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

HRID 418957

反応式

HRID 418957 の反応式
[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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 8028Tetrahydrofuran溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-6cc9a4fbac8d4d9a9d2f9e2edbfb79ed
出典データセット
uspto-grants-2012_01
特許番号
US08093302B2

関連ノート

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