Oxygen → 12,14-Dihydroxy-3-oxocard-20(22)-enolide

HRID 1075763Notes

Reaction equation

HRID 1075763 reaction equation
[H][H].[CH3:3][C@@:4]12[C@H:13]3[CH2:14][C@@H:15]([OH:29])[C@:16]4([CH3:28])[C@@H:20]([C:21]5[CH2:26][O:25][C:23](=[O:24])[CH:22]=5)[CH2:19][CH2:18][C@:17]4([OH:27])[C@@H:12]3[CH2:11][CH2:10][C@@H:9]1[CH2:8][C@@H:7]([OH:30])[CH2:6][CH2:5]2.O=O>O.CC(C)=O.[Pt]=O>[CH3:3][C@@:4]12[CH:13]3[CH2:14][C@@H:15]([OH:29])[C@:16]4([CH3:28])[C@@H:20]([C:21]5[CH2:26][O:25][C:23](=[O:24])[CH:22]=5)[CH2:19][CH2:18][C@:17]4([OH:27])[CH:12]3[CH2:11][CH2:10][C@@H:9]1[CH2:8][C:7](=[O:30])[CH2:6][CH2:5]2

Participants

7

Reactant 3

HCID 977OxygenHCID 15478DigoxigeninHCID 178418361HCID 178418361, compound2×

Product 1

HCID 2050312,14-Dihydroxy-3-oxocard-20(22)-enolide

Reagents, catalysts & solvents 3

HCID 82844Platinum oxide (PtO)CatalystHCID 180AcetoneSolventHCID 962WaterSolvent2×

Procedure

Platinum oxide (Adams' catalyst) (500 mg.) was suspended in water (50 ml.) and a continuous stream of hydrogen passed for 1 hour. The hydrogen was displaced by nitrogen and digoxigenin (2.0 g.), in acetone (200 ml.) and water (50 ml.), added. A continuous stream of oxygen was passed through the mixture for 18 hours. The catalyst was removed by filtration, washed with acetone, the washings added to the filtrate and the filtrate concentrated in vacuo. The residue was dissolved in chloroform, washed with water and the solution dried (magnesium sulphate). Evaporation of the solvent in vacuo gave a gum which crystallised from acetone/ether. The 3-dehydrodigoxigenin melted at 251.2°C. and had [α] D25 + 39.1° (c = 0.48 in methanol).

Workup

  1. customThe catalyst was removed by filtration
  2. washwashed with acetone
  3. additionthe washings added to the filtrate
  4. concentrationthe filtrate concentrated in vacuo
  5. dissolutionThe residue was dissolved in chloroform
  6. washwashed with water
  7. dry with materialthe solution dried (magnesium sulphate)
  8. customEvaporation of the solvent in vacuo
  9. customgave a gum which
  10. customcrystallised from acetone/ether
  11. custom[α] D25 + 39.1° (c = 0.48 in methanol)

Sources & evidence

ORD record
ord-5bb261c2b6a5418fb6020369d9a31e4d
Source dataset
uspto-grants-1976_05
Patent number
US03954739

Reaction notes

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