1-(3-sulfanylphenyl)ethanone

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A suspension of 3′-mercaptoacetophenone (Reference compound No. 4-1, 0.50 g, 3.3 mmol), potassium carbonate (0.55 g, 4.0 mmol) and 4-fluoronitrobenzene (0.42 mL, 4.0 mmol) in N,N-dimethylformamide (20 mL) was stirred at room temperature for 8.5 hours. Water (30 mL) was added to the reaction mixture, extracted with mixed solvent (30 mL) which consists of hexane and ethyl acetate (3:1). The organic layer was washed with brine (30 mL), dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (1.2 g) quantitatively as a yellow solid. extracted with mixed solvent (30 mL) which The organic layer was washed with brine (30 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

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

Procedure: A suspension of 3′-mercaptoacetophenone (Reference compound No. 4-1, 0.50 g, 3.3 mmol), potassium carbonate (0.55 g, 4.0 mmol) and 4-fluoronitrobenzene (0.42 mL, 4.0 mmol) in N,N-dimethylformamide (20 mL) was stirred at room temperature for 8.5 hours. Water (30 mL) was added to the reaction mixture, extracted with mixed solvent (30 mL) which consists of hexane and ethyl acetate (3:1). The organic layer was washed with brine (30 mL), dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (1.2 g) quantitatively as a yellow solid. extracted with mixed solvent (30 mL) which The organic layer was washed with brine (30 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

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

Procedure: A suspension of 3′-mercaptoacetophenone (Reference compound No. 4-1, 1.5 g, 9.9 mmol), potassium carbonate (1.6 g, 12 mmol) and iodomethane (740 μL, 12 mmol) in N,N-dimethylformamide was stirred at 50° C. for 75 minutes. Water (50 mL) was added to the reaction mixture, extracted with a mixed solvent (50 mL) which consists of hexane and ethyl acetate (3:1). The organic layer was washed with brine (50 mL), dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (1.3 g) as a brown oil (Yield 77%). extracted with a mixed solvent (50 mL) which The organic layer was washed with brine (50 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3′-bromoacetophenone (10 g, 50 mmol), N,N-diisopropylethylamine (18 mL, 0.10 mol), 3-mercaptopropionic acid 2-ethylhexyl ester (11 mL, 48 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.29 g, 0.50 mmol) and tris(dibenzylideneacetone)palladium(0) (0.46 g, 0.50 mmol) in 1,4-dioxane (250 mL) was stirred at 100° C. for 2 days. After the reaction solution was filtered with celite, the filtrate was concentrated in vacuo until the volume became one third approximately. Water (200 mL) was added thereto, extracted with ethyl acetate (200 mL). The organic layer was washed with brine (200 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give a mixture including 3-(3-acetylphenyl)thiopropionic acid 2-ethylhexyl ester (19 g). This mixture (17 g) was dissolved in tetrahydrofuran (200 mL), sodium ethoxide (7.0 g, 0.10 mol) in ethanol (40 mL) was added thereto, and then the whole was stirred at 50° C. for 2 hours. Water (200 mL) was added to the reaction solution and washed with ethyl acetate (200 mL). 1N Hydrochloric acid (100 mL) was added to the aqueous layer and extracted with ethyl acetate (300 mL), then the organic layer was washed with brine (100 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (6.2 g) as a brown oil (Yield 81%). After the reaction solution was filtered with celite the filtrate was concentrated in vacuo until the volume Water (200 mL) was added extracted with ethyl acetate (200 mL) The organic layer was washed with brine (200 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure to give a mixture washed with ethyl acetate (200 mL) 1N Hydrochloric acid (100 mL) was added to the aqueous layer extracted with ethyl acetate (300 mL) the organic layer was washed with brine (100 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3′-bromoacetophenone (10 g, 50 mmol), N,N-diisopropylethylamine (18 mL, 0.10 mol), 3-mercaptopropionic acid 2-ethylhexyl ester (11 mL, 48 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.29 g, 0.50 mmol) and tris(dibenzylideneacetone)palladium(0) (0.46 g, 0.50 mmol) in 1,4-dioxane (250 mL) was stirred at 100° C. for 2 days. After the reaction solution was filtered with celite, the filtrate was concentrated in vacuo until the volume became one third approximately. Water (200 mL) was added thereto, extracted with ethyl acetate (200 mL). The organic layer was washed with brine (200 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give a mixture including 3-(3-acetylphenyl)thiopropionic acid 2-ethylhexyl ester (19 g). This mixture (17 g) was dissolved in tetrahydrofuran (200 mL), sodium ethoxide (7.0 g, 0.10 mol) in ethanol (40 mL) was added thereto, and then the whole was stirred at 50° C. for 2 hours. Water (200 mL) was added to the reaction solution and washed with ethyl acetate (200 mL). 1N Hydrochloric acid (100 mL) was added to the aqueous layer and extracted with ethyl acetate (300 mL), then the organic layer was washed with brine (100 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (6.2 g) as a brown oil (Yield 81%). After the reaction solution was filtered with celite the filtrate was concentrated in vacuo until the volume Water (200 mL) was added extracted with ethyl acetate (200 mL) The organic layer was washed with brine (200 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure to give a mixture washed with ethyl acetate (200 mL) 1N Hydrochloric acid (100 mL) was added to the aqueous layer extracted with ethyl acetate (300 mL) the organic layer was washed with brine (100 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

