Benzene → Diethyl tetrafluorosuccinate

HRID 1955296Notes

Reaction equation

HRID 1955296 reaction equation
[F:1][C:2]([F:12])([C:9]([OH:11])=[O:10])[C:3]([F:8])([F:7])[C:4]([OH:6])=[O:5].[C:13]1(C)C=CC(S(O)(=O)=O)=C[CH:14]=1.[CH:24]1C=CC=C[CH:25]=1>>[F:1][C:2]([F:12])([C:9]([O:11][CH2:24][CH3:25])=[O:10])[C:3]([F:7])([F:8])[C:4]([O:6][CH2:13][CH3:14])=[O:5]

Participants

4

Reactant 3

HCID 241BenzeneHCID 6101p-Toluenesulfonic acidHCID 678332,2,3,3-Tetrafluorobutanedioic acid

Product 1

HCID 67834Diethyl tetrafluorosuccinate

Procedure

First, diethyl tetrafluorosuccinate was prepared. Benzene (1 L) was refluxed in a 2 L 2-necked round bottom flask equipped with a Dean-Stark trap, condenser and magnetic stir bar. The azeotrope was removed. Absolute ethanol (500 ml) was added to the flask. The Dean-Stark trap was filled with activated 4 Å molecular sieves, and the solvents were refluxed through the sieves for 1 hour. The Dean-Stark trap was then placed with a Sohxlet extractor apparatus, and a Sohxlet thimble was filled with activated molecular sieves and placed in the apparatus. The tetrafluorosuccinic acid (50.37 g, 0.265 mol) was added to the flask along with p-toluene sulfonic acid (4 g). The reaction was refluxed for 24 hours. The wet sieves were periodically removed and replaced with fresh sieves. The reaction was followed by NMR. After 24 hours, the reaction was allowed to cool, and the solvents were removed in vacuo. The resulting oil was taken up to 200 ml pentane and washed three times with 50 ml saturated NaHCO3 solution. The pentane was removed in vacuo to give 53.42 g (82%) of the clear oil diethyl tetrafluorosuccinate. The following data verifies the formation of diethyl tetrafluorosuccinate: NMR (360 MHz, CDCl3) 1H δ 1.36 (t, 6H, J=7.16 Hz), 4.39 (q, 4H, J=7.16 Hz).

Workup

  1. customequipped with a Dean-Stark trap, condenser and magnetic stir bar
  2. customThe azeotrope was removed
  3. additionAbsolute ethanol (500 ml) was added to the flask
  4. additionThe Dean-Stark trap was filled with activated 4 Å molecular sieves
  5. temperaturethe solvents were refluxed through the sieves for 1 hour
  6. additiona Sohxlet thimble was filled with activated molecular sieves
  7. temperatureThe reaction was refluxed for 24 hours
  8. customThe wet sieves were periodically removed
  9. temperatureto cool
  10. customthe solvents were removed in vacuo
  11. washwashed three times with 50 ml saturated NaHCO3 solution
  12. customThe pentane was removed in vacuo

Sources & evidence

ORD record
ord-7ee632d4aec645709c0ff7779dd37b6a
Source dataset
uspto-grants-2000_09
Patent number
US06124452

Reaction notes

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