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

HRID 418957

Reaction equation

HRID 418957 reaction equation
[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

Participants

7

Reactant 4

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

Product 1

HCID 666520666-Methoxy-10-(4-methoxy-phenyl)-5-nitro-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-oneYield 87.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-6cc9a4fbac8d4d9a9d2f9e2edbfb79ed
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Linked notes

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