2-Bromo-1,3-diisopropylbenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:-29.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Diisopropylbromobenzene (21.58 g, 0.0895 mol) was cooled to -23° C. under nitrogen and 2.5 M n-butyl lithium in hexanes (36 mL) was added dropwise as the temperature further cooled to -29° C. When the addition was complete, the reaction mixture was warmed to 0° C. and was stirred 1 hour at zero and was then poured onto a large excess of crushed dry ice. The mixture was stirred with a glass rod. When the dry ice had sublimed, hydrochloric acid (1N, 200 mL) was added and the mixture was extracted with ethyl ether, the ether washed with brine, dried (magnesium sulfate), filtered, and concentrated to a yellow oil. The oil was taken up in ether (200 mL), the ether solution extracted with sodium hydroxide solution (1N, 200 mL), the layers separated, the aqueous layer made acidic with 1.5N hydrochloric acid, brine added, and the aqueous layer extracted with ether (200 mL). The ether layer was washed with brine (50 mL), dried (magnesium sulfate), filtered and concentrated to an oil which solidified on standing, 13.42 g, 72.7%. When the addition the reaction mixture was warmed to 0° C. The mixture was stirred with a glass rod the mixture was extracted with ethyl ether the ether washed with brine dried (magnesium sulfate) filtered concentrated to a yellow oil the ether solution extracted with sodium hydroxide solution (1N, 200 mL) the layers separated added the aqueous layer extracted with ether (200 mL) The ether layer was washed with brine (50 mL) dried (magnesium sulfate) filtered concentrated to an oil which

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

実験手順: 6.8 ml of a 1.6M solution of butyllithium in hexane was added dropwise at -78° C. while stirring to a solution of 2.6 g of 2-bromo-1,3-diisopropylbenzene in 16 ml of tetrahydrofuran. The mixture was stirred at the same temperature for 30 minutes and thereafter treated with a solution of 1.3 g of N-formylpiperdine in 1.5 ml of tetrahydrofuran. Thereafter, the mixture was left to warm to room temperature over a period of 6 hours. The mixture was cooled to 0° C. and treated with 12 ml of 3N hydrochloric acid. The aqueous solution was extracted four times with diethyl ether and the combined organic extracts were washed with saturated sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated to dryness. The residue was chromatographed on silica gel with dichloromethane as the eluent and yielded 1.07 g of 2,6-diisopropylbenzaldehyde as an oil. Thereafter, the mixture was left The mixture was cooled to 0° C. The aqueous solution was extracted four times with diethyl ether the combined organic extracts were washed with saturated sodium chloride solution dried over anhydrous magnesium sulphate evaporated to dryness The residue was chromatographed on silica gel with dichloromethane as the eluent

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

実験手順: 6.8 ml of a 1.6M solution of butyllithium in hexane was added dropwise at -78° C. while stirring to a solution of 2.6 g of 2-bromo-1,3-diisopropylbenzene in 16 ml of tetrahydrofuran. The mixture was stirred at the same temperature for 30 minutes and thereafter treated with a solution of 1.3 g of N-formylpiperdine in 1.5 ml of tetrahydrofuran. Thereafter, the mixture was left to warm to room temperature over a period of 6 hours. The mixture was cooled to 0° C. and treated with 12 ml of 3N hydrochloric acid. The aqueous solution was extracted four times with diethyl ether and the combined organic extracts were washed with saturated sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated to dryness. The residue was chromatographed on silica gel with dichloromethane as the eluent and yielded 1.07 g of 2,6-diisopropylbenzaldehyde as an oil. Thereafter, the mixture was left The mixture was cooled to 0° C. The aqueous solution was extracted four times with diethyl ether the combined organic extracts were washed with saturated sodium chloride solution dried over anhydrous magnesium sulphate evaporated to dryness The residue was chromatographed on silica gel with dichloromethane as the eluent

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

実験手順: 2,6 diisopropylbromobenzene (see J. Org. Chem., 42(14):2426-2431 (1977) forpreparation) (30 g, 124.4 mmol) was added to a suspension of Li powder (1.9g, 273.6 mmol) in ether (100 mL) heated under reflux, the heating was continued for another 4 hours, cooled, and the mixture was poured into ethylene oxide which was precooled to -78° C. The mixture was warmed slowly to room temperature, saturated NH4Cl solution was added slowly with caution, the ether layer was separated and washed with brine, dried over MgSO4, filtered, and the solvent was evaporated to dryness. After column chromatography (3:1 hexane:ethyl acetate) pure 2,6-diisopropylphenylethanol was obtained (17 g, 6.3%); NMR (CDCl3): δ 1.2-1.3 (m, 12H) , 3.05 (t, 2H), 3.15-3.35 (m, 2H), 3.7-3.8 (t, 2H), 7.1-7.3 (m, 3H) ppm. heated under reflux cooled was precooled to -78° C the ether layer was separated washed with brine dried over MgSO4 filtered the solvent was evaporated to dryness

