobutyrate (4.5 ml) was added at room temperature and-was stirred at room temperature for 14 hours. After the addition of 50 ml of ethyl acetate, the mixture was washed with 30 ml of water twice, 3 ml of a 1N hydrochloric acid, and 30 ml of water three times. After drying with anhydrous sodium sulfate, the mixture was concentrated. The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification. The resulting effective fractions were concentrated to yield methyl 4-(2-formylphenylthio)butyrate (5.45 g, Yield 95%). the mixture was washed with 30 ml of water twice After drying with anhydrous sodium sulfate the mixture was concentrated The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification The resulting effective fractions were concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a cooled mixture of 7-chloro-2-(5-formylbenzofuran-2-yl)quinoline (0.77 g), N,N-dimethyl-3-mercaptopropionamide (0.37 g) and methyl 4-mercaptobutyrate (0.37 g) in acetonitrile (15 ml), boron trifluoride etherate (1.38 ml) was added dropwise at 0° C. After being stored in refrigerator for 18 hours, the resulting mixture was poured into ice-water, adjusted to pH 7 with aqueous sodium hydrogen carbonate solution and extracted with diethyl ether. The organic layer was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to give a mixture containing 3 compounds. The mixture was subjected to column chromatography on silica gel and eluted with toluene, successively a mixture of toluene and ethyl acetate (8:2) and at last a mixture of chloroform and methanol (10:1). The fractions eluted with toluene were concentrated under reduced pressure to give an oil of 7-chloro-2-{5-[bis(3-methoxycarbonylpropylthio)methyl]-benzofuran-2-yl}quinoline (0.25 g). was added dropwise at 0° C extracted with diethyl ether The organic layer was washed with brine dried over magnesium sulfate concentrated under reduced pressure to give a mixture containing 3 compounds eluted with toluene successively a mixture of toluene and ethyl acetate (8:2) at last a mixture of chloroform and methanol (10:1) The fractions eluted with toluene were concentrated under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a cooled mixture of 4-tert-butyl-2-(5-formylbenzofuran-2-yl)thiazole (0.713 g), N,N-dimethyl-3-mercaptopropionamide (0.37 g) and methyl 4-mercaptobutyrate (0.37 g) in acetonitrile (15 ml), boron trifluoride etherate (1.38 ml) was added dropwise at 0° C. After being stored in refrigerator for 18 hours, the resulting mixture was poured into ice-water, adjusted to pH 7 with aqueous sodium hydrogen carbonate solution and extracted with diethyl ether. The organic layer was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to give a mixture containing 3 compounds. The mixture was subjected to column chromatography on silica gel and eluted with toluene, successively a mixture of toluene and ethyl acetate (20:1 to 3:1) and at last a mixture of chloroform and methanol (10:1). The fractions eluted with toluene were concentrated under reduced pressure to give an oil of 4-tert-butyl-2-{5-[bis-(3-methoxycarbonylpropylthio)methyl]benzofuran-2-yl}thiazole (0.3 g). was added dropwise at 0° C extracted with diethyl ether The organic layer was washed with brine dried over magnesium sulfate concentrated under reduced pressure to give a mixture containing 3 compounds eluted with toluene successively a mixture of toluene and ethyl acetate (20:1 to 3:1) at last a mixture of chloroform and methanol (10:1) The fractions eluted with toluene were concentrated under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under an argon atmosphere, 2-fluorobenzaldehyde (3 g) was dissolved in 9 ml of dimethylformamide and potassium carbonate (5.01 g) was added. Methyl 4-mercaptobutyrate (4.5 ml) was added at room temperature and-was stirred at room temperature for 14 hours. After the addition of 50 ml of ethyl acetate, the mixture was washed with 30 ml of water twice, 3 ml of a 1N hydrochloric acid, and 30 ml of water three times. After drying with anhydrous sodium sulfate, the mixture was concentrated. The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification. The resulting effective fractions were concentrated to yield methyl 4-(2-formylphenylthio)butyrate (5.45 g, Yield 95%). the mixture was washed with 30 ml of water twice After drying with anhydrous sodium sulfate the mixture was concentrated The concentrated matter was subjected to silica gel chromatography (hexane/ethyl acetate=6/1) purification The resulting effective fractions were concentrated