2-bromo-1-(4-chlorophenyl)propan-1-one

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A mixture of 2-bromo-4′-chloropropiophenone (45.0 g), thiobenzamide (24.7 g), sodium acetate (14.8 g) and ethanol (400 mL) was stirred with heating under reflux for 3 hrs. The reaction mixture was poured into water, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated to give 4-(4-chlorophenyl)-5-methyl-2-phenylthiazole (35.1 g, 68%) as crystals. Recrystallization from ethyl acetate-hexane gave colorless prism crystals. melting point: 90–91° C. with heating under reflux for 3 hrs the mixture was extracted with ethyl acetate The organic layer was washed with water dried over anhydrous magnesium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: The 2-bromo-4'-chloropropiophenone (58.1 g), which had been prepared in Example 5, and triphenyl phosphine (61.6 g) were dissolved in 250 ml of acetonitrile. The resulting solution was heated under reflex for 1.5 hours. After the completion of the reaction, the reaction mixture was cooled with ice, and the crystalline material thus formed was separated by filtration, washed with cold acetonitrile and dried in air to give triphenyl[1-(4-chlorophenyl)-1-oxo-2-propyl]-phosphonium bromide (79.0 g). mp 258°-258.5° C. The resulting solution was heated under reflex for 1.5 hours After the completion of the reaction the reaction mixture was cooled with ice the crystalline material thus formed was separated by filtration washed with cold acetonitrile dried in air

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

実験手順: The 2-bromo-4'-chloropropiophenone (58.1 g), which had been prepared in Example 5, and triphenyl phosphine (61.6 g) were dissolved in 250 ml of acetonitrile. The resulting solution was heated under reflex for 1.5 hours. After the completion of the reaction, the reaction mixture was cooled with ice, and the crystalline material thus formed was separated by filtration, washed with cold acetonitrile and dried in air to give triphenyl[1-(4-chlorophenyl)-1-oxo-2-propyl]-phosphonium bromide (79.0 g). mp 258°-258.5° C. The resulting solution was heated under reflex for 1.5 hours After the completion of the reaction the reaction mixture was cooled with ice the crystalline material thus formed was separated by filtration washed with cold acetonitrile dried in air

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

実験手順: 4'-chloropropiophenone (39.6 g) and anhydrous aluminum chlorid (0.1 g) were dissolved in 100 ml of chloroform. To the resulting solution was protionwise added bromine (37.6 g) at a temperature of 30° to 35° C. The reaction mixture was stirred at room temperature for 30 minutes. Then nitrogen was blown into the reaction mixture to remove the formed hydrogen bromide therefrom. Thereafter, the solvent was distilled off under reduced pressure to give 2-bromo-4'-chloropropiophenone (58.1 g). mp 77.5°-79.5° C. at a temperature of 30° to 35° C to remove the formed hydrogen bromide Thereafter, the solvent was distilled off under reduced pressure

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

実験手順: 4'-chloropropiophenone (39.6 g) and anhydrous aluminum chlorid (0.1 g) were dissolved in 100 ml of chloroform. To the resulting solution was protionwise added bromine (37.6 g) at a temperature of 30° to 35° C. The reaction mixture was stirred at room temperature for 30 minutes. Then nitrogen was blown into the reaction mixture to remove the formed hydrogen bromide therefrom. Thereafter, the solvent was distilled off under reduced pressure to give 2-bromo-4'-chloropropiophenone (58.1 g). mp 77.5°-79.5° C. at a temperature of 30° to 35° C to remove the formed hydrogen bromide Thereafter, the solvent was distilled off under reduced pressure

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

実験手順: To a mixture of 3.08 g of 2-bromo-4′-chloropropiophenone, 1.79 g of 3-thiopheneacetic acid, acetonitrile and 10 ml of DMF was added 1.53 g of triethylamine, and the mixture was stirred for 2 hours at room temperature. The resultant mixture was cooled to 0° C., and 4.60 g of 1,8-diazabicyclo[5.4.0]undec-7-ene was added dropwise into this, and the mixture was stirred for 3 hours at room temperature. Then, the reaction mixture was stirred for 11 hours at room temperature while blowing air into the reaction mixture. To the reaction mixture was added 200 ml of 1 mol/L hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with a saturated sodium hydrogen carbonate aqueous solution and saturated brine sequentially, and dried over anhydrous magnesium sulfate, then, concentrated under reduced pressure to obtain 3.98 g of 4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(3-thienyl)-2(5H)-furanone. was stirred for 3 hours at room temperature Then, the reaction mixture was stirred for 11 hours at room temperature extracted with ethyl acetate The organic layer was washed with a saturated sodium hydrogen carbonate aqueous solution and saturated brine sequentially dried over anhydrous magnesium sulfate concentrated under reduced pressure

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

実験手順: To a mixture of 3.08 g of 2-bromo-4′-chloropropiophenone, 1.79 g of 3-thiopheneacetic acid, acetonitrile and 10 ml of DMF was added 1.53 g of triethylamine, and the mixture was stirred for 2 hours at room temperature. The resultant mixture was cooled to 0° C., and 4.60 g of 1,8-diazabicyclo[5.4.0]undec-7-ene was added dropwise into this, and the mixture was stirred for 3 hours at room temperature. Then, the reaction mixture was stirred for 11 hours at room temperature while blowing air into the reaction mixture. To the reaction mixture was added 200 ml of 1 mol/L hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with a saturated sodium hydrogen carbonate aqueous solution and saturated brine sequentially, and dried over anhydrous magnesium sulfate, then, concentrated under reduced pressure to obtain 3.98 g of 4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(3-thienyl)-2(5H)-furanone. was stirred for 3 hours at room temperature Then, the reaction mixture was stirred for 11 hours at room temperature extracted with ethyl acetate The organic layer was washed with a saturated sodium hydrogen carbonate aqueous solution and saturated brine sequentially dried over anhydrous magnesium sulfate concentrated under reduced pressure

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 10.12 g of 4′-chloropropiophenone, 0.1 ml of hydrobromic acid (48% aqueous solution) and 60 ml of acetic acid was cooled to 0° C. under a nitrogen atmosphere. Into the mixture, 3.1 ml of bromine was added dropwise, then, the mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure, to obtain 14.34 g of 2-bromo-4′-chloropropiophenone. to warm to room temperature The reaction mixture was concentrated under reduced pressure