N-bromobutanimide → HCID 66620898, Verbindung

HRID 79846

Reaktionsgleichung

Reaktionsgleichung von HRID 79846
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[C:12]3[C:7](=[CH:8][C:9](Br)=[CH:10][CH:11]=3)[CH2:6][CH2:5][C:4]=2[CH:3]=1.C([Sn](CCCC)(CCCC)[C:22]([O:24]CC)=[CH2:23])CCC.C1C(=O)N(Br)C(=O)C1.[C:43]([O:47][C:48]([N:50]1[CH2:54][CH2:53][CH2:52][CH:51]1[C:55]([OH:57])=[O:56])=[O:49])([CH3:46])([CH3:45])[CH3:44].CCN(C(C)C)C(C)C>O1CCOCC1.C(OCC)(=O)C.C(#N)C.O>[C:43]([O:47][C:48]([N:50]1[CH2:54][CH2:53][CH2:52][CH:51]1[C:55]([O:57][CH2:23][C:22]([C:9]1[CH:10]=[CH:11][C:12]2[C:13]3[C:4](=[CH:3][C:2]([Br:1])=[CH:15][CH:14]=3)[CH2:5][CH2:6][C:7]=2[CH:8]=1)=[O:24])=[O:56])=[O:49])([CH3:46])([CH3:44])[CH3:45]

Komponenten

10

Edukt 5

HCID 67184N-bromobutanimideHCID 81531DiisopropylethylamineHCID 2684721-[(Tert-butoxy)carbonyl]pyrrolidine-2-carboxylic acidHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 28250532,7-Dibromo-9,10-dihydrophenanthrene

Produkt 1

HCID 66620898HCID 66620898, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittelHCID 8857Ethyl AcetateLösungsmittel2×HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

Pd(Ph3)4 (347 mg, 0.3 mmol) and PdCl2(Ph3)2 (210 mg, 0.3 mmol) were added to a mixture 2,7-dibromo-9,10-dihydro-phenanthrene (2.5 g, 7.4 mmol) and tributyl(1-ethoxyvinyl)tin (2.5 mL, 7.4 mL) in 70 mL dioxane. The reaction mixture was flushed with nitrogen, heated at 80° C. for 16 hours, then cooled to ambient temperature. Water (20 mL) and NBS (1.39 g, 7.8 mmol) were added and the mixture was stirred at room temperature for 40 minutes, then diluted with ethyl acetate (300 mL). Washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The obtained residue was suspended in acetonitrile (70 mL). To it was added a solution of pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester (3.2 g, 14.9 mmol) and DIPEA (2.4 mL, 14.1 mmol) in 20 mL acetonitrile. The mixture was stirred at room temperature for 16 hours, then diluted with ethyl acetate (300 mL). The organic layer was washed with NaHCO3 solution and water, dried over Na2SO4, filtered and concentrated in vacuo. The obtained residue was purified by flash chromatography to provide the desired product pyrrolidine-1,2-dicarboxylic acid 2-[2-(7-bromo-9,10-dihydro-phenanthren-2-yl)-2-oxo-ethyl]ester 1-tert-butyl ester as a white solid (1.76 g, 46% over two steps). m/z 514.2, 516.2 (M+H)+.

Aufarbeitung

  1. customThe reaction mixture was flushed with nitrogen
  2. temperaturecooled to ambient temperature
  3. washWashed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. stirringThe mixture was stirred at room temperature for 16 hours
  8. washThe organic layer was washed with NaHCO3 solution and water
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe obtained residue was purified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-c65e66a12a6244769980051025db2495
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08841278B2

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