反应详情

11.31 g (0.47 mole) of magnesium flakes were added to 300 ml of diethyl ether, followed by a small amount of iodine. The mixture was then allowed to stand for 1 hour, after which a solution of 102.87 g (0.46 mole) of 1-bromo-3,4-dichlorobenzene in 150 ml of diethyl ether was slowly added dropwise. A further 150 ml of diethyl ether was added, and then 60.33 g (44.3 mmole) of anhydrous zinc chloride was slowly added and the mixture was stirred for 1 hour. 3.10 g (4.42 mmole) of dichlorobis(triphenylphosphine)palladium (II) were then added, and a solution of 34.15 ml (42.8 mmole) of diketene in 600 ml of diethyl ether was added dropwise. The reaction mixture was then stirred at room temperature for 30 minutes, after which it was poured into 1 liter of ice-cooled 1 N aqueous hydrochloric acid and extracted three times, each time with 500 ml of diethyl ether. The combined organic extracts were extracted three times, each time with 700 ml of a 1 N aqueous solution of sodium hydroxide. The combined aqueous extracts were acidified with concentrated aqueous hydrochloric acid, whilst ice-cooling, and extracted three times, each time with 500 ml of diethyl ether, and then the combined organic extracts were dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting residue was dissolved in 350 ml of methanol. 10 ml of concentrated aqueous sulfuric acid were added, and the solution was heated under reflux for 30 minutes. At the end of this time, the reaction mixture was cooled in air and neutralised with a saturated aqueous solution of sodium hydrogencarbonate. The methanol was then removed by distillation under reduced pressure, and the resulting residue was extracted with three times, each time with 200 ml of methylene chloride. The combined organic extracts were dried over anhydrous magnesium sulfate, and then the solvent was removed by distillation under reduced pressure. The resulting residue was distilled under reduced pressure to obtain 69.13 g (yield 62%) of the title compound as a pale yellow oil, boiling at 144-146° C. (5 mm Hg).

1. stirringThe reaction mixture was then stirred at room temperature for 30 minutes
2. extractionextracted three times
3. extractionThe combined organic extracts were extracted three times
4. temperaturecooling
5. extractionextracted three times
6. dry with materialeach time with 500 ml of diethyl ether, and then the combined organic extracts were dried over anhydrous magnesium sulfate
7. customThe solvent was removed by distillation under reduced pressure
8. dissolutionthe resulting residue was dissolved in 350 ml of methanol
9. addition10 ml of concentrated aqueous sulfuric acid were added
10. temperaturethe solution was heated
11. temperatureunder reflux for 30 minutes
12. temperatureAt the end of this time, the reaction mixture was cooled in air
13. customThe methanol was then removed by distillation under reduced pressure
14. extractionthe resulting residue was extracted with three times
15. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
16. customthe solvent was removed by distillation under reduced pressure
17. distillationThe resulting residue was distilled under reduced pressure