Hydrochloric Acid → Triethylammonium 1,1,3,3,3-pentafluoro-2-(methacryloyloxy)propane-1-sulfonate

HRID 2361535Notes

Reaction equation

HRID 2361535 reaction equation
[F:1][C:2]([F:19])([S:15]([O-:18])(=[O:17])=[O:16])[CH:3]([O:8][C:9](=[O:14])[C:10](C)([CH3:12])[CH3:11])[C:4]([F:7])([F:6])[F:5].[CH2:20]([NH+:22]([CH2:25][CH3:26])[CH2:23][CH3:24])[CH3:21].O.[Na].C(N(CC)CC)C.C(OC(=O)C(C)=C)(=O)C(C)=C.Cl>CO.CN(C)C1C=CN=CC=1.C(#N)C>[F:19][C:2]([F:1])([S:15]([O-:18])(=[O:16])=[O:17])[CH:3]([O:8][C:9](=[O:14])[C:10]([CH3:12])=[CH2:11])[C:4]([F:5])([F:7])[F:6].[CH2:20]([NH+:22]([CH2:25][CH3:26])[CH2:23][CH3:24])[CH3:21]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 12974Methacrylic anhydrideHCID 71353970Sodium monohydrateHCID 86618175Triethylammonium 1,1,3,3,3-pentafluoro-2-(pivaloyloxy)propane-1-sulfonate

Product 1

HCID 86656197Triethylammonium 1,1,3,3,3-pentafluoro-2-(methacryloyloxy)propane-1-sulfonate

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 887MethanolSolventHCID 6342AcetonitrileSolvent

Procedure

Triethylammonium 1,1,3,3,3-pentafluoro-2-(pivaloyloxy)propane-1-sulfonate prepared by the method disclosed in Japanese Patent Laid-Open (kokai) No. 2007-304490 is dissolved in methanol and 2 equivalents of 25 wt % aqueous solution of sodium hydrate was added thereto. After confirming a separation of a pivaloyloxy group by 19F-NMR, 2.1 equivalents of 12N hydrochloric acid was added and both methanol and water were removed by evaporation under reduced pressure, and then ethyl ether was added to the obtained residue to perform recrystallization. The crude substance containing sodium chloride was filtrated and then triethylamine (1.5 equivalents), 4-dimethylamino pyridine (0.025 equivalent) and acetonitrile (4 fold of the crude substance by weight) were added and the mixture was iced-cooled. Then, methacrylic acid anhydride (1.0 equivalent) was dropped and the mixture was stirred overnight. 3N hydrochloric acid was added to the reaction solution to make the solution acidic, and acetonitrile was removed by evaporation under reduced pressure at low temperature, and thereafter, the solution was dissolved in dichloromethane and then washed by water. After dichloromethane was removed by evaporation under reduced pressure, the obtained crude substance was used for the next reaction without purification.

Workup

  1. customa separation of a pivaloyloxy group by 19F-NMR, 2.1 equivalents of 12N hydrochloric acid
  2. additionwas added
  3. customboth methanol and water were removed by evaporation under reduced pressure
  4. additionethyl ether was added to the obtained residue
  5. customrecrystallization
  6. additionThe crude substance containing sodium chloride
  7. filtrationwas filtrated
  8. temperaturethe mixture was iced-cooled
  9. customacetonitrile was removed by evaporation under reduced pressure at low temperature
  10. dissolutionthe solution was dissolved in dichloromethane
  11. washwashed by water
  12. customAfter dichloromethane was removed by evaporation under reduced pressure
  13. customthe obtained crude substance
  14. customwas used for the next reaction without purification

Sources & evidence

ORD record
ord-4093e1d6b15e47b39cc9201498fa6615
Source dataset
uspto-grants-2014_04
Patent number
US08691490B2

Reaction notes

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