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

HRID 30842

反応式

HRID 30842 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:20])[CH2:9][CH:10]([CH2:16][CH2:17][O:18][CH3:19])[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:4][CH:3]=1.[N+:21]([C:24]1[CH:29]=[CH:28][C:27](B(O)O)=[CH:26][CH:25]=1)([O-:23])=[O:22].C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.O1CCOCC1>[CH3:19][O:18][CH2:17][CH2:16][CH:10]([CH2:9][C:8]([C:5]1[CH:6]=[CH:7][C:2]([C:27]2[CH:28]=[CH:29][C:24]([N+:21]([O-:23])=[O:22])=[CH:25][CH:26]=2)=[CH:3][CH:4]=1)=[O:20])[C:11]([O:13][CH2:14][CH3:15])=[O:12]

参加物

6

反応物 3

HCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 21985699Ethyl 4-(4-bromophenyl)-2-(2-methoxyethyl)-4-oxobutanoate

生成物 1

HCID 21985760Ethyl 2-(2-methoxyethyl)-4-(4'-nitro-1,1'-biphenyl-4-yl)-4-oxobutanoate収率 88%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
85 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-59e3f8af2caf4e39b0bc1df1e46b291d
出典データセット
uspto-grants-2008_09
特許番号
US07423156B2

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