反应详情

A suspension of 35.9 g (0.617 mol) of flame-dried KF in 750 ml of diglyme was stirred at 0° while 140.0 g (0.617 mol) of 3-bromotetrafluoropropionyl fluoride from part B was added. The mixture was stirred at 0°-5° for another 30 min and then was treated with 141.9 g (0.617 mol) of perfluoroallyl fluorosulfate. The reaction mixture was stirred for 4 h at 0°-5° and then poured into 3 liters of water. The resulting lower layer was washed with 500 ml of water, dried over CaSO4, and distilled to give 132.5 g (57%) of perfluoro(7-bromo4-oxa-1-heptene), bp 96°-99°, trace impurity only by GC. A sample from a similar synthesis was analyzed. IR (CCl4): 5.59μ (CF=CF2). NMR (CCl4): 19F -64.4 (t of m, JFF 9.9 Hz, 2 F, CFBr), -71.9 (d of d of t of d, JFF 24.9, 13.8, ~13, 7.3 Hz, 2F, OCF2C=), -82.8 (t of t of m, JFF ~13, 9.9 Hz, 2F, CF2O), -92.0 (d of d of t of t, JFF 52.0, 39.3, 7.3 Hz, 1F, cis-CF2CF=CFF), -105.3 (d of d of t, JFF 117.7, 52.0, 24.9 Hz, 1F, trans-CF2CF=CFF), -121.9 (m, 2F, CF2), and -190.6 ppm (d of d of t of t, JFF 117.7, 39.3, 13.8, 1.6 Hz, 1F, CF2CF=).

1. additionwas added
2. stirringThe reaction mixture was stirred for 4 h at 0°-5°
3. washThe resulting lower layer was washed with 500 ml of water
4. dry with materialdried over CaSO4
5. distillationdistilled