反应详情

温度

-30 °C

Well-dried butoxyltriphenylphosphonium bromide (58.1 g) and THF (200 ml) were mixed under a nitrogen atmosphere and cooled to −30° C. Then, potassium t-butoxide (t-BuOK; 16.3 g) was put in thereto in twice in the temperature range of −30° C. to 20° C. After the mixture had been stirred at −20° C. for 30 minutes, the compound (37) (20.0 g) dissolved in THF (100 ml) was added dropwise thereto in the temperature range of −30° C. to −20° C. After the reaction mixture had been stirred at −10° C. for 30 minutes, it was poured into a mixture of water (400 ml) and toluene (400 ml), and mixed. The mixture was then allowed to stand until it had separated into two phases of organic and aqueous phases, and an extractive operation was carried out. The organic phase obtained was fractionated, washed with water, and then dried over anhydrous magnesium sulfate. The solution obtained was concentrated under reduced pressure, and the residue obtained was purified with a fractional operation by means of column chromatography using toluene as the eluent and silica gel as the stationary phase powder. The eluent obtained was concentrated under reduced pressure. The residue was mixed with sodium benzenesulfonate dihydrate (31.0 g) and Solmix A-11 (100 ml), and heated under reflux for 8 hours. The reaction mixture was cooled to 30° C., and then water (200 ml) and toluene (200 ml) were added and mixed thereto. The mixture was then allowed to stand until it had separated into two phases of organic and aqueous phases, and an extractive operation was carried out. The organic phase obtained was fractionated, washed with water, a saturated aqueous solution of sodium hydrogencarbonate and water, and then dried over anhydrous magnesium sulfate. The solution obtained was concentrated under reduced pressure, and the residue obtained was purified with a fractional operation by means of column chromatography using a mixed solvent of toluene and heptane (volume ratio; toluene: heptane=1:1) as the eluent and silica gel as the stationary phase powder. The residue was further purified by means of recrystallization from Solmix A-11, and dried, giving 15.8 g of 1-(3-fluorophenyl)-trans-4-(1-pentenyl)cyclohexane (40). The yield based on the compound (37) was 66.2%.

1. customtwice in the temperature range of −30° C. to 20° C
2. additionwas added dropwise
3. customin the temperature range of −30° C. to −20° C
4. stirringAfter the reaction mixture had been stirred at −10° C. for 30 minutes
5. additionmixed
6. customhad separated into two phases of organic and aqueous phases
7. customThe organic phase obtained
8. washwashed with water
9. dry with materialdried over anhydrous magnesium sulfate
10. customThe solution obtained
11. concentrationwas concentrated under reduced pressure
12. customthe residue obtained
13. customwas purified with a fractional operation by means of column chromatography
14. customThe eluent obtained
15. concentrationwas concentrated under reduced pressure
16. additionThe residue was mixed with sodium benzenesulfonate dihydrate (31.0 g) and Solmix A-11 (100 ml)
17. temperatureheated
18. temperatureunder reflux for 8 hours
19. temperatureThe reaction mixture was cooled to 30° C.
20. additionwater (200 ml) and toluene (200 ml) were added
21. additionmixed
22. customhad separated into two phases of organic and aqueous phases
23. customThe organic phase obtained
24. washwashed with water
25. dry with materiala saturated aqueous solution of sodium hydrogencarbonate and water, and then dried over anhydrous magnesium sulfate
26. customThe solution obtained
27. concentrationwas concentrated under reduced pressure
28. customthe residue obtained
29. customwas purified with a fractional operation by means of column chromatography
30. customThe residue was further purified by means of recrystallization from Solmix A-11
31. customdried