Water → 6,7-Dimethyl-4-oxo-1,2,3,4-tetrahydrophenanthrene

HRID 1488329ノート

反応式

HRID 1488329 の反応式
CC([O-])(C)C.[K+].[CH3:7][C:8]1[CH:9]=[C:10]2[C:19](=[CH:20][C:21]=1[CH3:22])[CH:18]=[CH:17][C:16]1[CH2:15][CH2:14][CH2:13][C:12](=[O:23])[C:11]2=1.[CH2:24](I)[CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH:33]=[CH2:34].O>C1C=CC=CC=1>[CH3:7][C:8]1[CH:9]=[C:10]2[C:19](=[CH:20][C:21]=1[CH3:22])[CH:18]=[CH:17][C:16]1[CH2:15][CH2:14][CH:13]([CH2:34][CH2:33][CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH:25]=[CH2:24])[C:12](=[O:23])[C:11]2=1.[CH3:7][C:8]1[CH:9]=[C:10]2[C:19](=[CH:20][C:21]=1[CH3:22])[CH:18]=[CH:17][C:16]1[CH2:15][CH2:14][CH2:13][C:12](=[O:23])[C:11]2=1

参加物

7

反応物 4

HCID 962WaterHCID 1111946211-Iodoundec-1-eneHCID 229045956,7-Dimethyl-4-oxo-1,2,3,4-tetrahydrophenanthreneHCID 23665647Potassium tert-butoxide

生成物 2

HCID 229045886,7-Dimethyl-4-oxo-3-(10-undecenyl)-1,2,3,4-tetrahydrophenanthrene収率 39%HCID 229045956,7-Dimethyl-4-oxo-1,2,3,4-tetrahydrophenanthrene収率 47%

試薬・触媒・溶媒 1

HCID 241Benzene溶媒2 回

反応条件

温度
60 °C

実験手順

t-BuOK (3.6 g, 0.032 mole) was dissolved in 250 ml of dry benzene at 40°-50° C. To the stirred solution was added 6,7-Dimethyl-4-oxo-1,2,3,4-tetrahydrophenanthrene (3.6 g, 0.016 mole) in 50 ml of dry benzene and then, 10-undecenyl iodide (4.58 g, 0.016 mole) at 30° C. under N2. The mixture was heated to 60° C. for 2.5 hr under N2. After cooling the reaction mixture to room temperature, water was added. The whole mixture was extracted twice with diethylether. The combined diethylether solution was dried over anhydrous MgSO4 and then concentrated. Flash column chromatography of the residue on silica gel afforded 6,7-Dimethyl-4-oxo-3-(10-undecenyl)-1,2,3,4-tetrahydrophenanthrene as a sticky brown solid (2.36 g, 0.0063 mole, 39% yield) as a desired product, and unreacted 6,7-Dimethyl-4-oxo-1,2,3,4-tetrahydrophenanthrene (1.70 g, 47% recovered). 1H NMR (CDCl3) δ 1.29-1.62 (m, 14H), 1.86-2.08 (m, 4H), 2.21-2.35 (m, 2H), 2.40 (s, 3H), 2.46 (s, 3H), 2.52-2.63 (m, 1H), 3.07-3.13 (m, 2H), 4.90-5.04 (m, 2H), 5.75-5.89 (m, 1H), 7.17 (d, J=8.2 Hz, 1H), 7.53 (s, 1H), 7.77 (d, J=8.2 Hz, 1H), 9.10 (s, 1H), IR (KBr) cm-1 2920, 2850, 1669, 1600, exact (EI) mass. calcd. for C27H36O: 376.2766, Found: 376.2766.

後処理

  1. customat 30° C.
  2. temperatureAfter cooling the reaction mixture to room temperature
  3. extractionThe whole mixture was extracted twice with diethylether
  4. dry with materialThe combined diethylether solution was dried over anhydrous MgSO4
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-961409ea418b45199d6f0a2d80afad19
出典データセット
uspto-grants-1997_10
特許番号
US05674387

反応ノート

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