Cesium fluoride → 3-Bromo-4-(4'-(trifluoromethyl)phenyl)furan-2-(5H)-one

HRID 2043312Notes

Reaction equation

HRID 2043312 reaction equation
[Br:1][C:2]1[C:3](=[O:8])[O:4][CH2:5][C:6]=1Br.[F:9][C:10]([F:21])([F:20])[C:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.[F-].[Cs+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.O.[Cl-].[Na+].O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:1][C:2]1[C:3](=[O:8])[O:4][CH2:5][C:6]=1[C:14]1[CH:15]=[CH:16][C:11]([C:10]([F:21])([F:20])[F:9])=[CH:12][CH:13]=1

Participants

9

Reactant 3

HCID 25953Cesium fluorideHCID 1546383,4-Dibromo-2(5H)-furanoneHCID 27343894-(Trifluoromethyl)phenylboronic acid

Product 1

HCID 248260413-Bromo-4-(4'-(trifluoromethyl)phenyl)furan-2-(5H)-oneYield 47.4%

Reagents, catalysts & solvents 5

HCID 67553Tetrabutylammonium IodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture containing 3,4-dibromofuran-2(5H)-one (0.518 g, 2.142 mmol), 4-trifluoromethylphenylboronic acid (0.509 g, 2.680 mmol), trans-dichlorobis(triphenylphosphine)palladium (II) (0.069 g, 9.831×10−2 mmol), tetrabutylammonium iodide (0.038 g, 1.029×10−1 mmol) and cesium fluoride (0.872 g, 5.740 mmol) in toluene (10 mL) and water (10 mL) was stirred at room temperature for 72 h under nitrogen. Brine (50 mL) was added and the product extracted with ethyl acetate (3×50 mL). The organic fractions were combined, washed with brine (3×50 mL), dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give an orange solid. The resulting solid was chromatographed (silica gel: eluent 25:75 dichloromethane/light petroleum) to give 3-bromo-4-(4′-(trifluoromethyl)phenyl)furan-2-(5H)-one 16 (0.312 g, 47%) as a pale yellow powder. Further purification by recrystallisation from dichloromethane/light petroleum furnished colourless needles, (ref. PDS-2-115); 1H NMR (CDCl3, 300 MHz) δ 7.94 (d, 2H, J=8.3 Hz, H3′, H5′), 7.78 (d, 2H, J=8.3 Hz, H2′, H6′), 5.21 (s, 2H, H5).

Workup

  1. extractionthe product extracted with ethyl acetate (3×50 mL)
  2. washwashed with brine (3×50 mL)
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customevaporated to dryness under reduced pressure
  5. customto give an orange solid
  6. customThe resulting solid was chromatographed (silica gel: eluent 25:75 dichloromethane/light petroleum)

Sources & evidence

ORD record
ord-b53d7ce4ef354ba3a6d16d461bc86c5a
Source dataset
uspto-grants-2013_11
Patent number
US08586618B2

Reaction notes

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