4-bromo-N,N-diethylaniline

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen stream, a solution of magnesium (5.3 g, 1.00 equivalent), a small amount of iodine and a small amount of 1,2-dibromoethane in tetrahydrofuran (30 mL) was stirred at room temperature for 30 min. A solution of 4-bromo-N,N-diethylaniline (49.7 g, 0.217 moL) in tetrahydrofuran (100 mL) was added to the mixture at 25° C. to 35° C. over 1 hr, and the mixture was stirred at 40° C. for 40 min. Then, a solution of diethyl phosphite (9.20 g, 0.30 equivalent) in tetrahydrofuran (20 mL) was added to the mixture at 20° C. to 25° C. for 15 min. 6M Hydrochloric acid (30 mL) and water (30 mL) were added to the mixture at 3° C. to 15° C., and then ethyl acetate (100 mL) was added thereto. The mixture was partitioned, and the organic layer was washed successively with water (30 mL), 5%-aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL), dried over anhydrous magnesium sulfate and filtered naturally. Then, the organic layer was concentrated under reduced pressure. The residue was recrystallized from n-heptane to give the title compound (19.82 g, white crystals). yield 87%. melting point 129.1° C. The mixture was partitioned the organic layer was washed successively with water (30 mL), 5%-aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL) dried over anhydrous magnesium sulfate filtered naturally Then, the organic layer was concentrated under reduced pressure The residue was recrystallized from n-heptane

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen stream, a solution of magnesium (5.3 g, 1.00 equivalent), a small amount of iodine and a small amount of 1,2-dibromoethane in tetrahydrofuran (30 mL) was stirred at room temperature for 30 min. A solution of 4-bromo-N,N-diethylaniline (49.7 g, 0.217 moL) in tetrahydrofuran (100 mL) was added to the mixture at 25° C. to 35° C. over 1 hr, and the mixture was stirred at 40° C. for 40 min. Then, a solution of diethyl phosphite (9.20 g, 0.30 equivalent) in tetrahydrofuran (20 mL) was added to the mixture at 20° C. to 25° C. for 15 min. 6M Hydrochloric acid (30 mL) and water (30 mL) were added to the mixture at 3° C. to 15° C., and then ethyl acetate (100 mL) was added thereto. The mixture was partitioned, and the organic layer was washed successively with water (30 mL), 5%-aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL), dried over anhydrous magnesium sulfate and filtered naturally. Then, the organic layer was concentrated under reduced pressure. The residue was recrystallized from n-heptane to give the title compound (19.82 g, white crystals). yield 87%. melting point 129.1° C. The mixture was partitioned the organic layer was washed successively with water (30 mL), 5%-aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL) dried over anhydrous magnesium sulfate filtered naturally Then, the organic layer was concentrated under reduced pressure The residue was recrystallized from n-heptane

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness

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

Procedure: After adding dropwise 100 ml of a benzene solution containing 8 g of acetophenone to a tetrahydrofuran solution of 4-diethylaminophenylmagnesium bromide prepared from 2 g of magnesium, 16 g of 4-bromodiethylaniline, and 100 ml of tetrahydrofuran, stirring was continued under reflux for 5 hours. After cooling, 200 ml of a saturated aqueous ammonium chloride solution was added thereto. The mixture was subjected to hydrolysis, and an organic layer was separated and washed with water. After distilling off the solvent, the residue was dissolved in benzene, and the solution was stirred and refluxed with the addition of 0.1 g of p-toluenesulfonic acid for one hour. After distilling off the solvent, the residue was dissolved in benzene, and the product was separated and purified by silica gel column chromatography. under reflux for 5 hours After cooling The mixture was subjected to hydrolysis an organic layer was separated washed with water After distilling off the solvent the residue was dissolved in benzene the solution was stirred refluxed with the addition of 0.1 g of p-toluenesulfonic acid for one hour After distilling off the solvent the residue was dissolved in benzene the product was separated purified by silica gel column chromatography

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

Procedure: After adding dropwise 100 ml of a benzene solution containing 8 g of acetophenone to a tetrahydrofuran solution of 4-diethylaminophenylmagnesium bromide prepared from 2 g of magnesium, 16 g of 4-bromodiethylaniline, and 100 ml of tetrahydrofuran, stirring was continued under reflux for 5 hours. After cooling, 200 ml of a saturated aqueous ammonium chloride solution was added thereto. The mixture was subjected to hydrolysis, and an organic layer was separated and washed with water. After distilling off the solvent, the residue was dissolved in benzene, and the solution was stirred and refluxed with the addition of 0.1 g of p-toluenesulfonic acid for one hour. After distilling off the solvent, the residue was dissolved in benzene, and the product was separated and purified by silica gel column chromatography. under reflux for 5 hours After cooling The mixture was subjected to hydrolysis an organic layer was separated washed with water After distilling off the solvent the residue was dissolved in benzene the solution was stirred refluxed with the addition of 0.1 g of p-toluenesulfonic acid for one hour After distilling off the solvent the residue was dissolved in benzene the product was separated purified by silica gel column chromatography

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under a nitrogen stream, a solution of magnesium (5.3 g, 1.00 equivalent), a small amount of iodine and a small amount of 1,2-dibromoethane in tetrahydrofuran (30 mL) was stirred at room temperature for 30 min. A solution of 4-bromo-N,N-diethylaniline (49.7 g, 0.217 moL) in tetrahydrofuran (100 mL) was added to the mixture at 25° C. to 35° C. over 1 hr, and the mixture was stirred at 40° C. for 40 min. Then, a solution of diethyl phosphite (9.20 g, 0.30 equivalent) in tetrahydrofuran (20 mL) was added to the mixture at 20° C. to 25° C. for 15 min. 6M Hydrochloric acid (30 mL) and water (30 mL) were added to the mixture at 3° C. to 15° C., and then ethyl acetate (100 mL) was added thereto. The mixture was partitioned, and the organic layer was washed successively with water (30 mL), 5%-aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL), dried over anhydrous magnesium sulfate and filtered naturally. Then, the organic layer was concentrated under reduced pressure. The residue was recrystallized from n-heptane to give the title compound (19.82 g, white crystals). yield 87%. melting point 129.1° C. The mixture was partitioned the organic layer was washed successively with water (30 mL), 5%-aqueous sodium hydrogen carbonate solution (30 mL) and saturated brine (30 mL) dried over anhydrous magnesium sulfate filtered naturally Then, the organic layer was concentrated under reduced pressure The residue was recrystallized from n-heptane

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

Procedure: 93 g of bromine were added dropwise to a solution of 86 g of N,N-diethylaniline in 400 ml of acetic acid and the mixture was poured into an ice-water mixture. The mixture was extracted with methylene chloride and the organic phase was washed with aqueous sodium bicarbonate solution, dried and evaporated to dryness to obtain 125 g of 4-(N,N-diethylamino)-bromobenzene boiling at 97° C. at 0.6 mm Hg. The mixture was extracted with methylene chloride the organic phase was washed with aqueous sodium bicarbonate solution dried evaporated to dryness