Hydrogen Peroxide → 3-Desoxy-3-carboxamidonaltrexone

HRID 2384595ノート

反応式

HRID 2384595 の反応式
[CH:1]1([CH2:4][N:5]2[CH2:24][CH2:23][C@:12]34[C:13]5[C:14]6[O:22][C@H:11]3[C:10](=[O:25])[CH2:9][CH2:8][C@@:7]4([OH:26])[C@H:6]2[CH2:19][C:18]=5[CH:17]=[CH:16][C:15]=6[C:20]#[N:21])[CH2:3][CH2:2]1.C(=O)([O-])[O-:28].[K+].[K+].OO>CS(C)=O.C(Cl)Cl>[CH:1]1([CH2:4][N:5]2[CH2:24][CH2:23][C@:12]34[C:13]5[C:14]6[O:22][C@H:11]3[C:10](=[O:25])[CH2:9][CH2:8][C@@:7]4([OH:26])[C@H:6]2[CH2:19][C:18]=5[CH:17]=[CH:16][C:15]=6[C:20]([NH2:21])=[O:28])[CH2:3][CH2:2]1

参加物

6

反応物 3

HCID 784Hydrogen PeroxideHCID 11430Potassium CarbonateHCID 15425895HCID 15425895、化合物

生成物 1

HCID 100219463-Desoxy-3-carboxamidonaltrexone収率 71.4%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 6344Dichloromethane溶媒

実験手順

To an ice/water cooled suspension of (5a)-17-(cyclopropylmethyl)-14-hydroxy-6-oxo-4,5-epoxymorphinan-3-carbonitrile [P2] (6.0 g, 17.1 mmol) and potassium carbonate (7.09 g, 51.37 mmol) in DMSO (120 mL) was added hydrogen peroxide (25 mL, 35 wt. % in H2O) drop wise at a rate to ensure the temperature remained below 20° C. The mixture was stirred for 2 hours then diluted with DCM (800 mL). The solution was washed with water (3×500 mL) before the organic phase was dried (MgSO4). Filtration and removal of the solvent under reduced pressure gave crude product that was purified by trituration with methanol giving (5a)-17-(cyclopropylmethyl)-14-hydroxy-6-oxo-4,5-epoxymorphinan-3-carboxamide [P3] (4.50 g, 71% yield); LC/MS (r.t. 10.1 minutes [5 to 95% B]), 369 (M+H)+.

後処理

  1. customremained below 20° C
  2. washThe solution was washed with water (3×500 mL) before the organic phase
  3. dry with materialwas dried (MgSO4)
  4. filtrationFiltration and removal of the solvent under reduced pressure
  5. customgave crude product that
  6. customwas purified by trituration with methanol

出典と根拠

ORDレコード
ord-675e2dfb2bdc4f28a8596c5cdb60cca5
出典データセット
uspto-grants-2012_09
特許番号
US08263807B2

反応ノート

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