Pentafluorophenol → Perfluoro-6-phenoxy-4-oxa-1-heptene

HRID 1702860

Reaktionsgleichung

Reaktionsgleichung von HRID 1702860
[F-].[K+].[F:3][C:4]([O:12][C:13]1[C:18]([F:19])=[C:17]([F:20])[C:16]([F:21])=[C:15]([F:22])[C:14]=1[F:23])([C:8]([F:11])([F:10])[F:9])[C:5]([F:7])=[O:6].[F:24]C1C(O)=C(F)C(F)=C(F)C=1F.S(F)(O[C:40]([F:47])([F:46])[C:41]([F:45])=[C:42]([F:44])[F:43])(=O)=O>COCCOCCOC>[F:43][C:42]([F:44])=[C:41]([F:45])[C:40]([F:47])([F:46])[O:6][C:5]([F:24])([F:7])[C:4]([F:3])([O:12][C:13]1[C:14]([F:23])=[C:15]([F:22])[C:16]([F:21])=[C:17]([F:20])[C:18]=1[F:19])[C:8]([F:11])([F:10])[F:9]

Komponenten

6

Edukt 4

HCID 13041PentafluorophenolHCID 90764Propanoyl fluoride, 2,3,3,3-tetrafluoro-2-(2,3,4,5,6-pentafluorophenoxy)-HCID 522689Potassium Fluoride2×HCID 2776028Pentafluoroallyl fluorosulphate

Produkt 1

HCID 86737799Perfluoro-6-phenoxy-4-oxa-1-hepteneAusbeute 17 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8150DiglymeLösungsmittel

Versuchsvorschrift

A suspension of 17.4 g (0.30 mol) of flame-dried KF in 500 ml of diglyme was stirred at 5° while 86.1 g (0.26 mol) of perfluoro-2-phenoxypropionyl fluoride prepared by reaction of a metal salt of pentafluorophenol with HFPO) was added dropwise. The mixture was stirred for 30 min at 5°, after which the KF had partially dissolved. Then 69.0 g (0.30 mol) of perfluoroallyl fluorosulfate was added dropwise, and the mixture was stirred at 5°-10° for 3 hr. The cooling bath was removed, and the mixture was stirred overnight. The reaction mixture was then drowned in 2 l. of water, and the lower layer was washed with 1 l., then with 500 ml of water, dried over CaSO4, filtered and distilled to afford 20.8 g (17%) of perfluoro-6-phenoxy-4-oxa-1-heptene, bp 68°-75° (10 mm). A late fraction was analyzed. IR (neat): 5.58 (CF=CF2), 6.57 and 6.80 (arom. C=C), 7.5-9 IR (neat): 5.58 (CF=CF2), 6.57 and 6.80 (arom. C=C), 7.5-9μ (CF, C--O), with a weak peak at 5.64 (--OCF=CFCF3). NMR (CCl4): 19F-77.8 (d of d of t of d, JFF 25.5, 13.7, ~13, 7.2 Hz, 2F, OCF2C=), -79.8 (m, 3F, CF3), -83.0 (m, 2F, CF2O), -91.7 (d of d of t, JFF 52.0, 39.2, 7.2 Hz, 1F, cis-CF2CF=CFF), -105.1 (d of d of t, JFF 118.0, 52.0, 25.5 Hz, 1F, trans-CF2CF=CFF), -139.9 (t of m, JFF 18.7 Hz, 1F, CF), -150.8 (m, 2F, arom. CF), -156.1 (t, JFF 21.0 Hz, 1F, arom. CF), -162.3 (m, 2F, arom. CF), and - 190.6 ppm (d of d of t of t, JFF 118.0, 39.2, 13.7, 1.6 Hz, 1F, CF2CF=). Impurity bands ascribable to the isomer C6F5OCF(CF3)CF2OCF=CFCF3 were also present.

Aufarbeitung

  1. additionwas added dropwise
  2. stirringthe mixture was stirred at 5°-10° for 3 hr
  3. customThe cooling bath was removed
  4. stirringthe mixture was stirred overnight
  5. washof water, and the lower layer was washed with 1 l
  6. dry with material, then with 500 ml of water, dried over CaSO4
  7. filtrationfiltered
  8. distillationdistilled

Quellen und Nachweise

ORD-Eintrag
ord-0320153c3d194abe9c6ec9116d7ca255
Quelldatensatz
uspto-grants-1982_09
Patentnummer
US04349650

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