Cesium carbonate → 5-(2,5-Dihydro-furan-2-yl)2,4-dimethoxy-benzaldehyde

HRID 10749

反応式

HRID 10749 の反応式
Br[C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].[O:14]1[CH:18]=[CH:17][CH2:16][CH2:15]1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.[Pd].O.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[O:14]1[CH2:18][CH:17]=[CH:16][CH:15]1[C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=[O:8]

参加物

8

反応物 3

HCID 10796Cesium carbonate2 回HCID 709342,3-Dihydrofuran2 回HCID 6683465-Bromo-2,4-dimethoxybenzaldehyde

生成物 1

HCID 219810145-(2,5-Dihydro-furan-2-yl)2,4-dimethoxy-benzaldehyde収率 50%

試薬・触媒・溶媒 4

HCID 23938Palladium触媒HCID 178418851HCID 178418851、化合物触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
45 °C

実験手順

Ex-121A: 5-Bromo-2,4-dimethoxybenzaldehyde (1.0 g, 4.0 mmol) and 2,3-dihydrofuran (0.85 g, 12.2 mmol) were dissolved in dioxane (10.0 mL). Nitrogen was bubbled into the solution for 15 min followed by the sequential addition of cesium carbonate (1.4 g, 4.5 mmol) and bis(tri-t-butylphosphine)palladium (0) (0.021 g, 0.041 mmol). The solution was immediately heated to 45° C. and aged for 72 h. Additional equivalents of cesium carbonate (0.70 g, 2.1 mmol), 2,3-dihydrofuran (0.85 g, 12.2 mmol), and Pd catalyst (0.0021 g, 0.0041 mmol) were added after 24 h and 48 h to drive the reaction to completion. Upon completion, as determined by HPLC, the reaction was diluted with water (30 mL) and extracted with ethyl acetate (3×30 mL). The combined organic extracts were dried over sodium sulfate and concentrated to an orange oil. Silica gel chromatography (ethyl acetate/hexanes, 1:2) afforded 0.32 g (50%) of 5-(2,5-dihydro-furan-2-yl)-2,4-dimethoxy-benzaldehyde as a pale yellow solid, mp 84–85° C. 1H-NMR (300 MHz, CDCl3) δ 10.29 (s, 1H), 7.79 (s, 1H), 6.42 (s, 1H), 5.99–6.06 (m, 2H), 5.89–5.92 (m, 1H), 4.80–4.87 (m, 1H), 4.71–4.77 (m, 1H), 3.95 (s, 3H), 3.92 (s, 3H). MS (EI) m/z=234 ([M]+, 100%). Anal. Calcd. C13H14O4: C, 66.66; H, 6.02. Found: C, 66.49; H, 6.08.

後処理

  1. customNitrogen was bubbled into the solution for 15 min
  2. customthe reaction to completion
  3. extractionextracted with ethyl acetate (3×30 mL)
  4. dry with materialThe combined organic extracts were dried over sodium sulfate
  5. concentrationconcentrated to an orange oil

出典と根拠

ORDレコード
ord-6afee8efff1c471f86bb728d2c260d3f
出典データセット
uspto-grants-2006_08
特許番号
US07094801B2

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