4-Bromoanisole → 6-Methoxy-10-(4-methoxy-phenyl)-5-nitro-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-one

HRID 418957

Reaktionsgleichung

Reaktionsgleichung von HRID 418957
[CH3:1][O:2][C:3]1[C:4]([N+:18]([O-:20])=[O:19])=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH2:12][CH:11]1[CH:6]2[CH2:7][CH2:8][CH2:9][CH2:10]1.Br[C:22]1[CH:27]=[CH:26][C:25]([O:28][CH3:29])=[CH:24][CH:23]=1.C(P)(C)(C)C.CC(C)([O-])C.[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCCC1>[CH3:1][O:2][C:3]1[C:4]([N+:18]([O-:20])=[O:19])=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH:12]([C:22]1[CH:27]=[CH:26][C:25]([O:28][CH3:29])=[CH:24][CH:23]=1)[CH:11]1[CH:6]2[CH2:7][CH2:8][CH2:9][CH2:10]1

Komponenten

7

Edukt 4

HCID 77304-BromoanisoleHCID 123165tert-ButylphosphineHCID 23676156Sodium t-butoxideHCID 666522766-Methoxy-5-nitro-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-one

Produkt 1

HCID 666520666-Methoxy-10-(4-methoxy-phenyl)-5-nitro-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-oneAusbeute 87,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Combine 6-Methoxy-5-nitro-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-one (0.377 g, 1.37 mmol), 4-bromoanisole (0.258 g, 1.37 mmol), palladium acetate (15.5 mg, 0.07 mmol), t-butyl phosphine (0.042 g, 0.208 mmol), sodium t-butoxide (0.145 g, 1.51 mmol), tetrahydrofuran (12.0 mL), and stir under nitrogen atmosphere at 80° C. in a glass bomb. After 18 hours, quench reaction with acetic acid (5 mL) in a glove box and extract with ethyl acetate. Wash the ethyl acetate with sodium bicarbonate solution and then brine, dry over sodium sulfate, and concentrate in vacuum. Flash chromatograph using 0% to 20% ethyl acetate/hexanes to yield the titled compound (0.455 g, 87%) as a yellow foam. TLC Rf=0.16 in 6:1 hexanes:ethyl acetate. 1H NMR (CDCl3): 8.23 (d, 1H, J=8.8 Hz), 7.06 (m, 3H), 6.92 (m, 2H), 4.01 (m, 4H), 3.83 (s, 3H), 3.10 (dt, 1H, J=8.4, 4.3 Hz), 2.76 (m, 1H), 1.82 (m, 4H), 1.47 (m, 4H).

Aufarbeitung

  1. customquench
  2. customreaction with acetic acid (5 mL) in a glove box
  3. extractionextract with ethyl acetate
  4. washWash the ethyl acetate with sodium bicarbonate solution
  5. dry with materialbrine, dry over sodium sulfate
  6. concentrationconcentrate in vacuum

Quellen und Nachweise

ORD-Eintrag
ord-6cc9a4fbac8d4d9a9d2f9e2edbfb79ed
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08093302B2

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