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

実験手順: 2,6 diisopropylbromobenzene (see J. Org. Chem., 42(14):2426-2431 (1977) forpreparation) (30 g, 124.4 mmol) was added to a suspension of Li powder (1.9g, 273.6 mmol) in ether (100 mL) heated under reflux, the heating was continued for another 4 hours, cooled, and the mixture was poured into ethylene oxide which was precooled to -78° C. The mixture was warmed slowly to room temperature, saturated NH4Cl solution was added slowly with caution, the ether layer was separated and washed with brine, dried over MgSO4, filtered, and the solvent was evaporated to dryness. After column chromatography (3:1 hexane:ethyl acetate) pure 2,6-diisopropylphenylethanol was obtained (17 g, 6.3%); NMR (CDCl3): δ 1.2-1.3 (m, 12H) , 3.05 (t, 2H), 3.15-3.35 (m, 2H), 3.7-3.8 (t, 2H), 7.1-7.3 (m, 3H) ppm. heated under reflux cooled was precooled to -78° C the ether layer was separated washed with brine dried over MgSO4 filtered the solvent was evaporated to dryness

反応条件: temp:-29.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Diisopropylbromobenzene (21.58 g, 0.0895 mol) was cooled to -23° C. under nitrogen and 2.5M n-butyl lithium in hexanes (36 mL) was added dropwise as the temperature further cooled to -29° C. When the addition was complete, the reaction mixture was warmed to 0° C. and was stirred 1 hour at zero and was then poured onto a large excess of crushed dry ice. The mixture was stirred with a glass rod. When the dry ice had sublimed, hydrochloric acid (1N, 200 mL) was added and the mixture was extracted with ethyl ether, the ether washed with brine, dried (magnesium sulfate), filtered, and concentrated to a yellow oil. The oil was taken up in ether (200 mL), the ether solution extracted with sodium hydroxide solution (1N, 200 mL), the layers separated, the aqueous layer made acidic with 1.5N hydrochloric acid, brine added, and the aqueous layer extracted with ether (200 mL). The ether layer was washed with brine (50 mL), dried (magnesium sulfate), filtered and concentrated to an oil which solidified on standing, 13.42 g, 72.7%. When the addition the reaction mixture was warmed to 0° C. The mixture was stirred with a glass rod the mixture was extracted with ethyl ether the ether washed with brine dried (magnesium sulfate) filtered concentrated to a yellow oil the ether solution extracted with sodium hydroxide solution (1N, 200 mL) the layers separated added the aqueous layer extracted with ether (200 mL) The ether layer was washed with brine (50 mL) dried (magnesium sulfate) filtered concentrated to an oil which

反応条件: temp:-29.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Diisopropylbromobenzene (21.58 g, 0.0895 mol) was cooled to -23° C. under nitrogen and 2.5M n-butyl lithium in hexanes (36 mL) was added dropwise as the temperature further cooled to -29° C. When the addition was complete, the reaction mixture was warmed to 0° C. and was stirred 1 hour at zero and was then poured onto a large excess of crushed dry ice. The mixture was stirred with a glass rod. When the dry ice had sublimed, hydrochloric acid (1N, 200 mL) was added and the mixture was extracted with ethyl ether, the ether washed with brine, dried (magnesium sulfate), filtered, and concentrated to a yellow oil. The oil was taken up in ether (200 mL), the ether solution extracted with sodium hydroxide solution (1N, 200 mL), the layers separated, the aqueous layer made acidic with 1.5N hydrochloric acid, brine added, and the aqueous layer extracted with ether (200 mL). The ether layer was washed with brine (50 mL), dried (magnesium sulfate), filtered and concentrated to an oil which solidified on standing, 13.42 g, 72.7%. When the addition the reaction mixture was warmed to 0° C. The mixture was stirred with a glass rod the mixture was extracted with ethyl ether the ether washed with brine dried (magnesium sulfate) filtered concentrated to a yellow oil the ether solution extracted with sodium hydroxide solution (1N, 200 mL) the layers separated added the aqueous layer extracted with ether (200 mL) The ether layer was washed with brine (50 mL) dried (magnesium sulfate) filtered concentrated to an oil which

