Hydrochloric Acid → Gossyplure

Temperature

0 °C

1,5,9-Tetradecatriene (10 g, 0.052 mol), n-butylmagnesium chloride (24.8 mL of 2.5M in tetrahydrofuran; 0.062 mol) and titanium tetrachloride (0.52 g, 0.0027 mol) were stirred under an inert atmosphere at about 65° C. for about 4.5 hours. The reaction mixture was then cooled to 0° C. and cuprous bromide (0.14 g, 1.0 mmol) was added. 2-Bromoethyl acetate (6.9 mL, 0.063 mol) was then added dropwise and the mixture allowed to warm slowly to room temperature and stirred for several hours at room temperature. Reaction temperature was then raised to 60° C. for 4 hours before the mixture was cooled, acidified with aqueous HCl, then extracted with hexane. The hexane extract was washed with saturated sodium bicarbonate solution, dried over MgSO4, filtered and solvent removed on the rotary evaporator. GLC analysis of this crude reaction product indicated an 11% yield of gossyplure. It should be recognized that while this reaction represents successful production of gossyplure from 1,5,9 -tetradecatriene in one reaction vessel, the reaction parameters have not been optimized. Consequently, significantly improved yields of gossyplure can be expected upon optimization of various reaction parameters.

1. temperatureto warm slowly to room temperature
2. customReaction temperature
3. temperaturewas then raised to 60° C. for 4 hours before the mixture
4. temperaturewas cooled
5. extractionextracted with hexane
6. extractionThe hexane extract
7. washwas washed with saturated sodium bicarbonate solution
8. dry with materialdried over MgSO4
9. filtrationfiltered
10. customsolvent removed on the rotary evaporator
11. customGLC analysis of this crude reaction product

ORD record

ord-1f34b334c3154079baa5ace48e010c6f

Source dataset

uspto-grants-1987_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04687867