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

HRID 1062921Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1062921
[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]

Komponenten

5

Edukt 3

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

Produkt 1

HCID 22821830Cholan-24-oic acid, 3-oxo-, methyl ester, (5alpha)-Ausbeute 41,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-83de01f46a1447bc9e60c4d223f79fbd
Quelldatensatz
uspto-grants-2005_11
Patentnummer
US06962909B2

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