反应详情

38 ml of a 1M solution of ethyl magnesium bromide in THF were added dropwise, at room temperature, to a solution of 5 grams of 1-decyne in 15 ml of anhydrous THF, under an inert atmosphere. With the addition complete, the mixture was maintained under stirring for 30 min at room temperature and then heated under reflux for 1 h 30 min. The mixture was cooled to room temperature and then 286 mg of copper(I) chloride were added and the mixture was again heated under reflux for 1 hour. It was then cooled to between 40° C. and 50° C. and 12.5 g of 1,4-dichloro-2-butyne dissolved in 25 ml of anhydrous THF were added. The mixture was refluxed for 1 hour and then maintained under stirring for 15 h at room temperature before heating again under reflux for 2 h. The reaction medium was then cooled to 4° C. and hydrolyzed with care with a saturated aqueous solution of NH4Cl. The medium was then extracted 3 times with diethyl ether and the combined organic phases were washed 3 times with water and then with a saturated aqueous solution of NaCl before being dried over Na2SO4, filtered and concentrated under vacuum in a rotary evaporator. The oily residue containing 1,4-dichloro-2-butyne in excess was purified by distillation under reduced pressure to give 1-chloro-2,5-tetradecadiyne (b.p.=111-114° C., 0.36 mbar) in the form of an orange-colored oil (yield 52.4%).

1. temperatureWith the addition complete, the mixture was maintained
2. temperatureheated
3. temperatureunder reflux for 1 h 30 min
4. temperatureThe mixture was cooled to room temperature
5. temperaturethe mixture was again heated
6. temperatureunder reflux for 1 hour
7. temperatureIt was then cooled to between 40° C. and 50° C.
8. additionwere added
9. temperatureThe mixture was refluxed for 1 hour
10. temperaturemaintained
11. stirringunder stirring for 15 h at room temperature
12. temperaturebefore heating again
13. temperatureunder reflux for 2 h
14. extractionThe medium was then extracted 3 times with diethyl ether
15. washthe combined organic phases were washed 3 times with water
16. dry with materialwith a saturated aqueous solution of NaCl before being dried over Na2SO4
17. filtrationfiltered
18. concentrationconcentrated under vacuum in a rotary evaporator
19. additionThe oily residue containing 1,4-dichloro-2-butyne
20. distillationin excess was purified by distillation under reduced pressure