Acetic Acid → 2,2-Difluoroethenyl 4-methylbenzene-1-sulfonate

HRID 1436640Notes

Reaction equation

HRID 1436640 reaction equation
C([Li])CCC.[F:6][C:7](F)([F:20])[CH2:8][O:9][S:10]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)(=[O:12])=[O:11].C(O)(=O)C.C(OCC)(=O)C>C1COCC1>[F:20][C:7]([F:6])=[CH:8][O:9][S:10]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)(=[O:11])=[O:12]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 8857Ethyl AcetateHCID 67942Ethanol, 2,2,2-trifluoro-, 1-(4-methylbenzenesulfonate)HCID 178418339Butyllithium

Product 1

HCID 109773662,2-Difluoroethenyl 4-methylbenzene-1-sulfonateYield 47.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Add n-butyllithium (1.6 M in hexanes, 4.9 mL, 7.8 mmol) dropwise over 5 min to a solution of 2,2,2-trifluoroethyl-p-toluene sulfonate (1.0 g, 3.9 mmol) in THF (20 mL) at −78° C. Stir for 30 min, add acetic acid (225 μL, 3.9 mmol) and stir for 30 min. Warm to room temperature, add ethyl acetate and extract with saturated aqueous ammonium chloride, and saturated aqueous sodium bicarbonate. Dry (magnesium sulfate), concentrate and purify (silica gel chromatography, eluting with 0:100 to 15:85 ethyl acetate:hexanes) to give the title compound as an oil (430 mg, 47%).

Workup

  1. stirringstir for 30 min
  2. extractionextract with saturated aqueous ammonium chloride, and saturated aqueous sodium bicarbonate
  3. dry with materialDry (magnesium sulfate)
  4. concentrationconcentrate
  5. custompurify
  6. wash(silica gel chromatography, eluting with 0:100 to 15:85 ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-5260bac620324b1db61f7ceea865017a
Source dataset
uspto-grants-2009_11
Patent number
US07618978B2

Reaction notes

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