Cesium fluoride → HCID 754016, compound

HRID 2043320Notes

Reaction equation

HRID 2043320 reaction equation
Br[CH:2]=[C:3]1[O:7][C:6](=[O:8])[CH:5]=[CH:4]1.[CH3:9][O:10][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>[CH3:9][O:10][C:11]1[CH:16]=[CH:15][C:14](/[CH:2]=[C:3]2/[CH:4]=[CH:5][C:6](=[O:8])[O:7]/2)=[CH:13][CH:12]=1

Participants

9

Reactant 3

HCID 25953Cesium fluorideHCID 201262(4-Methoxyphenyl)boronic acidHCID 672283605-(Bromomethylidene)furan-2(5H)-one

Product 1

HCID 754016HCID 754016, compound

Reagents, catalysts & solvents 5

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

Procedure

A mixture containing 5-bromomethylene-2(5H) furanone (0.175 g, 1 mmol), 4-methoxyphenylboronic acid (0.182 g, 1.2 mmol), trans-dichlorobis(triphenylphosphine)palladium (II) (0.035 g, 0.05 mmol), tetrabutylammonium iodide (0.018 g, 0.05 mmol) and cesium fluoride (0.456 g, 3 mmol) in toluene (10 mL) and water (10 mL) were stirred at reflux for 24 hours under nitrogen. After cooling, brine (50 mL) was added and the product extracted with ethyl acetate (50 mL×3). The organic fractions were combined, washed with brine (50 mL×3), dried over anhydrous sodium sulfate and evaporated to dryness to give a brown solid. The resulting solid was chromatographed (silica gel: eluent 50:50 dichloromethane/light petroleum) giving the desired product 33 as a yellow powder. Yield 0.163 g (80%), m.p. 118-120° C., 1H NMR (CDCl3) δ 7.76-7.71 (m, 2H, H3′ and H5′), 7.45 (d, J=5.2 Hz, 1H, H4), 6.93-6.88 (m, 2H, H2′ and H6′), 6.14-6.12 (m, 1H, H3), 5.97 (bs, 1H, H6), 3.83 (s, 3H). 13C NMR (CDCl3, 75 MHz) δ 170.5 (C), 160.5 (C), 147.0 (C), 145.0 (C), 132.4 (CH), 125.6 (CH), 116.8 (CH), 114.3 (CH), 114.2 (CH), 55.3 CH3). IR (Nujol) 1789, 1737, 1604, 1551, 1509, 1458, 1376, 1302, 1258, 1175, 1119, 1025, 931, 893, 813 cm−1.

Workup

  1. temperatureat reflux for 24 hours under nitrogen
  2. temperatureAfter cooling
  3. extractionthe product extracted with ethyl acetate (50 mL×3)
  4. washwashed with brine (50 mL×3)
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated to dryness
  7. customto give a brown solid
  8. customThe resulting solid was chromatographed (silica gel: eluent 50:50 dichloromethane/light petroleum)

Sources & evidence

ORD record
ord-c502ae36b2ed4f088418ce750585de53
Source dataset
uspto-grants-2013_11
Patent number
US08586618B2

Reaction notes

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