2-(4-chlorophenyl)-1-(2,4-dichlorophenyl)ethanone

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 solution of 4-chlorobenzyl 2,4-dichlorophenyl ketone (4.5 g, 14.4 mmol) and dimethylformamide dimethylacetal (7.7 mL, 58 mmol) in DMF (60 mL) was heated at 75° C. for 20 h. The volatiles were removed in vacuo to provide the crude 3-dimethylamino-1-(2,4-dichlorophenyl)-2-(4-chlorophenyl)prop-2-en-1-one (14.4 mmol assumed) which was used directly in the next step. HPLC/MS: 354 (M+1), 356 (M+3); Rt=3.47 min The volatiles were removed in vacuo

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

実験手順: A solution of 4-chlorobenzyl bromide (Lancaster Chemical) (10.0 g, 48.6 mmol) in 40 mL ether was added under nitrogen to a suspension of magnesium turnings (Alpha Chemical Inc.) in ether (60 mL) over 10 minutes. The suspension was stirred for 2 h and the supernatant was cannulated under nitrogen into another round bottom flask fitted with a magnetic stirrer bar. Then 2,4-dichlorobenzonitrile (7.0 g, 40.5 mmol) in 65 mL ether was slowly added under nitrogen to the Grignard solution and the mixture was stirred over night at room temperature. The imine precipitated out of solution and the mixture was refluxed for 3 h. The reaction mixture was cooled and poured into a flask containing 50 mL ethyl acetate and 50 mL 2N HCl. Stirred vigorously to hydrolyze the imine, separated the organic layer and dried it over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent volume reduced under reduced pressure. The crude product was flash chromatographed on silica gel (92/8 hexanes/ethyl acetate) to give product. 1H NMR 500 MHz (CDCl3): δ 4.40 (s, 2H), 7.2-7.6 (m, 7H). the supernatant was cannulated under nitrogen into another round bottom flask fitted with a magnetic stirrer bar the mixture was stirred over night at room temperature The imine precipitated out of solution the mixture was refluxed for 3 h The reaction mixture was cooled poured into a flask containing 50 mL ethyl acetate and 50 mL 2N HCl Stirred vigorously separated the organic layer dried it over anhydrous magnesium sulfate The desiccant was filtered off chromatographed on silica gel (92/8 hexanes/ethyl acetate) to give product

反応条件: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 420 ml of a 2M solution of the sodium salt of hexamethyldisilazane in THF are cooled to −60° C. under a nitrogen atmosphere, 350 ml of THF are added, then, dropwise, a solution of 57.6 g of 4-chlorophenylacetic acid in 70 ml of THF is added and the mixture is left stirring at −60° C. for one hour. 66 g of methyl 2,4-dichlorobenzoate are subsequently added dropwise at −60° C., the mixture is left stirring at −60° C. for 40 minutes and then the temperature is allowed to rise to 0° C. The reaction mixture is poured onto an ice/1 liter of 2N HCl mixture and extracted with ether, the organic phase is dried over Na2SO4, the solvent is concentrated under vacuum to a volume of 150 ml, 200 ml of pentane are added and the crystalline product formed is filtered off. 60 g of the expected compound are obtained. the mixture is left the mixture is left stirring at −60° C. for 40 minutes to rise to 0° C extracted with ether the organic phase is dried over Na2SO4 the solvent is concentrated under vacuum to a volume of 150 ml, 200 ml of pentane are added the crystalline product formed is filtered off

