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

HRID 418895Notes

Reaction equation

HRID 418895 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[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:19]1[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=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[CH:4]=[C:5]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH:12]([C:19]1[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=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 110316906-methoxy-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-oneHCID 23676156Sodium t-butoxide

Product 1

HCID 666519296-Methoxy-10-(4-methoxy-phenyl)-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-oneYield 55%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Combine 6-methoxy-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-one (1.0 g, 4.3 mmol), 4-bromoanisole (0.81 g, 4.3 mmol), palladium acetate (49.0 mg, 0.218 mmol), t-butyl phosphine (0.133 g, 0.658 mmol), sodium t-butoxide (0.457 g, 4.7 mmol), tetrahydrofuran (38.0 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 vacuo. Add diethyl ether and collect precipitate to yield the titled compound (0.78 g, 55%) as a white solid. TLC Rf=0.26 in 5:1 hexanes:ethyl acetate. 1H NMR (CDCl3): 8.04 (d, 1H, J=8.8 Hz), 7.06 (d, 2H, J=8.4 Hz), 6.86 (m, 3H), 6.75 (m, 1H), 3.89 (m, 4H), 3.80 (s, 3H), 3.01 (m, 1H), 2.65 (m, 1H), 1.81 (m, 3H), 1.46 (m, 5H).

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 vacuo
  7. customAdd diethyl ether and collect precipitate

Sources & evidence

ORD record
ord-8e2aae57785e4b55a971be0f1304a860
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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