Hydrogen Peroxide → N-(1,1-Dimethylethyl)-4,5-epoxy3-oxoandrostane-17beta-carboxamide

HRID 1109000Notes

Reaction equation

HRID 1109000 reaction equation
[CH3:1][C:2]([NH:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:9]12[CH3:10])[C@:22]1([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH2:20][CH2:21]1)[CH2:16][CH2:15]3)=[O:7])([CH3:4])[CH3:3].[OH:28]O.[OH-].[Na+]>CO.ClCCl.O>[CH3:4][C:2]([NH:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:9]12[CH3:10])[C@:22]1([CH3:23])[C:17]2([O:28][CH:18]2[C:19](=[O:27])[CH2:20][CH2:21]1)[CH2:16][CH2:15]3)=[O:7])([CH3:1])[CH3:3]

Participants

7

Reactant 3

HCID 784Hydrogen PeroxideHCID 14798Sodium Hydroxide2×HCID 475445(8S,9S,10R,13S,14S,17S)-N-tert-butyl-10,13-dimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthrene-17-carboxamide

Product 1

HCID 86745913N-(1,1-Dimethylethyl)-4,5-epoxy3-oxoandrostane-17beta-carboxamideYield 66.2%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of N-(1,1-dimethylethyl)-3-oxoandrost-4-ene-17β-carboxamide (4.77 g, 12.8 mmole) in methanol (55 mL) and dichloromethane (11 mL) was cooled to 12° C. and treated in one portion with 30% aqueous hydrogen peroxide (3.3 mL) followed by dropwise addition of an aqueous sodium hydroxide solution prepared by dissolving sodium hydroxide (0.38 g) in water (2.2 mL). After one hour, the cooling bath was removed and the reaction was stirred for an additional 3 hours. Most of the solvent was then removed in vacuo. The residue was dissolved in dichloromethane and purified by flash chromatography (hexane-20% ethyl acetate and hexane-40% ethyl acetate) to give N-(1,1-Dimethylethyl)-4,5-epoxy-3-oxoandrostane-17β-carboxamide (3.3 g, 66.2%) as a solid foam. This material was a mixture of the 4α,5β- and 4β,5β-isomers and it was used as is in further reactions.

Workup

  1. customprepared
  2. customthe cooling bath was removed
  3. customMost of the solvent was then removed in vacuo
  4. dissolutionThe residue was dissolved in dichloromethane
  5. custompurified by flash chromatography (hexane-20% ethyl acetate and hexane-40% ethyl acetate)

Sources & evidence

ORD record
ord-910f32eaa0fb441abf030663bf6d6ac1
Source dataset
uspto-grants-1994_06
Patent number
US05318961

Reaction notes

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