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

HRID 732497

Reaction equation

HRID 732497 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-1d3857bc200c4ba4b6155d3a47f970d4
Source dataset
uspto-grants-2009_09
Patent number
US07585885B2

Linked notes

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