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

HRID 357691ノート

反応式

HRID 357691 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

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, 29%). 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).

後処理

  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

出典と根拠

ORDレコード
ord-821047a16cc6479db941eada80c1f50f
出典データセット
uspto-grants-1998_11
特許番号
US05840936

反応ノート

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