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

Procedure: A suspension of 3′-mercaptoacetophenone (Reference compound No. 4-1, 0.50 g, 3.3 mmol), potassium carbonate (0.55 g, 4.0 mmol) and 4-fluoronitrobenzene (0.42 mL, 4.0 mmol) in N,N-dimethylformamide (20 mL) was stirred at room temperature for 8.5 hours. Water (30 mL) was added to the reaction mixture, extracted with mixed solvent (30 mL) which consists of hexane and ethyl acetate (3:1). The organic layer was washed with brine (30 mL), dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (1.2 g) quantitatively as a yellow solid. extracted with mixed solvent (30 mL) which The organic layer was washed with brine (30 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

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

Procedure: A suspension of 3′-mercaptoacetophenone (Reference compound No. 4-1, 1.5 g, 9.9 mmol), potassium carbonate (1.6 g, 12 mmol) and iodomethane (740 μL, 12 mmol) in N,N-dimethylformamide was stirred at 50° C. for 75 minutes. Water (50 mL) was added to the reaction mixture, extracted with a mixed solvent (50 mL) which consists of hexane and ethyl acetate (3:1). The organic layer was washed with brine (50 mL), dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (1.3 g) as a brown oil (Yield 77%). extracted with a mixed solvent (50 mL) which The organic layer was washed with brine (50 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 3′-bromoacetophenone (10 g, 50 mmol), N,N-diisopropylethylamine (18 mL, 0.10 mol), 3-mercaptopropionic acid 2-ethylhexyl ester (11 mL, 48 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.29 g, 0.50 mmol) and tris(dibenzylideneacetone)palladium(0) (0.46 g, 0.50 mmol) in 1,4-dioxane (250 mL) was stirred at 100° C. for 2 days. After the reaction solution was filtered with celite, the filtrate was concentrated in vacuo until the volume became one third approximately. Water (200 mL) was added thereto, extracted with ethyl acetate (200 mL). The organic layer was washed with brine (200 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give a mixture including 3-(3-acetylphenyl)thiopropionic acid 2-ethylhexyl ester (19 g). This mixture (17 g) was dissolved in tetrahydrofuran (200 mL), sodium ethoxide (7.0 g, 0.10 mol) in ethanol (40 mL) was added thereto, and then the whole was stirred at 50° C. for 2 hours. Water (200 mL) was added to the reaction solution and washed with ethyl acetate (200 mL). 1N Hydrochloric acid (100 mL) was added to the aqueous layer and extracted with ethyl acetate (300 mL), then the organic layer was washed with brine (100 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (6.2 g) as a brown oil (Yield 81%). After the reaction solution was filtered with celite the filtrate was concentrated in vacuo until the volume Water (200 mL) was added extracted with ethyl acetate (200 mL) The organic layer was washed with brine (200 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure to give a mixture washed with ethyl acetate (200 mL) 1N Hydrochloric acid (100 mL) was added to the aqueous layer extracted with ethyl acetate (300 mL) the organic layer was washed with brine (100 mL) dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure