Ammonium Chloride → 7beta-Ethyl-estr-4-ene-3,17-dione

HRID 352312

反応式

HRID 352312 の反応式
[CH3:1][CH2:2][Mg+].[Br-].[CH3:5][C@:6]12[CH2:22][CH2:21][C@H:20]3[C@@H:11]([CH:12]=[CH:13][C:14]4[C@@H:19]3[CH2:18][CH2:17][C:16](=[O:23])[CH:15]=4)[C@@H:10]1[CH2:9][CH2:8][C:7]2=[O:24].[NH4+].[Cl-].CCOC(C)=O.CCCCCC>C1COCC1>[CH2:1]([C@H:12]1[CH2:13][C:14]2[C@H:19]([CH2:18][CH2:17][C:16](=[O:23])[CH:15]=2)[C@@H:20]2[C@@H:11]1[C@H:10]1[C@@:6]([CH2:22][CH2:21]2)([CH3:5])[C:7](=[O:24])[CH2:8][CH2:9]1)[CH3:2]

参加物

6

反応物 4

HCID 25517Ammonium ChlorideHCID 128845Estra-4,6-diene-3,17-dioneHCID 21226206Ethyl acetate hexaneHCID 178461630HCID 178461630、化合物

生成物 1

HCID 154550417beta-Ethyl-estr-4-ene-3,17-dione収率 39%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

To a mixture of CuI(Bu3P)4 (15.7 g, 40 mmol) in THF (50 mL) was added a 1.0 M solution of EtMgBr in THF (40 mL, 40 mmol) at −30° C., and stirred for 20 min. The reaction mixture was cooled to −78° C. and dione 54 (3.5 g, 12.94 mmol) was added. The reaction mixture was warmed to −30° C. for 0.5 h, and poured into saturated aqueous NH4Cl. The mixture was extracted with EtOAc. The combined organic layers were dried over anhydrous MgSO4, filtered, and then concentrated to afford a solid. Chromatography (20% EtOAc/hexane) yielded dione 55 as a yellow solid (1.5 g, 39%). The major 7α-ethyl isomer of 55: 1H NMR (300 MHz, CDCl3) δ0.89 (t, J=7.0 Hz, 3, CH2CH3), 0.93 (s, 3, CH3), 2.60 (dd, J=2.4, 14.3 Hz, 1), 5.85 (s, 1).

後処理

  1. temperatureThe reaction mixture was warmed to −30° C. for 0.5 h
  2. extractionThe mixture was extracted with EtOAc
  3. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto afford a solid

出典と根拠

ORDレコード
ord-b960e9d9350e498a8a053bf68183462e
出典データセット
uspto-grants-2004_06
特許番号
US06747018B2

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