반응 #648962

반응 방정식

copper (I) cyanide

isobutylmagnesium bromide

n-butyl lithium

allyl bromide

tert-butyl 5-bromo-2-chlorobenzoate

→

title compound

tert-Butyl 5-allyl-2-chlorobenzoate

용매

THF

반응 조건

후처리

1. 1
   온도the reaction mixture was cooled to −40° C.
2. 2
   workup.ADDITIONwas added
3. 3
   workup.STIRRINGThe resulting suspension was stirred at −40° C. for 15 min
4. 4
   workup.STIRRINGAfter stirring at −40° C. for another 2 h
5. 5
   기타the reaction mixture was quenched with sat. aq. NH4Cl
6. 6
   온도warmed to RT
7. 7
   workup.ADDITIONThe biphasic mixture was poured into more sat. aq. NH4Cl
8. 8
   추출extracted with ether
9. 9
   세척The combined organic extracts were washed with brine
10. 10
    건조dried over MgSO4
11. 11
    여과filtered
12. 12
    기타Concentration of the filtrate in vacuo afforded a brown oil
13. 13
    기타Purification of the crude product
14. 14
    기타thus obtained by way of flash chromatography (SiO2, Hex→19:1 (v/v) Hex:ether)

실험 절차

At 0° C., isobutylmagnesium bromide (2.0 M ether solution, 1.2 eq.) and n-butyl lithium (2.5 M hexane solution, 2.4 eq.) were added to anhydrous THF (0.3 M). After stirring at 0° C. for 30 min, the reaction mixture was cooled to −40° C. and tert-butyl 5-bromo-2-chlorobenzoate from the previous step (1 eq.) was added over 15 min. The now red solution was stirred at −40° C. for 1 h before copper (I) cyanide (30% loading) was added. The resulting suspension was stirred at −40° C. for 15 min and then added allyl bromide (3 eq.). After stirring at −40° C. for another 2 h, the reaction mixture was quenched with sat. aq. NH4Cl and warmed to RT. The biphasic mixture was poured into more sat. aq. NH4Cl and extracted with ether. The combined organic extracts were washed with brine, dried over MgSO4 and filtered. Concentration of the filtrate in vacuo afforded a brown oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→19:1 (v/v) Hex:ether) afforded the title compound as a light yellow oil.

출처