Hippuristanol → HCID 49864735, 화합물

HRID 1677836노트

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HRID 1677836 반응식
[CH3:1][C@@H:2]1[C:31]([CH3:33])([CH3:32])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C@H:22]([OH:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C@@H:13]([OH:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1>N1C=CC=CC=1.O=[Cr](=O)(O[Cr](=O)([O-])=O)[O-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.CCOCC>[CH3:1][C@@H:2]1[C:31]([CH3:32])([CH3:33])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C@H:22]([OH:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C:13](=[O:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1.[CH3:1][C@@H:2]1[C:31]([CH3:32])([CH3:33])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C:22](=[O:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C:13](=[O:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1

참가 물질

6

반응물 1

HCID 9981822Hippuristanol

생성물 2

HCID 49864734HCID 49864734, 화합물수율 28%HCID 49864735HCID 49864735, 화합물수율 56%

시약·촉매·용매 3

HCID 1049Pyridine용매HCID 3283Diethyl Ether용매HCID 2724130Cornforth reagent용매

실험 절차

Oxidation of hippuristanol (1) to yield hippuristanol 11-one (4) and hippuristanol 3, 11-dione (5). To an ice-cooled solution of hippuristanol (1, 31.7 mg) in pyridine (0.5 mL), Cornforth reagent (0.7 mL) was added dropwise. The mixture was kept stirring for 30 min. in an ice bath, then 3 hr at RT. The mixture was taken up in ether and the suspension was filtered. The filtrate was washed with dilute hydrochloric acid, dried over Na2SO4, and concentrated. The resulting product was separated on silica TLC (CHCl3/EtOAc, 3:1, v/v) to give 8.8 mg of hippuristanol 11-one (4, 28%) and 17.7 mg of hippuristanol 3,11-dione (5, 56%). Hippuristanol 3,11-dione (5). white crystals. mp 181-183.5° C.; 1H NMR (CDCl3) δ 4.42 (m, 2H), 3.02 (s, 1H), 2.82 (ddd, J=13.0, 6.5, 2.0 Hz, 1H), 2.63 (d, J=12.0 Hz, 1H), 2.45 (dt, J=6.5, 14.5 Hz, 1H), 2.37 (dd, J=13.0, 8.0 Hz, 1H), 1.31 (s, 3H), 1.22 (s, 6H), 1.20 (s, 3H), 1.11 (s, 3H), 0.99 (d, J=7.0 Hz, 3H); 13C NMR (CDCl3) δ 211.6, 210.0, 115.0, 84.9, 80.4, 79.1, 63.9, 63.4, 58.8, 54.5, 46.9, 46.3, 44.3, 41.8, 40.5, 38.0, 37.0, 35.5, 35.2, 33.7, 32.4, 28.7, 28.5, 28.2, 23.0, 17.3, 14.8, 11.0; IR (KBr) 3510, 1695 cm−1; EIMS m/z 458 (M+, 5), 316 (92), 84 (100%).

후처리

  1. additionwas added dropwise
  2. custom3 hr
  3. customat RT
  4. filtrationthe suspension was filtered
  5. washThe filtrate was washed with dilute hydrochloric acid
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe resulting product was separated on silica TLC (CHCl3/EtOAc, 3:1

출처 및 근거

ORD 기록
ord-c35980a653c54caf8eb75a8521aa20ad
출처 데이터셋
uspto-grants-2011_08
특허 번호
US08008346B2

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