반응 #501164

반응 방정식

magnesium

iodine

t-butylacetylene

magnesium

ethane

ethyl bromide

acrolein

→

6,6-dimethylhept-1-en-4-yn-3-ol

수율 48.5%

용매

toluene

tetrahydrofuran

toluene

toluene

toluene

반응 조건

후처리

1. 1
   기타At dry
2. 2
   기타(−60° C)
3. 3
   온도The mixture was heated to 450-50° C.
4. 4
   workup.ADDITIONwas added dropwise
5. 5
   기타had practically been consumed
6. 6
   온도The mixture was cooled
7. 7
   workup.ADDITIONwas added gradually
8. 8
   기타Progress of the reaction
9. 9
   온도The reaction mixture was cooled to 0° C.-5° C.
10. 10
    workup.ADDITIONwas added gradually during 1 hour
11. 11
    온도The mixture was heated to room temperature
12. 12
    workup.STIRRINGstirred for 4 hours
13. 13
    기타The reaction mixture was quenched with ammonium chloride solution
14. 14
    기타The phases were separated
15. 15
    추출The organic phase was extracted with toluene (3×50 ml)
16. 16
    세척The combined organic phases were washed with water to neutrality
17. 17
    기타The solution was dried
18. 18
    기타The crude product was obtained (20.2 gr., 65% yield)
19. 19
    workup.DISTILLATIONThe crude product was distilled (boiling point 68° C.-69.5° C. at 12 mbar)

실험 절차

At dry and inert atmosphere, magnesium (6.4 gr., 0.26 mole) was heated with a trace of iodine until brown vapors evolved (−60° C). It was cooled down to room temperature and toluene (300 ml) and tetrahydrofuran (30 ml) were added. The mixture was heated to 450-50° C. and a mixture of ethyl bromide (30 gr., 0.26 mole) and toluene (30 ml) was added dropwise. The mixture was stirred at 50° C. until all the magnesium had practically been consumed. The mixture was cooled and a mixture of t-butylacetylene (20 gr., 0.24 mole) mixed with toluene (20 ml) was added gradually. The mixture was stirred at 30°-40° C. for 4-6 hours. Progress of the reaction could be monitored by the evolution of ethane. The reaction mixture was cooled to 0° C.-5° C. and a mixture of acrolein (stabilized by hydroquinone) (14 gr., 0.25 mole) diluted with toluene (20 ml) was added gradually during 1 hour. The mixture was heated to room temperature and stirred for 4 hours. The reaction mixture was quenched with ammonium chloride solution. The phases were separated. The organic phase was extracted with toluene (3×50 ml). The combined organic phases were washed with water to neutrality. The solution was dried and the solvent stripped. The crude product was obtained (20.2 gr., 65% yield). The crude product was distilled (boiling point 68° C.-69.5° C. at 12 mbar) to give pure 6,6-dimethylhept-1-en-4-yn-3-ol (16.1 gr., 48%).

출처