Carbon Dioxide → 2,4,5,6-Tetrafluoro-[1,1'-biphenyl]-3-carboxylic acid

HRID 1995125Notes

Reaction equation

HRID 1995125 reaction equation
[F:1][C:2]1[C:7]([F:8])=[C:6]([F:9])[CH:5]=[C:4]([F:10])[C:3]=1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C([Li])CCC.[C:22](=[O:24])=[O:23].Cl>C(OCC)C.CCCCCC>[F:10][C:4]1[C:5]([C:22]([OH:24])=[O:23])=[C:6]([F:9])[C:7]([F:8])=[C:2]([F:1])[C:3]=1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 128530492,3,4,6-TetrafluorobiphenylHCID 178418339Butyllithium

Product 1

HCID 128530502,4,5,6-Tetrafluoro-[1,1'-biphenyl]-3-carboxylic acid

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

Under a dry argon atmosphere, a stirred solution of 2,3,4,6-tetrafluoro-[1,1'-biphenyl] (23.0 g, 0.102 mole) in 400 ml of diethyl ether was cooled to -65°. During a 11/4 hour period 63.4 ml of a 1.6 M solution of n-butyl lithium in hexane was added to the reaction mixture, which was then stirred at -65° for 23/4 hours. During a one hour period, freshly crushed dry ice (750 g) was added to the mixture. The stirred reaction mixture was then allowed to warm to room temperature. The mixture was cooled; 400 ml of 6 N aqueous hydrochloric acid was added and the resultant mixture stirred vigorously for two hours. The mixture was poured into a separatory funnel, the aqueous phase separated and extracted with three 300 ml portions of diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a solid residue. The solid was recrystallized from toluene:n-heptane (1:1) to give 2,4,5,6-tetrafluoro-[1,1'-biphenyl]-3-carboxylic acid (mp, 189°-190.5°).

Workup

  1. customThe stirred reaction mixture
  2. temperatureThe mixture was cooled
  3. additionThe mixture was poured into a separatory funnel
  4. customthe aqueous phase separated
  5. extractionextracted with three 300 ml portions of diethyl ether
  6. dry with materialThe combined extracts were dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give a solid residue
  10. customThe solid was recrystallized from toluene:n-heptane (1:1)

Sources & evidence

ORD record
ord-674280aea6214b7fa5ece8248a3a0d6e
Source dataset
uspto-grants-1983_09
Patent number
US04402973

Reaction notes

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