ethoxybenzene

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:

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:

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:

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

実験手順: 25.1 g of 1-p-ethylphenyl-2-nitro-1-hexanol and 14.6 g of ethoxybenzene are dissolved in 80 ml of methylene chloride, and the solution is added dropwise at 0° C, with vigorous stirring, to 90 g of conc. sulphuric acid and 10 ml of water. After 2 hours' stirring at room temperature, the mixture is poured on to 400 ml of ice water. The product is taken up in methylene chloride and washed with saturated sodium bicarbonate solution. After the solvent has been removed by evaporation, the oil remaining behind is dried in high vacuum at 60° C for 2 hours. There is obtained the compound of the formula ##STR7## as viscous, dark yellow oil having a refractive index of nD22 = 1.5452. washed with saturated sodium bicarbonate solution After the solvent has been removed by evaporation the oil remaining behind is dried in high vacuum at 60° C for 2 hours There is obtained the compound of the formula ##STR7## as viscous, dark yellow oil

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: To a stirred suspension of commercial 5-bromo-2-chlorobenzoic acid (250 g, 1.06 mol) in 450 mL of CH2Cl2 containing oxalyl chloride (1.1 mol) was added 1.5 mL of DMF. Once the vigorous evolution of gas ceased, the reaction was stirred overnight prior to removal of the volatiles under vacuum using a rotary evaporator. After dissolving the crude 5-bromo-2-chlorobenzoyl chloride in 200 ml of CH2Cl2, the yellow solution was transferred to a 2 L 3-neck flask equipped with an overhead stirrer and an internal thermometer. The stirred mixture was cooled to −3° prior to adding phenetole (130 g, 1.08 mol). AlCl3 (140 g, 1.07 mol) was added via a solid addition funnel over 30 min to insure that the temperature did not exceed 4°. The copious amounts of HCl gas which began to evolve after 60% of the AlCl3 had been added were trapped by passing the gas over a stirred conc. NaOH solution. HPLC revealed the reaction to be 95% complete 10 minutes after the addition was finished. After the mixture was stirred at 4° for 1 hr, the reaction was quenched by pouring over ice. Subsequently, the suspension was diluted with H2O (1 L ) and extracted 3× with CH2Cl2. The combined organic extracts were washed 2× with 1N HCl, 1× with H2O, 2× with 1M NaOH, and 2× with brine prior to drying over Na2SO4. After removal of the volatiles, HPLC revealed the residue to be a 1:7 mixture of ortho/para isomers. Recrystallization 2× from 400 mL of absolute EtOH yielded 230 g (64%) of 5-bromo-2-chloro-4′-ethoxybenzophenone. to removal of the volatiles under vacuum a rotary evaporator After dissolving the crude 5-bromo-2-chlorobenzoyl chloride in 200 ml of CH2Cl2 the yellow solution was transferred to a 2 L 3-neck flask equipped with an overhead stirrer The stirred mixture was cooled to −3° did not exceed 4° had been added the reaction 95% complete 10 minutes after the addition After the mixture was stirred at 4° for 1 hr the reaction was quenched by pouring over ice Subsequently, the suspension was diluted with H2O (1 L ) extracted 3× with CH2Cl2 The combined organic extracts were washed 2× with 1N HCl, 1× with H2O, 2× with 1M NaOH, and 2× with brine to drying over Na2SO4 After removal of the volatiles, HPLC a 1:7 mixture of ortho/para isomers Recrystallization 2× from 400 mL of absolute EtOH