Dimethylformamide → 2H-Perfluoroisopropyl 2-fluoroacrylate

HRID 1614784Notes

Reaction equation

HRID 1614784 reaction equation
CN(C)C=O.[F:6][C:7](=[CH2:11])[C:8]([O-:10])=[O:9].[NH4+].S(Cl)(Cl)=O.C(N(CC)CC)C.[F:24][C:25]([F:33])([F:32])[CH:26](O)[C:27]([F:30])([F:29])[F:28]>CC1C=CC=CC=1C>[F:6][C:7](=[CH2:11])[C:8]([O:10][CH:26]([C:27]([F:30])([F:29])[F:28])[C:25]([F:33])([F:32])[F:24])=[O:9]

Participants

7

Reactant 5

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 135291,1,1,3,3,3-Hexafluoro-2-propanolHCID 24386Thionyl ChlorideHCID 10986169Ammonium alpha-fluoroacrylate

Product 1

HCID 27783592H-Perfluoroisopropyl 2-fluoroacrylateYield 52%

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Conditions

Temperature
80 °C

Procedure

A 2-Liter glass flask which had been equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel was charged with 1.2 l of o-xylene, 29 g (0.4 mol) of dimethylformamide and 200 g (1.87 mol) of ammonium α-fluoroacrylate. To this initial charge were then added dropwise in the course of 1 hour 238 g (2.0 mol) of thionyl chloride. The reaction mixture was then maintained at a temperature of 80° C. for 2 hours. After subsequently cooling down to a temperature of 0° C., the mixture had added to it a mixture of 202 g (2 mol) of triethylamine and 336 g (2 mol) of hexafluoroisopropanol in the course of 30 minutes. The resulting mixture was stirred for a further 30 minutes, and the resulting precipitate was filtered off. The filtrate was treated with 1 g of hydroquinone monomethyl ether and rapidly distilled under a pressure of 266 mbar. The fraction obtained within the temperature range from 45° to 85° C. was washed with hydrochloric acid (2.4 molar) and with water, was dried and was distilled again, giving 232 g (52 percent of theory) of pure hexafluoroisopropyl α-fluoroacrylate. This ester was a colorless liquid with a refractive index nD23 =1.3145, a boiling point of 46.8° C. (at 213 mbar) and a density of 1.453 g/cm3 (at 25° C.). In the wavelength range from 380 to 680 nm this ester had an average transmission of more than 99 percent.

Workup

  1. customA 2-Liter glass flask which had been equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel
  2. additionTo this initial charge
  3. temperatureAfter subsequently cooling down to a temperature of 0° C.
  4. additionthe mixture had added to it
  5. filtrationthe resulting precipitate was filtered off
  6. additionThe filtrate was treated with 1 g of hydroquinone monomethyl ether
  7. distillationrapidly distilled under a pressure of 266 mbar
  8. customThe fraction obtained within the temperature range from 45° to 85° C.
  9. washwas washed with hydrochloric acid (2.4 molar) and with water
  10. customwas dried
  11. distillationwas distilled again

Sources & evidence

ORD record
ord-475ddcddfc724b359f764e684471c952
Source dataset
uspto-grants-1993_03
Patent number
US05198925

Reaction notes

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