Sodium Carbonate → Ethyl 2-(2-methoxyethyl)-4-(4'-nitro-1,1'-biphenyl-4-yl)-4-oxobutanoate

温度

85 °C

To a 150 mL 3-neck flask fitted with a reflux condenser was added ethyl 4-(4-bromophenyl)-2-(2-methoxyethyl)-4-oxobutanoate (1.06 g, 3.09 mmol) and 4-nitro-phenyl boronic acid (0.62 g, 3.70 mmol) dissolved in toluene (30 mL) and dioxane (8.50 mL), followed by addition of saturated aqueous sodium carbonate solution (8.50 mL). A thin-gauge needle was inserted into the bi-phasic mixture and degassed with argon over 30 minutes, at which point 1,2-bis[(diphenylphosphino) ferrocene] dichloropalladium(II) (0.13 g, 0.15 mmol) was added, followed by an additional 15 minutes of degassing. The reaction mixture was heated at 85° C. for 16 h, and then the resulting dark-colored reaction mixture was allowed to cool, and was diluted with ethyl acetate (75 mL) and saturated aqueous sodium chloride solution (75 mL). The layers were separated, the aqueous layer was extracted twice with ethyl acetate (50 mL), and the combined organic layers were washed with saturated aqueous sodium chloride solution (75 mL), dried over anhydrous magnesium sulfate, and filtered in vacuo through 2 cm Celite®/2 cm silica. The filtrate was concentrated in vacuo, leaving a dark red-brown oil, that was purified by flash chromatography (4:1 hexane/ethyl acetate, then 3:1 hexane/ethyl acetate, then 2:1 hexane/ethyl acetate) to afford ethyl 2-(2-methoxyethyl)-4-(4′-nitro-1,1′-biphenyl-4-yl)-4-oxobutanoate (1.04 g, 88%). LC-MS ret. time 3.38 min, m/z 385.9 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.27 (t, 3H), 1.80–1.95 (m, 1H), 1.95–2.10 (m, 1H), 3.10–3.25 (m, 2H), 3.40–3.58 (m, 3H), 4.17 (q, 2H), 7.67–7.82 (2d, 4H), 8.10 (d, 2H), 8.33 (d, 2H).

1. customTo a 150 mL 3-neck flask fitted with a reflux condenser
2. additionwas added
3. customof degassing
4. temperatureto cool
5. additionwas diluted with ethyl acetate (75 mL) and saturated aqueous sodium chloride solution (75 mL)
6. customThe layers were separated
7. extractionthe aqueous layer was extracted twice with ethyl acetate (50 mL)
8. washthe combined organic layers were washed with saturated aqueous sodium chloride solution (75 mL)
9. dry with materialdried over anhydrous magnesium sulfate
10. filtrationfiltered in vacuo through 2 cm Celite®/2 cm silica
11. concentrationThe filtrate was concentrated in vacuo
12. customleaving a dark red-brown oil, that
13. customwas purified by flash chromatography (4:1 hexane/ethyl acetate

ORDレコード

ord-5dcca08f75f24c8a9f19bca88699582c

出典データセット

uspto-grants-2006_08

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07091228B2