2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro-4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro-4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro-4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 4-bromo-3,5-dichlorobenzotrifluoride (1 g, 3.4 mmol) in 1.2 mL tetrahydrofurane was slowly added to isopropylmagnesium bromide (15% in THF, 3.3 g, 3.4 mmol) at max. −10° C. After complete addition the reaction mixture was stirred for 30 min at −10° C. Dimethylformamide (0.275 g, 3.7 mmol) was added and the mixture was slowly warmed up. The mixture was quenched with saturated ammonium chloride solution and extracted three times with ethyl acetate. The combined organic phases were dried on sodium sulfate, filtered and evaporated. The crude product was used without any further purification, brown oil (741 mg, 89%). −10° C After complete addition the reaction mixture the mixture was slowly warmed up The mixture was quenched with saturated ammonium chloride solution extracted three times with ethyl acetate The combined organic phases were dried on sodium sulfate filtered evaporated The crude product was used without any further purification, brown oil (741 mg, 89%)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro-4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro-4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: n-Butyllithium (1.6M in hexane, 330 ml) was added dropwise with stirring to a solution of 2,6-dichloro-4-trifluoromethylbromobenzene (163.3 g) in ether while maintaining the temperature below -70° C. The mixture was stirred for 1 hour at -78° C. then ethyl chloroformate (61.7 g) was added while maintaining the temperature below -70° C. The mixture was stirred at room temperature overnight. It was cooled to 0° C. and a saturated aqueous solution of ammonium chloride was added. The layers were separated and the organic layer was washed with water, dried (Na2SO4) and filtered. The filtrate was evaporated to dryness and the residue was distilled to give ethyl 2,6-dichloro4-trifluoromethylbenzoate (123.9 g) as a colourless liquid bp 90°-96° C. at 5 mmHg. while maintaining the temperature below -70° C while maintaining the temperature below -70° C The mixture was stirred at room temperature overnight It was cooled to 0° C. The layers were separated the organic layer was washed with water dried (Na2SO4) filtered The filtrate was evaporated to dryness the residue was distilled

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 4-bromo-3,5-dichlorobenzotrifluoride (1 g, 3.4 mmol) in 1.2 mL tetrahydrofurane was slowly added to isopropylmagnesium bromide (15% in THF, 3.3 g, 3.4 mmol) at max. −10° C. After complete addition the reaction mixture was stirred for 30 min at −10° C. Dimethylformamide (0.275 g, 3.7 mmol) was added and the mixture was slowly warmed up. The mixture was quenched with saturated ammonium chloride solution and extracted three times with ethyl acetate. The combined organic phases were dried on sodium sulfate, filtered and evaporated. The crude product was used without any further purification, brown oil (741 mg, 89%). −10° C After complete addition the reaction mixture the mixture was slowly warmed up The mixture was quenched with saturated ammonium chloride solution extracted three times with ethyl acetate The combined organic phases were dried on sodium sulfate filtered evaporated The crude product was used without any further purification, brown oil (741 mg, 89%)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Bromo-2,6-dichloro-4- trifluoromethylbenzene (80 g, 0.27 mol) was dissolved in anhydrous diethyl ether (480 ml) and the solution was cooled to -78° C. Butyllithium (2.5M solution in hexane, 100 ml) was added dropwise with stirring in an atmosphere of nitrogen while maintaining the temperature below -70° C. After stirring for a further 1 hour at -78° C. N-formylpiperidine (30.8 g, 0.27 mol) was added dropwise. The mixture was stirred at -78° C. overnight and allowed to warm slowly to 0° C. Hydrochloric acid (2M, 200 ml) was added dropwise to the solution with ice-cooling. The two layers were separated and the organic phase was washed with water, dried over anhydrous sodium sulphate and evaporated to dryness. The oily residue was dissolved in a mixture of ethyl acetate and petroleum spirit (b.p. 60°-80° C.) (1:10) and the solution was filtered through a column of silica. Evaporation of the filtrate and distillation of the resultant oil gave 2,6-dichloro-4-trifluoromethylbenzaldehyde (43.7 g) as a colourless liquid, b.p. 115° C. at 14 mmHg. while maintaining the temperature below -70° C After stirring for a further 1 hour at -78° C The mixture was stirred at -78° C. overnight to warm slowly to 0° C cooling The two layers were separated the organic phase was washed with water dried over anhydrous sodium sulphate evaporated to dryness The oily residue was dissolved in a mixture of ethyl acetate and petroleum spirit (b.p. 60°-80° C.) (1:10) the solution was filtered through a column of silica Evaporation of the filtrate and distillation of the resultant oil