反応 #4819

反応方程式

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

収率 2.1%

溶媒

dimethylformamide

diethylether

water

diethylether

brine

diethylether

diethylether

反応条件

後処理

1. 1
   温度cooled to -70°
2. 2
   workup.ADDITIONmole) was then added dropwise at such a rate that the temperature of the reaction mixture
3. 3
   その他did not exceed -65°
4. 4
   workup.ADDITIONWhen the addition
5. 5
   その他did 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
   その他the aqueous layer was separated
10. 10
    抽出extracted with diethylether (2×25 ml)
11. 11
    乾燥The combined diethylether extracts were dried (MgSO4)
12. 12
    その他evaporated
13. 13
    その他to give a pale yellow liquid which
14. 14
    workup.STIRRINGStirring
15. 15
    workup.WAITwas continued for 2.5 hours at room temperature
16. 16
    その他The aqueous layer was separated
17. 17
    抽出extracted with diethylether (2×50 ml)
18. 18
    乾燥the combined diethylether extracts were dried (MgSO4)
19. 19
    その他evaporated
20. 20
    その他flash chromatographed on silica (230-400 mesh)
21. 21
    洗浄eluting with ethyl acetate

実験手順

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.

出典