Sodium Carbonate → Ethyl 2-[2-(4'-nitro-1,1'-biphenyl-4-yl)-2-oxoethyl]pentanoate

HRID 9528

반응식

HRID 9528 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:19])[CH2:9][CH:10]([CH2:16][CH2:17][CH3:18])[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:4][CH:3]=1.[N+:20]([C:23]1[CH:28]=[CH:27][C:26](B(O)O)=[CH:25][CH:24]=1)([O-:22])=[O:21].C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.O1CCOCC1>[N+:20]([C:23]1[CH:28]=[CH:27][C:26]([C:2]2[CH:7]=[CH:6][C:5]([C:8](=[O:19])[CH2:9][CH:10]([CH2:16][CH2:17][CH3:18])[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:4][CH:3]=2)=[CH:25][CH:24]=1)([O-:22])=[O:21]

참가 물질

6

반응물 3

HCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 21985789Ethyl 2-[2-(4-bromophenyl)-2-oxoethyl]pentanoate

생성물 1

HCID 21985687Ethyl 2-[2-(4'-nitro-1,1'-biphenyl-4-yl)-2-oxoethyl]pentanoate수율 48%

시약·촉매·용매 2

HCID 1140Toluene용매HCID 312751,4-Dioxane용매

반응 조건

온도
85 °C

실험 절차

To a 150 mL 3-neck flask fitted with a reflux condenser was added ethyl 2-[2-(4-bromophenyl)-2-oxoethyl]pentanoate (1.33 g, 4.10 mmol) and 4-nitro phenyl boronic acid (0.81 g, 4.9 mmol), dissolved in toluene (37 mL) and dioxane (10 mL), followed by addition of saturated aqueous sodium carbonate (11 mL). A thin-gauge needle was inserted into the bi-phasic mixture and the mixture was degassed with argon over 30 minutes, at which point 1,2-bis[(diphenylphosphino) ferrocene] dichloropalladium(II) (0.17 g, 0.20 mmol) was added, followed by 15 minutes of degassing. The mixture was heated to 85° C. for 16 h. The very darkly colored reaction mixture was allowed to cool, and diluted with ethyl acetate (100 mL) and saturated aqueous sodium chloride solution (100 mL). The layers were separated, the aqueous layer 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 under reduced pressure, leaving a dark red-brown oil, that was purified by flash chromatography (10:1 hexane:ethyl acetate, then 7:1 hexane:ethyl acetate, then 4:1 hexane:ethyl acetate) to afford ethyl 2-[2-(4′-nitro-1,1′-biphenyl-4-yl)-2-oxoethyl]pentanoate (0.71 g, 48%). LC-MS ret. time 3.88 min, m/z 369.8 (MH+); 1H NMR (300 MHz, CDCl3) δ 0.95 (t, 3H), 1.30 (t, 3H), 1.35–1.50 (m, 2H), 1.60–1.83 (m, 2H), 3.0–3.18 (m, 2H), 3.5 (dd, 1H), 4.20 (q, 2H), 7.65–7.88 (overlapping d, 4H), 8.10 (d, 2H), 8.35 (d, 2H).

후처리

  1. customTo a 150 mL 3-neck flask fitted with a reflux condenser
  2. additionwas added
  3. customof degassing
  4. temperatureto cool
  5. additiondiluted with ethyl acetate (100 mL) and saturated aqueous sodium chloride solution (100 mL)
  6. customThe layers were separated
  7. extractionthe aqueous layer 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 under reduced pressure
  12. customleaving a dark red-brown oil, that
  13. customwas purified by flash chromatography (10:1 hexane

출처 및 근거

ORD 기록
ord-a78d2dcb1e5548479df3ef45416b6e74
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07091228B2

연결된 노트

불러오는 중…