Carbon Dioxide → 4-Chloro-2-fluoro-3-methylbenzoic acid

HRID 1586347Notes

Reaction equation

HRID 1586347 reaction equation
[Cl:1][C:2]1[C:7]([CH3:8])=[C:6]([F:9])[CH:5]=[CH:4][CH:3]=1.C([Li])CCC.[C:15](=[O:17])=[O:16].[Cl-].[NH4+]>C1COCC1.CCCCCC>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:15]([OH:17])=[O:16])=[C:6]([F:9])[C:7]=1[CH3:8]

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 99332-Chloro-6-fluorotolueneHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 153137624-Chloro-2-fluoro-3-methylbenzoic acidYield 24%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-70 °C

Procedure

29.0 g (0.2 mol) of 6-chloro-2-fluorotoluene are dissolved with stirring in 200 ml of dry THF. After cooling to -70° C., 151 ml (0.24 mol) of n-butyllithium in solution in hexane are added dropwise. After two hours, the reaction mixture, maintained at -70° C., is poured on solid carbon dioxide. After returning to room temperature, an aqueous ammonium chloride solution is added. The aqueous phase is extracted with ether, acidified with 6N hydrochloric acid and extracted with ether. The organic phases are dried over magnesium sulphate and concentrated to dryness. The residue is washed with heptane to give 9.0 g (0.048 mol) of 4-chloro-2-fluoro-3-methylbenzoic acid in the form of a white powder (yield: 24%; melting point: 198°)

Workup

  1. temperaturethe reaction mixture, maintained at -70° C.
  2. customAfter returning to room temperature
  3. extractionThe aqueous phase is extracted with ether
  4. extractionextracted with ether
  5. dry with materialThe organic phases are dried over magnesium sulphate
  6. concentrationconcentrated to dryness
  7. washThe residue is washed with heptane

Sources & evidence

ORD record
ord-123c1a654b0b4be084c079bc372fb2ce
Source dataset
uspto-grants-1999_08
Patent number
US05945382

Reaction notes

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