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

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).

1. stirringThe resulting mixture was stirred for 72 hr at room temperature
2. customDMF was evaporated on a rotary evaporator at 45° C.
3. additionThe residue was diluted with 300 ml of ice water containing 30 ml of glacial acetic acid
4. customA lower layer was separated
5. extractionthe aqueous layer was extracted with 2×25 ml of methylene chloride
6. washThe combined organic layers were washed with 3×100 ml of water
7. dry with materialdried over anhydrous magnesium chloride
8. filtrationfiltered
9. distillationdistilled under vacuum in a Kugelrohr apparatus at 65-87° C.
10. dissolutionwas dissolved in 100 ml of hexane
11. washwashed with 4×200 ml water
12. dry with materialdried over anhydrous magnesium sulfate
13. filtrationfiltered
14. distillationdistilled in a Kugelrohr apparatus at 70-80° C.

ORD record

ord-589ef9aafb764c77a3134f3612bd2bec

Source dataset

uspto-grants-2003_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06503686B1