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0 °C

A 12 l flask equipped with a reflux condenser, Firestone valve, mechanical stirrer, and addition funnel was flushed with N2. 500 g of oleyl alcohol and 1500 ml of tetrahydrofuran were added to the flask and the reaction mixture was cooled to 0° C. 1330 ml of n-butyllithium (1.6M in hexane) was added dropwise while maintaining the temperature below 5° C. The addition of butyllithium was completed in approximately 45 min. 420.6 g of p-toluenesulfonyl chloride was then added and the temperature was increased to 35°-40° C. using a heating mantle. The temperature was held at 40° C. for 3 hr. The reaction mixture was then cooled to 0° C. using a dry ice/isopropanol bath. 10 g of cuprous bromide was added followed by the dropwise addition of 1120 ml of n-pentylmagnesium bromide (2.5M in diethyl ether). This addition was completed in 48 min and the temperature was maintained near 0° C. during this time. The reaction mixture was stirred for 1 hr following the addition of n-pentylmagnesium bromide, then warmed to room temperature and held overnight under N2. 6.5 l of 4M HCl was added followed by phase separation. The organic phase was washed with 3 l of saturated sodium bicarbonate solution, followed by 2 volumes of a 1M KOH/MeOH solution (an aqueous KOH/MeOH solution as prepared by mixing one part of methanol and one part of water, with a final KOH concentration of 1M) the aqueous phase is then decanted. The organic solvent was removed by rotor evaporation and the residue distilled at 0.1 mm Hg vacuum. The distilled yield based on pure oleyl alcohol was 92.3%, with the final product containing 75% cis isomer.

1. customA 12 l flask equipped with a reflux condenser
2. additionFirestone valve, mechanical stirrer, and addition funnel
3. customwas flushed with N2
4. addition500 g of oleyl alcohol and 1500 ml of tetrahydrofuran were added to the flask
5. addition1330 ml of n-butyllithium (1.6M in hexane) was added dropwise
6. temperaturewhile maintaining the temperature below 5° C
7. additionThe addition of butyllithium
8. addition420.6 g of p-toluenesulfonyl chloride was then added
9. temperaturethe temperature was increased to 35°-40° C.
10. waitThe temperature was held at 40° C. for 3 hr
11. temperatureThe reaction mixture was then cooled to 0° C.
12. addition10 g of cuprous bromide was added
13. additionfollowed by the dropwise addition of 1120 ml of n-pentylmagnesium bromide (2.5M in diethyl ether)
14. additionThis addition
15. waitwas completed in 48 min
16. temperaturethe temperature was maintained near 0° C. during this time
17. additionthe addition of n-pentylmagnesium bromide
18. temperaturewarmed to room temperature
19. waitheld overnight under N2
20. addition6.5 l of 4M HCl was added
21. customfollowed by phase separation
22. washThe organic phase was washed with 3 l of saturated sodium bicarbonate solution
23. customas prepared
24. customwith a final KOH concentration of 1M) the aqueous phase is then decanted
25. customThe organic solvent was removed by rotor evaporation
26. distillationthe residue distilled at 0.1 mm Hg vacuum
27. customThe distilled yield