Toluene → Methyl 1-[2-(4'-nitro-1,1'-biphenyl-4-yl)-2-oxoethyl]cyclopentanecarboxylate

HRID 9531

반응식

HRID 9531 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:19])[CH2:9][C:10]2([C:15]([O:17][CH3:18])=[O:16])[CH2:14][CH2:13][CH2:12][CH2:11]2)=[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].C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>C(OCC)(=O)C.[Cl-].[Na+].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][C:10]3([C:15]([O:17][CH3:18])=[O:16])[CH2:14][CH2:13][CH2:12][CH2:11]3)=[CH:4][CH:3]=2)=[CH:25][CH:24]=1)([O-:22])=[O:21]

참가 물질

8

반응물 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 21985683Methyl 1-[2-(4-bromophenyl)-2-oxoethyl]cyclopentanecarboxylate

생성물 1

HCID 21985829Methyl 1-[2-(4'-nitro-1,1'-biphenyl-4-yl)-2-oxoethyl]cyclopentanecarboxylate수율 96.8%

시약·촉매·용매 3

HCID 5234Sodium Chloride용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

반응 조건

온도
85 °C

실험 절차

To a 150 mL 3-neck flask fitted with a reflux condenser was added methyl 1-[2-(4-bromophenyl)-2-oxoethyl]cyclopentanecarboxylate (1.58 g, 4.64 mmol), 4-nitro phenyl boronic acid (0.93 g, 5.6 mmol), toluene (45 mL), and dioxane (13 mL), followed by the addition of a saturated aqueous sodium carbonate solution (13 mL). The mixture was degassed using argon and 1,2-bis[(diphenylphosphino) ferrocene] dichloropalladium(II) (0.19 g, 0.23 mmol) was added, followed by an additional 15 minutes of degassing, and the deep red reaction mixture was heated to 85° C. for 16 h. The very darkly colored reaction mixture was allowed to cool, and then was diluted with ethyl acetate (100 mL) and saturated aqueous sodium chloride solution (100 mL). The layers were separated and the aqueous layer was extracted twice with ethyl acetate (50 mL). The combined organic layer was washed with saturated aqueous sodium chloride solution (100 mL), dried over anhydrous magnesium sulfate, and filtered under reduced pressure 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 (4:1/hexane:ethyl acetate, then 3:1/hexane:ethyl acetate, then 2:1/hexane:ethyl acetate) to afford methyl 1-[2-(4′-nitro-1,1′-biphenyl-4-yl)-2-oxoethyl]cyclopentanecarboxylate (1.65 g, 93%). LC-MS ret. time 3.56 min, m/z 368.0 (MH+); 1HNMR(300 MHz, CDCl3) δ 1.56–1.85 (overlapping signals, 6H), 2.23–2.37 (m, 2H), 3.45 (s, 2H), 3.67 (s, 3H), 7.70 (d, 2H), 7.77 (d, 2H), 8.06 (d, 2H), 8.34 (d, 2H).

후처리

  1. customTo a 150 mL 3-neck flask fitted with a reflux condenser
  2. customThe mixture was degassed
  3. additionwas added
  4. customof degassing
  5. customthe deep red reaction mixture
  6. temperatureto cool
  7. customThe layers were separated
  8. extractionthe aqueous layer was extracted twice with ethyl acetate (50 mL)
  9. washThe combined organic layer was washed with saturated aqueous sodium chloride solution (100 mL)
  10. dry with materialdried over anhydrous magnesium sulfate
  11. filtrationfiltered under reduced pressure through 2 cm Celite®/2 cm silica
  12. concentrationThe filtrate was concentrated under reduced pressure
  13. customleaving a dark red-brown oil, that
  14. customwas purified by flash chromatography (4:1/hexane

출처 및 근거

ORD 기록
ord-b2b04ebbc53f4f219f2866ba91f72edb
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07091228B2

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