1-(2-sulfanylphenyl)ethanone

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1-(2-sulfanylphenyl)ethanone (6.40 g, 42.05 mmol) in ethanol (80 mL) was added an aqueous solution of potassium hydroxide (7.08 g, 126.14 mmol in 30 mL of water) and an aqueous solution of 2-bromoethanamine hydrobromide (9.48 g, 46.25 mmol in 30 mL of water). After being stirred at room temperature for 6 hours, the reaction mixture was concentrated in vacuo to remove most of ethanol and extracted with dichloromethane (60 mL×3). The combined organic layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was purified by flash column chromatography to give 5.92 g of 5-methyl-2,3-dihydro-1,4-benzothiazepine. the reaction mixture was concentrated in vacuo to remove most of ethanol extracted with dichloromethane (60 mL×3) The combined organic layers were washed with brine (100 mL) dried over anhydrous sodium sulfate concentrated in vacuo The residue was purified by flash column chromatography

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of aluminium chloride (10.50 g, 78.8 mmol) in dry benzene (200 mL) was added a solution of 1-[2-(benzylsulfanyl)phenyl]ethan-1-one (11.93 g, 49.2 mmol) in dry benzene (100 mL) dropwise in an ice bath under argon atmosphere. After the reaction mixture being stirred at room temperature overnight, the reaction was quenched by the cautious addition of ice-water. The separated organic layer was washed with water and extracted with 5% aqueous solution of sodium hydroxide (300 mL). The aqueous layer was acidified to about pH 3 with concentrated hydrochloric acid (12 N) and extracted with dichloromethane (300 mL×3). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, concentrated in vacuo to afford 6.47 g of the crude product 1-(2-sulfanylphenyl)ethanone. the reaction was quenched by the cautious addition of ice-water The separated organic layer was washed with water extracted with 5% aqueous solution of sodium hydroxide (300 mL) extracted with dichloromethane (300 mL×3) The combined organic layers were washed with brine dried over anhydrous sodium sulfate concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of aluminium chloride (10.50 g, 78.8 mmol) in dry benzene (200 mL) was added a solution of 1-[2-(benzylsulfanyl)phenyl]ethan-1-one (11.93 g, 49.2 mmol) in dry benzene (100 mL) dropwise in an ice bath under argon atmosphere. After the reaction mixture being stirred at room temperature overnight, the reaction was quenched by the cautious addition of ice-water. The separated organic layer was washed with water and extracted with 5% aqueous solution of sodium hydroxide (300 mL). The aqueous layer was acidified to about pH 3 with concentrated hydrochloric acid (12 N) and extracted with dichloromethane (300 mL×3). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, concentrated in vacuo to afford 6.47 g of the crude product 1-(2-sulfanylphenyl)ethanone. the reaction was quenched by the cautious addition of ice-water The separated organic layer was washed with water extracted with 5% aqueous solution of sodium hydroxide (300 mL) extracted with dichloromethane (300 mL×3) The combined organic layers were washed with brine dried over anhydrous sodium sulfate concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The title compound was prepared from 1-(2-mercaptophenyl)ethanone and 1-bromopinacolone using the procedure in Step B Examples 36˜49. 1H NMR (CDCl3, 500 MHz) 7.82˜7.88 (m, 2H), 7.44˜7.50 (m, 2H), 2.60 (s, 3H), 1.41 (s, 9H). LC-MS: 4.06 min. (m/Z=233.4, 191). 4.06 min. (m/Z=233.4, 191)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Alternatively, such a 2-acetylphenol or 2-acetylthiophenol is condensed with ethylacetate and cyclized with dehydration to form a benzo[b]pyran which is then condensed with a Grignard reagent, e.g., ##STR10##

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1-(2-sulfanylphenyl)ethanone (6.40 g, 42.05 mmol) in ethanol (80 mL) was added an aqueous solution of potassium hydroxide (7.08 g, 126.14 mmol in 30 mL of water) and an aqueous solution of 2-bromoethanamine hydrobromide (9.48 g, 46.25 mmol in 30 mL of water). After being stirred at room temperature for 6 hours, the reaction mixture was concentrated in vacuo to remove most of ethanol and extracted with dichloromethane (60 mL×3). The combined organic layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was purified by flash column chromatography to give 5.92 g of 5-methyl-2,3-dihydro-1,4-benzothiazepine. the reaction mixture was concentrated in vacuo to remove most of ethanol extracted with dichloromethane (60 mL×3) The combined organic layers were washed with brine (100 mL) dried over anhydrous sodium sulfate concentrated in vacuo The residue was purified by flash column chromatography

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of aluminium chloride (10.50 g, 78.8 mmol) in dry benzene (200 mL) was added a solution of 1-[2-(benzylsulfanyl)phenyl]ethan-1-one (11.93 g, 49.2 mmol) in dry benzene (100 mL) dropwise in an ice bath under argon atmosphere. After the reaction mixture being stirred at room temperature overnight, the reaction was quenched by the cautious addition of ice-water. The separated organic layer was washed with water and extracted with 5% aqueous solution of sodium hydroxide (300 mL). The aqueous layer was acidified to about pH 3 with concentrated hydrochloric acid (12 N) and extracted with dichloromethane (300 mL×3). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, concentrated in vacuo to afford 6.47 g of the crude product 1-(2-sulfanylphenyl)ethanone. the reaction was quenched by the cautious addition of ice-water The separated organic layer was washed with water extracted with 5% aqueous solution of sodium hydroxide (300 mL) extracted with dichloromethane (300 mL×3) The combined organic layers were washed with brine dried over anhydrous sodium sulfate concentrated in vacuo