反応条件: temp:-29.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Diisopropylbromobenzene (21.58 g, 0.0895 mol) was cooled to -23° C. under nitrogen and 2.5M n-butyl lithium in hexanes (36 mL) was added dropwise as the temperature further cooled to -29° C. When the addition was complete, the reaction mixture was warmed to 0° C. and was stirred 1 hour at zero and was then poured onto a large excess of crushed dry ice. The mixture was stirred with a glass rod. When the dry ice had sublimed, hydrochloric acid (1N, 200 mL) was added and the mixture was extracted with ethyl ether, the ether washed with brine, dried (magnesium sulfate), filtered, and concentrated to a yellow oil. The oil was taken up in ether (200 mL), the ether solution extracted with sodium hydroxide solution (1N, 200 mL), the layers separated, the aqueous layer made acidic with 1.5N hydrochloric acid, brine added, and the aqueous layer extracted with ether (200 mL). The ether layer was washed with brine (50 mL), dried (magnesium sulfate), filtered and concentrated to an oil which solidified on standing, 13.42 g, 72.7%. When the addition the reaction mixture was warmed to 0° C. The mixture was stirred with a glass rod the mixture was extracted with ethyl ether the ether washed with brine dried (magnesium sulfate) filtered concentrated to a yellow oil the ether solution extracted with sodium hydroxide solution (1N, 200 mL) the layers separated added the aqueous layer extracted with ether (200 mL) The ether layer was washed with brine (50 mL) dried (magnesium sulfate) filtered concentrated to an oil which

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

実験手順: 2,6 diisopropylbromobenzene (see J. Org. Chem., 42(14):2426-2431 (1977) for preparation) (30 g, 124.4 mmol) was added to a suspension of Li powder (1.9 g, 273.6 mmol) in ether (100 nIL) heated under reflux, the heating was continued for another 4 hours, cooled, and the mixture was poured into ethylene oxide which was precooled to -78° C. The mixture was warmed slowly to room temperature, saturated NH4Cl solution was added slowly with caution, the ether layer was separated and washed with brine, dried over MgSO4, filtered, and the solvent was evaporated to dryness. After column chromatography (3:1 hexane:ethyl acetate) pure 2,6-diisopropylphenylethanol was obtained (17 g, 66.3%); NMR (CDCl3):δ 1.2-1.3 (m, 12H), 3.05 (t, 3.15-3.35 (m, 2H), 3.7-3.8 (t, 2H), 7.1-7.3 (m, 3H) ppm. heated under reflux cooled was precooled to -78° C the ether layer was separated washed with brine dried over MgSO4 filtered the solvent was evaporated to dryness

反応条件: temp:-29.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Diisopropylbromobenzene (21.58 g, 0.0895 mol) was cooled to -23° C. under nitrogen and 2.5 M n-butyl lithium in hexanes (36 mL) was added dropwise as the temperature further cooled to -29° C. When the addition was complete, the reaction mixture was warmed to 0° C. and was stirred 1 hour at zero and was then poured onto a large excess of crushed dry ice. The mixture was stirred with a glass rod. When the dry ice had sublimed, hydrochloric acid (1N, 200 mL) was added and the mixture was extracted with ethyl ether, the ether washed with brine, dried (magnesium sulfate), filtered, and concentrated to a yellow oil. The oil was taken up in ether (200 mL), the ether solution extracted with sodium hydroxide solution (1N, 200 mL), the layers separated, the aqueous layer made acidic with 1.5N hydrochloric acid, brine added, and the aqueous layer extracted with ether (200 mL). The ether layer was washed with brine (50 mL), dried (magnesium sulfate), filtered and concentrated to an oil which solidified on standing, 13.42 g, 72.7%. When the addition the reaction mixture was warmed to 0° C. The mixture was stirred with a glass rod the mixture was extracted with ethyl ether the ether washed with brine dried (magnesium sulfate) filtered concentrated to a yellow oil the ether solution extracted with sodium hydroxide solution (1N, 200 mL) the layers separated added the aqueous layer extracted with ether (200 mL) The ether layer was washed with brine (50 mL) dried (magnesium sulfate) filtered concentrated to an oil which

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

実験手順: 6.8 ml of a 1.6M solution of butyllithium in hexane was added dropwise at -78° C. while stirring to a solution of 2.6 g of 2-bromo-1,3-diisopropylbenzene in 16 ml of tetrahydrofuran. The mixture was stirred at the same temperature for 30 minutes and thereafter treated with a solution of 1.3 g of N-formylpiperdine in 1.5 ml of tetrahydrofuran. Thereafter, the mixture was left to warm to room temperature over a period of 6 hours. The mixture was cooled to 0° C. and treated with 12 ml of 3N hydrochloric acid. The aqueous solution was extracted four times with diethyl ether and the combined organic extracts were washed with saturated sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated to dryness. The residue was chromatographed on silica gel with dichloromethane as the eluent and yielded 1.07 g of 2,6-diisopropylbenzaldehyde as an oil. Thereafter, the mixture was left The mixture was cooled to 0° C. The aqueous solution was extracted four times with diethyl ether the combined organic extracts were washed with saturated sodium chloride solution dried over anhydrous magnesium sulphate evaporated to dryness The residue was chromatographed on silica gel with dichloromethane as the eluent