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

HRID 418895

反応式

HRID 418895 の反応式
[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

参加物

7

反応物 4

HCID 77304-BromoanisoleHCID 123165tert-ButylphosphineHCID 110316906-methoxy-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-oneHCID 23676156Sodium t-butoxide

生成物 1

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

試薬・触媒・溶媒 2

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

実験手順

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).

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 vacuo
  7. customAdd diethyl ether and collect precipitate

出典と根拠

ORDレコード
ord-8e2aae57785e4b55a971be0f1304a860
出典データセット
uspto-grants-2012_01
特許番号
US08093302B2

関連ノート

読み込み中…