반응 #4819

반응 방정식

1,2,4-triazole

potassium carbonate

1,3-dichloroacetone

ammonium chloride

phenylmagnesium bromide

heptafluoropropyl iodide

→

2-heptafluoropropyl-2-(1H-1,2,4-triazol-1-ylmethyl)oxirane

수율 2.1%

용매

dimethylformamide

diethylether

water

diethylether

brine

diethylether

diethylether

반응 조건

후처리

1. 1
   온도cooled to -70°
2. 2
   workup.ADDITIONmole) was then added dropwise at such a rate that the temperature of the reaction mixture
3. 3
   기타did not exceed -65°
4. 4
   workup.ADDITIONWhen the addition
5. 5
   기타did not exceed -65°
6. 6
   workup.ADDITIONWhen the addition
7. 7
   workup.STIRRINGstirring
8. 8
   workup.WAITwas continued at -70° for 1 hour
9. 9
   기타the aqueous layer was separated
10. 10
    추출extracted with diethylether (2×25 ml)
11. 11
    건조The combined diethylether extracts were dried (MgSO4)
12. 12
    기타evaporated
13. 13
    기타to give a pale yellow liquid which
14. 14
    workup.STIRRINGStirring
15. 15
    workup.WAITwas continued for 2.5 hours at room temperature
16. 16
    기타The aqueous layer was separated
17. 17
    추출extracted with diethylether (2×50 ml)
18. 18
    건조the combined diethylether extracts were dried (MgSO4)
19. 19
    기타evaporated
20. 20
    기타flash chromatographed on silica (230-400 mesh)
21. 21
    세척eluting with ethyl acetate

실험 절차

A solution of heptafluoropropyl iodide (14.58 g, 49.2 m.mole) in diethylether (65 ml) was stirred and cooled to -70°. A solution of phenylmagnesium bromide in diethylether (15.75 ml of a 3 molar solution; 47.25 m.mole) was then added dropwise at such a rate that the temperature of the reaction mixture did not exceed -65°. When the addition was complete, stirring was continued for 15 minutes and a solution of 1,3-dichloroacetone (5 g, 39.4 m.mole) in diethylether was then added dropwise, again at such a rate that the temperature of the reaction mixture did not exceed -65°. When the addition was complete, stirring was continued at -70° for 1 hour and then a saturated aqueous solution of ammonium chloride (50 ml) was added. The reaction mixture was allowed to warm to room temperature, water (25 ml) was added, and the aqueous layer was separated and extracted with diethylether (2×25 ml). The combined diethylether extracts were dried (MgSO4) and evaporated to give a pale yellow liquid which was immediately added to a stirred mixture of 1,2,4-triazole (2.7 g, 39.4 m.mole), anhydrous potassium carbonate (10.8 g, 78.75 m.mole) and dimethylformamide (DMF) (125 ml). Stirring was continued for 2.5 hours at room temperature and the reaction mixture was then poured into a mixture of diethylether (250 ml) and brine (800 ml). The aqueous layer was separated and extracted with diethylether (2×50 ml) and the combined diethylether extracts were dried (MgSO4) and evaporated. The residue was then flash chromatographed on silica (230-400 mesh), eluting with ethyl acetate to give, as a pale brown solid, 2-heptafluoropropyl-2-(1H-1,2,4-triazol-1-ylmethyl)oxirane (240 mg), which was used immediately in the next step.

출처