反应 #1720619

反应方程式

sodium hydride

5-Norbornene-2-methanol

1,1-Bis(trifluoromethyl)ethylene oxide

1,1-bis(trifluoromethyl)ethylene oxide

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title product

收率 88.0%

3-[(Bicyclo[2.2.1]hept-5-en-2-yl)methoxy]-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanol

收率 88.0%

溶剂

DMF

反应条件

后处理

1. 1
   workup.STIRRINGThe resulting mixture was stirred for 72 hr at room temperature
2. 2
   其他DMF was evaporated on a rotary evaporator at 45° C.
3. 3
   workup.ADDITIONThe residue was diluted with 300 ml of ice water containing 30 ml of glacial acetic acid
4. 4
   其他A lower layer was separated
5. 5
   萃取the aqueous layer was extracted with 2×25 ml of methylene chloride
6. 6
   洗涤The combined organic layers were washed with 3×100 ml of water
7. 7
   干燥dried over anhydrous magnesium chloride
8. 8
   过滤filtered
9. 9
   workup.DISTILLATIONdistilled under vacuum in a Kugelrohr apparatus at 65-87° C.
10. 10
    workup.DISSOLUTIONwas dissolved in 100 ml of hexane
11. 11
    洗涤washed with 4×200 ml water
12. 12
    干燥dried over anhydrous magnesium sulfate
13. 13
    过滤filtered
14. 14
    workup.DISTILLATIONdistilled in a Kugelrohr apparatus at 70-80° C.

实验过程

A dry round bottom flask with mechanical stirrer and condenser was charged under nitrogen with 28.8 g (1.2 mol) of 95% sodium hydride and 400 ml of anhydrous DMF (N,N′-dimethylformamide). 5-Norbornene-2-methanol (108.6 g, 0.875 mol) was added dropwise at room temperature over 0.5 hr. The resulting mixture was stirred for 3 hr. 1,1-Bis(trifluoromethyl)ethylene oxide (1, Hexafluoroisobutylene epoxide) (173.2 g, 0.96 mol) from Example 1 was added dropwise over 2 hr. The resulting mixture was stirred for 72 hr at room temperature. DMF was evaporated on a rotary evaporator at 45° C. and 1 mm. The residue was diluted with 300 ml of ice water containing 30 ml of glacial acetic acid. A lower layer was separated and the aqueous layer was extracted with 2×25 ml of methylene chloride. The combined organic layers were washed with 3×100 ml of water, dried over anhydrous magnesium chloride, filtered and distilled under vacuum in a Kugelrohr apparatus at 65-87° C. and 0.1 mm. An NMR spectrum revealed that the product was contaminated with small amounts of DMF so it was dissolved in 100 ml of hexane, washed with 4×200 ml water, dried over anhydrous magnesium sulfate, filtered and distilled in a Kugelrohr apparatus at 70-80° C. and 0.1 mm giving 233.9 g (88%) of the title product (3-[(bicyclo[2.2.1]hept-5-en-2-yl)methoxy]-1,1,1-trifluoro-2-(trifluoromethyl)-2-propanol, comonomer 2). In another preparation, the product was distilled through a 12″ Vigreux column indicating a bp of 52-53° C. at 0.1 mm. 1H NMR (δ, CD2Cl2) 0.5 to 4.3 (complex multiplets, 12 H), 5.90, 6.19 and 6.26 (m, 2H). 19F NMR (δ, CD2Cl2) −77.4 (s).

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