Water → Rotenol

HRID 1038279

反応式

HRID 1038279 の反応式
[CH3:1][C:2]([C@@H:4]1[O:29][C:7]2[CH:8]=[CH:9][C:10]3[C:23](=[O:24])[C@@H:22]4[C@@H:13]([CH2:14][O:15][C:16]5[C:21]4=[CH:20][C:19]([O:25][CH3:26])=[C:18]([O:27][CH3:28])[CH:17]=5)[O:12][C:11]=3[C:6]=2[CH2:5]1)=[CH2:3].[BH4-].[Na+].O>CO>[CH3:3][C:2]([C@@H:4]1[O:29][C:7]2[CH:8]=[CH:9][C:10]([C:23]([CH:22]3[C:21]4[C:16](=[CH:17][C:18]([O:27][CH3:28])=[C:19]([O:25][CH3:26])[CH:20]=4)[O:15][CH2:14][CH2:13]3)=[O:24])=[C:11]([OH:12])[C:6]=2[CH2:5]1)=[CH2:1]

参加物

5

反応物 3

HCID 962WaterHCID 6758RotenoneHCID 4311764Sodium borohydride

生成物 1

HCID 44257420Rotenol収率 99.9%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
0 °C

実験手順

12-Rotenol Synthesis: Rotenone (2 g, 5 mmol) was suspended in methanol (50 mL) and was cooled to 0° C. in an ice bath. Added solid NaBH4 (770 mg, 20 mmol) in one portion and the mixture was stirred for 1 h at 0° C. The reaction mixture was allowed to come to room temperature. Water (100 mL) was added, extracted with dichloromethane (3×50 mL), washed with brine, dried over anhydrous Na2SO4, filtered, and evaporated to obtain a fluffy solid, which was purified by flash column chromatography on silica gel using EtOAc:Hexane (1:3) to afford rotenol as colorless fluffy solid (1.98 g, 98%). m. p.: 80-82° C.; 1H NMR (CDCl3): δ 7.03 (d, 1H, J=7.96 Hz, 11-H); 6.68 (s, 1H, 1-H); 6.45 (s, 1H, 4-H), 6.44 (d, 1H, J=7.96 Hz, 10-H); 5.19 (t, 1H, J=8.89 Hz, 5′H); 5.07 (s, 1H, 7′H); 4.90 (br s, 2H, 7′-H and 12-H); 4.8-4.9 (ddd, 1H, J=5.14, 5.28, 10.68 Hz, 6a-H); 4.60 (dd, 1H, J=10.08, 10.68 Hz, 6′-Hβ); 4.22 (dd, 1H, J=5.14, 10.08 Hz, 6′-Hα); 3.84 (s, 3H, 3-OCH3); 3.83 (s, 3H, 2-OCH3); 3.37 (dd, 1H, J=4.97, 5.28 Hz, 12a-H); 3.28 (dd, 1H, J=8.89, 15.67 Hz, 4′-Hβ); 2.94 (dd, 1H, J=8.89, 15.67 Hz, 4′-Hα); 1.79 (s, 3H, 8′-CH3); 13C NMR (CDCl3): δ 188.73 (C-12); 167.14 (C-9); 157.73 (C-7a); 149.23 (C-3); 147.19 (C-4a); 143.61 (C-2); 142.83 (C-6′); 129.77 (C-11); 113.14 (C-11a); 112.80 (C-8); 112.40 (C-7′); 110.09 (C-1); 104.68 (C-10); 104.63 (C-12b); 100.70 (C-4); 87.66 (C-5′); 72.04 (C-6a); 66.10 (C-6); 56.13 (OCH3); 55.69 (OCH3); 44.41 (C-12a); 31.12 (C-4′); 17.00 (C-8′).

後処理

  1. customto come to room temperature
  2. extractionextracted with dichloromethane (3×50 mL)
  3. washwashed with brine
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. customevaporated
  7. customto obtain a fluffy solid, which
  8. customwas purified by flash column chromatography on silica gel

出典と根拠

ORDレコード
ord-3fcaa9eb753e40f69a2cadf8a953298d
出典データセット
uspto-grants-2013_10
特許番号
US08551448B2

関連ノート

読み込み中…