Cesium fluoride → HCID 11105918、化合物

HRID 2043319ノート

反応式

HRID 2043319 の反応式
Br[CH:2]=[C:3]1[O:7][C:6](=[O:8])[CH:5]=[CH:4]1.[S:9]1[CH:13]=[CH:12][CH:11]=[C:10]1B(O)O.[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>[S:9]1[CH:13]=[CH:12][CH:11]=[C:10]1/[CH:2]=[C:3]1/[CH:4]=[CH:5][C:6](=[O:8])[O:7]/1

参加物

9

反応物 3

HCID 25953Cesium fluorideHCID 27339602-Thiopheneboronic acidHCID 672283605-(Bromomethylidene)furan-2(5H)-one

生成物 1

HCID 11105918HCID 11105918、化合物

試薬・触媒・溶媒 5

HCID 67553Tetrabutylammonium Iodide触媒HCID 178418476HCID 178418476、化合物触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

A mixture containing 5-bromomethylene-2(5H)furanone (0.175 g, 1 mmol), 2-thiopheneboronic acid (0.154 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 32 as a yellow powder. Yield 0.170 g (95%), m.p. 100-102° C. 1H NMR (CDCl3) δ 7.50 (d, J=4.9 Hz, 1H, H3′), 7.46 (d, J=5.3 Hz, 1H, H4), 7.38 (d, J=3.4 Hz, 1H, H5′), 7.08-7.05 (m, 1H, H4′), 6.31 (s, 1H, H6), 6.17 (d, J=5.3 Hz, 1H, H3). 13C NMR (CDCl3, 75 MHz) δ 169.5 (C), 146.6 (C), 143.8 (CH), 136.0 (C), 131.3 (CH), 130.7 (CH), 127.7 (CH), 118.0 (CH), 107.5 (CH). IR (Nujol) 1777, 1738, 1459, 1417, 1376, 1107, 935, 886, 731 cm−1.

後処理

  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)

出典と根拠

ORDレコード
ord-5eacf4f945744735a5011a4c9882a875
出典データセット
uspto-grants-2013_11
特許番号
US08586618B2

反応ノート

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