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

HRID 10749

반응식

HRID 10749 반응식
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]

참가 물질

8

반응물 3

HCID 10796Cesium carbonate2회HCID 709342,3-Dihydrofuran2회HCID 6683465-Bromo-2,4-dimethoxybenzaldehyde

생성물 1

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

시약·촉매·용매 4

HCID 23938Palladium촉매HCID 178418851HCID 178418851, 화합물촉매HCID 962Water용매HCID 312751,4-Dioxane용매

반응 조건

온도
45 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-6afee8efff1c471f86bb728d2c260d3f
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07094801B2

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