Carbon Dioxide → 2,2,3,3,4,4-Hexafluoro-4-(1,2,2,2-tetrafluoroethoxy)butanoic acid

HRID 1914976Notes

Reaction equation

HRID 1914976 reaction equation
FC([C:4]([O:10][C:11]([C:14]([C:17]([C:20](F)=[O: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)(C(F)(F)C(F)=O)C(F)=[O:26].C(=O)([O-])[O-].[Na+].[Na+].C(=O)=O.S(=O)(=O)(O)O.[OH-].[Na+]>COCCOCCOC.O>[C:6]([CH:4]([O:10][C:11]([C:14]([C:17]([C:20]([OH:26])=[O:21])([F:19])[F:18])([F:15])[F:16])([F:13])[F:12])[F:5])([F:9])([F:7])[F:8]

Participants

9

Reactant 6

HCID 280Carbon Dioxide2×HCID 1118Sulfuric AcidHCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 2776618Tetrafluorosuccinyl fluorideHCID 112569172,2,3,3,4,4-Hexafluoro-4-[(1,1,1,2,3-pentafluoro-3-oxopropan-2-yl)oxy]butanoyl fluoride

Product 1

HCID 714258312,2,3,3,4,4-Hexafluoro-4-(1,2,2,2-tetrafluoroethoxy)butanoic acidYield 95%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 8150DiglymeSolvent

Procedure

A sample of diacid fluoride, FCOCF(CF3)—O—(CF2)3COF (503 g, 1.4 mol) prepared from the HFPO coupling of perfluorosuccinyl fluoride as described in US Pub. No. 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (387 g, 3.7 mol) in 650 g of diglyme at 78° C. to make the disalt. The reaction liberated CO2 gas. Distilled water (35 g, 1.9 mol) was added at 85° C. The mixture was heated up to 165° C. with CO2 off-gassing and held for 30 minutes. Reaction was cooled down and sulphuric acid (250 g, 2.6 mol) in 1250 g of water was added to make the reaction mixture acidic. To the bottom phase was added 60 g NaOH in 60 g of water. Dried the salt in vacuum oven at 112° C./15 mm and recovered 450 g. To the salt was added 300 g of 50% sulphuric acid and the lower fluorochemical phase was washed once with 200 g of 50% sulphuric acid. Vacuum distillation gave CF3—CFH—O—(CF2)3COOH (400 g, 1.3 mol) for a 95% yield having a boiling point of 111° C./15 mm Hg. The acid was treated with caustic followed by sulphuric acid and vacuum distilled. This was repeated a second time to yield a colorless acid. The surfactant CF3—CFH—O—(CF2)3COONH4 having a melting point of 64-68° C. was made quantitatively from the reaction of 208 g of acid reacted with excess ammonium hydroxide and dried.

Workup

  1. customReaction
  2. temperaturewas cooled down
  3. customDried the salt in vacuum oven at 112° C./15 mm
  4. customrecovered 450 g
  5. additionTo the salt was added 300 g of 50% sulphuric acid
  6. washthe lower fluorochemical phase was washed once with 200 g of 50% sulphuric acid
  7. distillationVacuum distillation

Sources & evidence

ORD record
ord-37af50787968476d90707e4f3d469751
Source dataset
uspto-grants-2013_12
Patent number
US08614265B2

Reaction notes

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