反应详情

A stirred suspension of 121.6 g (5.0 mol) of magnesium in 1 l. of anhydrous ether is treated with 0.6 g of mercuric chloride and about 100 mg of iodine. After several minutes, 3 ml of propargyl bromide is added and if no exotherm is noted, a small amount of reacting propargyl bromide and magnesium in ether is added. When the reaction begins, a mixture of 5.0 mol of cyclohexanone and 595 g (5.0 mol) of propargyl bromide is added dropwise at a rate that produces vigorous refluxing of the solution. (The propargyl bromide must always be present in some excess otherwise the reaction will stop. If this happens, the addition of about 1 ml of propargyl bromide will restart the reaction.) After about half of the propargyl bromide-cyclohexanone mixture has been added, another 500-750 ml of ether is used to dilute the reaction mixture. At the end of the addition, the reaction mixture is refluxed for at least 0.5 hour, cooled and poured into 4 liters of saturated ammonium chloride during good stirring. The ethereal layer is separated and the aqueous layer is washed with ether several times and the combined extract is washed twice with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. Evaporation of the ether yields 583 g (630 g theory) of a dark oil which is distilled giving purified 1-propargyl-1-hydroxycyclohexane.

1. waitAfter several minutes
2. additionis added dropwise at a rate that
3. customproduces vigorous
4. temperaturerefluxing of the solution
5. customthe reaction
6. additionto dilute the reaction mixture
7. additionAt the end of the addition
8. temperaturethe reaction mixture is refluxed for at least 0.5 hour
9. temperaturecooled
10. customThe ethereal layer is separated
11. washthe aqueous layer is washed with ether several times
12. extractionthe combined extract
13. washis washed twice with saturated sodium chloride solution
14. dry with materialdried over anhydrous magnesium sulfate
15. customEvaporation of the ether
16. customyields 583 g (630 g theory) of a dark oil which
17. distillationis distilled
18. customgiving
19. custompurified 1-propargyl-1-hydroxycyclohexane