反応条件: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 420 ml of a 2M solution of the sodium salt of hexamethyldisilazane in THF are cooled to −60° C. under a nitrogen atmosphere, 350 ml of THF are added, then, dropwise, a solution of 57.6 g of 4-chlorophenylacetic acid in 70 ml of THF is added and the mixture is left stirring at −60° C. for one hour. 66 g of methyl 2,4-dichlorobenzoate are subsequently added dropwise at −60° C., the mixture is left stirring at −60° C. for 40 minutes and then the temperature is allowed to rise to 0° C. The reaction mixture is poured onto an ice/1 liter of 2N HCl mixture and extracted with ether, the organic phase is dried over Na2SO4, the solvent is concentrated under vacuum to a volume of 150 ml, 200 ml of pentane are added and the crystalline product formed is filtered off. 60 g of the expected compound are obtained. the mixture is left the mixture is left stirring at −60° C. for 40 minutes to rise to 0° C extracted with ether the organic phase is dried over Na2SO4 the solvent is concentrated under vacuum to a volume of 150 ml, 200 ml of pentane are added the crystalline product formed is filtered off

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

実験手順: A solution of 4-chlorobenzyl 2,4-dichlorophenyl ketone (4.5 g, 14.4 mmol) and dimethyl-formamide dimethylacetal (7.7 mL, 58 mmol) in DMF (60 mL) was heated at 75° C. for 20 h. The volatiles were removed in vacuo to provide the crude product which was used directly in the next step. HPLC/MS: 354 (M+1), 356 (M+3); Rt=3.47 min. The volatiles were removed in vacuo

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

実験手順: A solution of 4-chlorobenzyl 2,4-dichlorophenyl ketone (4.5 g, 14.4 mmol) and dimethyl-formamide dimethylacetal (7.7 mL, 58 mmol) in DMF (60 mL) was heated at 75° C. for 20 h. The volatiles were removed in vacuo to provide the crude product which was used directly in the next step. HPLC/MS: 354 (M+1), 356 (M+3); Rt=3.47 min. The volatiles were removed in vacuo

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

実験手順: A solution of 4-chlorobenzyl 2,4-dichlorophenyl ketone (4.5 g, 14.4 mmol) and dimethyl-formamide dimethylacetal (7.7 mL, 58 mmol) in DMF (60 mL) was heated at 75° C. for 20 h. The volatiles were removed in vacuo to provide the crude product which was used directly in the next step. HPLC/MS: 354 (M+1), 356 (M+3); Rt=3.47 min. The volatiles were removed in vacuo

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

実験手順: A solution of 4-chlorobenzyl 2,4-dichlorophenyl ketone (4.5 g, 14.4 mmol) and dimethyl-formamide dimethylacetal (7.7 mL, 58 mmol) in DMF (60 mL) was heated at 75° C. for 20 h. The volatiles were removed in vacuo to provide the crude product which was used directly in the next step. HPLC/MS: 354 (M+1), 356 (M+3); Rt=3.47 min. The volatiles were removed in vacuo

反応条件: temp:-5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7 ml of POCl3 are added dropwise to a solution of 6.6 ml of DMF in 4 ml of dichloroethane, cooled to −5° C., under nitrogen, and then the temperature is allowed to rise and 7 g of 2-(4-chlorophenyl)-1-(2,4-dichlorophenyl)ethanone are added. The reaction medium is heated at 50° C. for 16 hours and then the mixture is poured into 100 ml of ice-cold water. The medium is extracted with DCM and then the organic phase is washed with a saturated NaHCO3 solution, water, and then an NaCl solution. 1.45 g of the expected compound are obtained, which compound crystallizes from isopropyl ether, m.p.=128° C. The reaction medium is heated at 50° C. for 16 hours The medium is extracted with DCM the organic phase is washed with a saturated NaHCO3 solution, water

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

実験手順: A solution of 4-chlorobenzyl 2,4-dichlorophenyl ketone (4.5 g, 14.4 mmol) and dimethyl-formamide dimethylacetal (7.7 mL, 58 mmol) in DMF (60 mL) was heated at 75° C. for 20 h. The volatiles were removed in vacuo to provide the crude product which was used directly in the next step. HPLC/MS: 354 (M+1), 356 (M+3); Rt=3.47 min. The volatiles were removed in vacuo