1-(4-chlorophenyl)-2,2,2-trifluoroethanone

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

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

Procedure: 2,2,2-Trifluoro-4'-chloroacetophenone (0.8 g, 3.84 mmole), trimethylsulphoxonium iodide (1.02 g, 4.6 mmole) and cetyltrimethylammonium bromide (0.1 g, 0.27 mmole) were stirred in a mixture of 1,1,1-trichloroethane (40 ml) and 18% sodium hydroxide solution (20 ml) at 75° for 2 hours. The mixture was then allowed to cool, the organic layer was separated, evaporated, and the residue was stirred in dimethylformamide (50 ml) with 1,2,4-triazole (1 g, 14.5 mmole) and anhydrous potassium carbonate (2 g, 14.5 mmole) at 90° for 4 hours. The mixture was then allowed to cool, ethyl acetate (100 ml) and water (50 ml) were added and the aqueous layer was separated. The organic layer was washed a further 6 times with water (200 ml in total), dried over magnesium sulphate, and evaporated to give a gum (104 mg) which was chromatographed on silica (230-400 mesh), eluting with ethyl acetate to give as a colorless solid the title compound, 84 mg (8%). One recrystallization from dichloromethane/hexane gave colorless crystals, 64 mg, m.p. 117°-118° C. to cool the organic layer was separated evaporated to cool the aqueous layer was separated The organic layer was washed a further 6 times with water (200 ml in total) dried over magnesium sulphate evaporated

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

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen atmosphere, 33.6 ml of n-butyllithium/hexane solution (1.2M solution) was added to a solution of 17.3 g of methoxymethyltriphenylphosphonium chloride in 150 ml of dry THF at -60° C. The reaction solution was stirred at -60° C. for 30 minutes and at -20° C. for 30 minutes. A solution of 7.0 g of 4-chloro-α,α,α-trifluoroacetophenone in 10 ml of dry THF was slowly added to the reaction solution at -60° C. The reaction solution was stirred at -60° C. for 1 hour and at room temperature for 12 hours. Thereafter, 200 ml of n-hexane was added to the reaction mixture and insoluble materials were filtered out. The filtrate was washed with dilute HCl-ice water and saturated sodium chloride solution successively and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and the residues was subjected to column chromatography on silica gel [eluted with n-hexane/ethyl acetate (40:1) mixture] to obtain 4.17 g of the desired compound (E/Z=ca. 1/1). The reaction solution was stirred at -60° C. for 1 hour and at room temperature for 12 hours were filtered out The filtrate was washed with dilute HCl-ice water and saturated sodium chloride solution successively dried over anhydrous magnesium sulfate The solvent was removed under reduced pressure

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen atmosphere, 110 ml of n-butyllithium/hexane solution (0.95M solution) was added to a solution of 20 g of p-bromochlorobenzene in 200 ml of dry THF at -60° C. The reaction solution was stirred at -60° C. for 1 hour and at -20° C. for 30 minutes. A solution of 17.8 g of ethyl trifluoroacetate in 20 ml of dry THF was added to the reaction solution at -60° C., followed by stirring at that temperature for 1 hour. The reaction solution was poured into dilute HCl-ice water and extracted twice with diethyl ether. The ether layers were combined and washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under a reduced pressure and the residue was subjected to distillation under a reduced pressure to obtain 13.1 g of the desired compound. by stirring at that temperature for 1 hour extracted twice with diethyl ether washed with saturated sodium chloride solution dried over anhydrous magnesium sulfate The solvent was removed under a reduced pressure the residue was subjected to distillation under a reduced pressure

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

Procedure: 1-(4-Chlorophenyl)-2,2,2-trifluoroethanone (2.00 g, 9.59 mmol) in nitromethane (10 mL) was stirred with potassium carbonate (1.32 g, 9.59 mmol) at room temperature for 1 hour. After addition of water, the reaction mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue (pale yellow amorphous, 3.3 g) was dissolved in ethanol (52 mL), then 6 M hydrochloric acid was added dropwise under cooling with ice, and zinc powder (3.13 g, 48.0 mmol) was gradually added. The reaction mixture was stirred for one day while the temperature was gradually raised to room temperature, and filtered through Celite. The filtrate was concentrated under reduced pressure. The residue was mixed with 28 wt % aqueous ammonia and extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1→1/1 (v/v)) to give the title compound as a colorless solid (609 mg, yield 26%). the reaction mixture was extracted with ethyl acetate the organic layer was dried over anhydrous magnesium sulfate concentrated under reduced pressure The resulting residue (pale yellow amorphous, 3.3 g) was dissolved in ethanol (52 mL) 6 M hydrochloric acid was added dropwise was gradually added filtered through Celite The filtrate was concentrated under reduced pressure The residue was mixed with 28 wt % aqueous ammonia extracted with chloroform the organic layer was dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was purified by silica gel column chromatography (hexane/ethyl acetate=3/1→1/1 (v/v))

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

Procedure: 4'-Chloro-2,2,2-trifluoroacetophenone (R. Fuchs, J. Org. Chem. 22, 993-994 (1957)) is reacted with benzyl-triphenylphosphonium chloride in the presence of an ethanolic solution of sodium ethoxide. The product is crystallized from hexane. 1-Phenyl-3,3,3-trifluoro-2-(4-chlorophenyl)-propene is obtained with a yield of 68%; m.p.: 63-66° C. The product is crystallized from hexane

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

Procedure: 2,2,2-Trifluoro-4'-chloroacetophenone (0.8 g, 3.84 mmole), trimethylsulphoxonium iodide (1.02 g, 4.6 mmole) and cetyltrimethylammonium bromide (0.1 g, 0.27 mmole) were stirred in a mixture of 1,1,1-trichloroethane (40 ml) and 18% sodium hydroxide solution (20 ml) at 75° for 2 hours. The mixture was then allowed to cool, the organic layer was separated, evaporated, and the residue was stirred in dimethylformamide (50 ml) with 1,2,4-triazole (1 g, 14.5 mmole) and anhydrous potassium carbonate (2 g, 14.5 mmole) at 90° for 4 hours. The mixture was then allowed to cool, ethyl acetate (100 ml) and water (50 ml) were added and the aqueous layer was separated. The organic layer was washed a further 6 times with water (200 ml in total), dried over magnesium sulphate, and evaporated to give a gum (104 mg) which was chromatographed on silica (230-400 mesh), eluting with ethyl acetate to give as a colorless solid the title compound, 84 mg (8%). One recrystallization from dichloromethane/hexane gave colorless crystals, 64 mg, m.p. 117°-118° C. to cool the organic layer was separated evaporated to cool the aqueous layer was separated The organic layer was washed a further 6 times with water (200 ml in total) dried over magnesium sulphate evaporated