Carbon Dioxide → 6-(1,2,2,2-Tetrafluoroethoxy)perfluorohexanoic acid

HRID 2355663Notes

Reaction equation

HRID 2355663 reaction equation
FC([C:4]([O:10][C:11]([C:14]([C:17]([C:20]([C:23]([C:26](F)=[O:27])([F:25])[F:24])([F:22])[F:21])([F:19])[F:18])([F:16])[F:15])([F:13])[F:12])([C:6]([F:9])([F:8])[F:7])[F:5])=O.FC(F)(F)C1(F)[O:35]C1(F)F.FC(F)(C(F)(F)C(F)(F)C(F)(F)C(F)=O)C(F)=O.C(=O)([O-])[O-].[Na+].[Na+].C(=O)=O.S(=O)(=O)(O)O>COCCOCCOC.O>[C:6]([CH:4]([O:10][C:11]([C:14]([C:17]([C:20]([C:23]([C:26]([OH:35])=[O:27])([F:24])[F:25])([F:21])[F:22])([F:19])[F:18])([F:15])[F:16])([F:12])[F:13])[F:5])([F:9])([F:7])[F:8]

Participants

9

Reactant 6

HCID 280Carbon Dioxide2×HCID 1118Sulfuric AcidHCID 9883Hexafluoropropylene oxideHCID 10340Sodium CarbonateHCID 123466Octafluoroadipoyl difluorideHCID 111670672,2,3,3,4,4,5,5,6,6-Decafluoro-6-[1,2,2,2-tetrafluoro-1-(fluorocarbonyl)ethoxy]hexanoyl fluoride

Product 1

HCID 1317279136-(1,2,2,2-Tetrafluoroethoxy)perfluorohexanoic acidYield 95%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8150DiglymeSolvent

Procedure

A sample of diacid fluoride, FCOCF(CF3)—O—(CF2)5COF (500 g, 1.1 mol) prepared from the hexafluoropropylene oxide (HFPO) coupling of perfluoroadipoyl fluoride as described in U.S. Pub. No. US 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (500 g, 4.7 mol) in 500 g of diglyme at 85° C. to make the disalt. The reaction liberated CO2 gas. Distilled water (25 g, 1.4 mol) was added at 85° C. The mixture was heated up to 168° C. with CO2 off-gassing and held for 30 minutes. Reaction was cooled down and sulphuric acid (350 g, 3.6 mol) in 1100 g of water was added to make the reaction mixture acidic. Bottom phase was washed with 400 g of 50% sulfuric acid and vacuum distilled to give CF3—CFH—O—(CF2)5COOH 426 g, 1.0 mol for a 95% yield having a boiling point of 132-135° C./15 mm. This was followed by the addition of 46 g NaOH in 63 g of water. Dried salts in vacuum oven at 112° C./15 mm Hg to give 386 g of slight yellow sticky solids. To the salt was added sulphuric acid and the lower fluorochemical phase was vacuum distilled. The previous process was repeated two more times to yield a colorless acid. The surfactant CF3—CFH—O—(CF2)5COONH4 having a melting point of 159-165° C. was made quantitatively from the reaction of 200 g of acid reacted with excess ammonium hydroxide and dried.

Workup

  1. customReaction
  2. temperaturewas cooled down
  3. washBottom phase was washed with 400 g of 50% sulfuric acid and vacuum
  4. distillationdistilled

Sources & evidence

ORD record
ord-a0484591879e4ba68cb26a88decc7433
Source dataset
uspto-grants-2010_07
Patent number
US07754795B2

Reaction notes

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