反応 #10845

ord-6afee8efff1c471f86bb728d2c260d3f

反応方程式

COc1cc(OC)c(C=O)cc1Br
5-Bromo-2,4-dimethoxybenzaldehyde
C1=COCC1
2,3-dihydrofuran
O=C([O-])[O-].[Cs+].[Cs+]
cesium carbonate
O=C([O-])[O-].[Cs+].[Cs+]
cesium carbonate
C1=COCC1
2,3-dihydrofuran
COc1cc(OC)c(C2C=CCO2)cc1C=O
5-(2,5-dihydro-furan-2-yl)-2,4-dimethoxy-benzaldehyde
収率 50.0%

反応条件

温度
45°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    その他Nitrogen was bubbled into the solution for 15 min
  2. 2
    その他the reaction to completion
  3. 3
    抽出extracted with ethyl acetate (3×30 mL)
  4. 4
    乾燥The combined organic extracts were dried over sodium sulfate
  5. 5
    濃縮concentrated to an orange oil

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.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US07094801B2uspto-grants-2006_08