Diglyme → Perfluoro-3-(octyloxy)propene

HRID 1578341Notes

Reaction equation

HRID 1578341 reaction equation
[F-:1].[K+].COCCOCCOC.[F:12][C:13]([F:36])([C:32]([F:35])([F:34])[F:33])[C:14]([F:31])([F:30])[C:15]([F:29])([F:28])[C:16]([F:27])([F:26])[C:17]([F:25])([F:24])[C:18]([F:23])([F:22])[C:19]([F:21])=[O:20].S(F)(O[C:41]([F:48])([F:47])[C:42]([F:46])=[C:43]([F:45])[F:44])(=O)=O>O>[F:44][C:43]([F:45])=[C:42]([F:46])[C:41]([F:48])([F:47])[O:20][C:19]([F:1])([F:21])[C:18]([F:23])([F:22])[C:17]([F:25])([F:24])[C:16]([F:27])([F:26])[C:15]([F:28])([F:29])[C:14]([F:30])([F:31])[C:13]([F:36])([F:12])[C:32]([F:33])([F:34])[F:35]

Participants

6

Reactant 4

HCID 8150DiglymeHCID 67634Octanoyl fluoride, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-HCID 522689Potassium FluorideHCID 2776028Pentafluoroallyl fluorosulphate

Product 1

HCID 20525317Perfluoro-3-(octyloxy)propeneYield 80%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

A mixture of potassium fluoride (5.80 g, 0.10 mol), diglyme (150 ml) and pentadecafluorooctanoyl fluoride (prepared by treating commercial perfluorooctanoic acid with sulfur tetrafluoride) (25.0 g, 0.06 mol) was stirred at 5° C. for 1 hour. Perfluoroallyl fluorosulfate (23.0 g, 0.10 mol) was added dropwise and the mixture was stirred at 5° C. for 4 hours, then at 25° C. for an additional 3 hours. The mixture was poured into water (1 l.), separated, and the lower layer was distilled from concentrated sulfuric acid to give perfluoro-3-(octyloxy)propene (27.1 g, 0.048 mol, 80%) bp 69°-70° C. (20 mm Hg) whose structure was confirmed by: λmax 5.59 (CF=CF2) and 8-9 μm (CF C-O); 19F NMR -71.8 (d J=25.1 Hz, each member d J=13.4 Hz, t J=13.4 Hz, d J=7.7 Hz) 2F, OCF2C=C, -81.6 (t J=10.0 Hz) 3F, CF3, -83.8 (m) 2F, CF2CF2O, -92.3 (d J=53.6 Hz, each member d J=39.9 Hz, t J=7.7 Hz) 1F, cis-CF2CF=CF, -105.5 (d J=117.8 Hz, each member d J=53.5 Hz, t J=25.1 Hz) 1F, trans-CF2CF=CF, -122.2 (m) 6F, CF2 , -122.9 (m) 2F, CF2, -125.7 (m) 2F, CF2, -126.5 (m) 2F, CF2, and -190.8 ppm (d J=117.8 Hz, each member d J=39.9 Hz, t 13.7 Hz, t 1.7 Hz) 1F, CF2CF=C.

Workup

  1. stirringthe mixture was stirred at 5° C. for 4 hours
  2. waitat 25° C. for an additional 3 hours
  3. customseparated
  4. distillationthe lower layer was distilled from concentrated sulfuric acid

Sources & evidence

ORD record
ord-a339cf1e6e49462f963fb5fa59f2cf8a
Source dataset
uspto-grants-1981_09
Patent number
US04292449

Reaction notes

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