Lithium → Cholan-24-oic acid, 3-oxo-, methyl ester, (5alpha)-

HRID 1062921노트

반응식

HRID 1062921 반응식
[CH3:1][O:2][C:3](=[O:28])[CH2:4][CH2:5][C@H:6]([C@@H:8]1[C@:25]2([CH3:26])[C@H:11]([C@H:12]3[C@H:22]([CH2:23][CH2:24]2)[C@:20]2([CH3:21])[C:15](=[CH:16][C:17](=[O:27])[CH2:18][CH2:19]2)[CH2:14][CH2:13]3)[CH2:10][CH2:9]1)[CH3:7].[Li].C(OCC)(=O)C.CCCCCC>CCOCC>[CH3:1][O:2][C:3](=[O:28])[CH2:4][CH2:5][C@H:6]([C@@H:8]1[C@:25]2([CH3:26])[C@H:11]([C@H:12]3[C@H:22]([CH2:23][CH2:24]2)[C@:20]2([CH3:21])[C@H:15]([CH2:16][C:17](=[O:27])[CH2:18][CH2:19]2)[CH2:14][CH2:13]3)[CH2:10][CH2:9]1)[CH3:7]

참가 물질

5

반응물 3

HCID 3028194LithiumHCID 110364803-Oxochol-4-en-24-oic acid methyl esterHCID 21226206Ethyl acetate hexane

생성물 1

HCID 22821830Cholan-24-oic acid, 3-oxo-, methyl ester, (5alpha)-수율 41.8%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

실험 절차

Into a solution of 3-oxo-4-cholenic acid methyl ester 3002 (13.0 g, 23.68 mmol) in dry ether (50 ml) was added distilled liquid ammonia (70 ml) at −78° C. Lithium (1.0 g, 144.1 mmol) was added in small portions until a blue coloration persisted for 10 minutes, after which the solution was quenched with solid NH4Cl (50 g). Ammonia was evaporated, and the resulting residue was partitioned between water (100 ml) and ether (150 ml). The aqueous solution was extracted further with ether (3×50 ml). The combined extracts were washed with brine (1×70 ml), dried (MgSO4), filtered and concentrated in vacuo to get the crude product. Flash chromatography of the crude product in silica gel using ethyl acetate:hexane (2:8) gave pure 3-oxo-5α-cholanic acid methyl ester 3003 (3.85 g, 29w). 1H NMR (400 MHz, CDCl3) δ: 0.69 (3H, s, 18-CH3, 0.91 (3H, d, 21-CH3), 1.02 (3H, s, 19-CH3) and 3.66 (3H, s, CO2CH3).

후처리

  1. distillationdistilled liquid ammonia (70 ml) at −78° C
  2. customafter which the solution was quenched with solid NH4Cl (50 g)
  3. customAmmonia was evaporated
  4. customthe resulting residue was partitioned between water (100 ml) and ether (150 ml)
  5. extractionThe aqueous solution was extracted further with ether (3×50 ml)
  6. washThe combined extracts were washed with brine (1×70 ml)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto get the crude product

출처 및 근거

ORD 기록
ord-83de01f46a1447bc9e60c4d223f79fbd
출처 데이터셋
uspto-grants-2005_11
특허 번호
US06962909B2

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