m-Chloroperbenzoic acid → Oxymorphone

HRID 515575Notes

Reaction equation

HRID 515575 reaction equation
CN1[C@@H]2CC3C=CC(O)=C4O[C@H]5C(OC)=CC=C2[C@]5(C=34)CC1.ClC1C=C(C=CC=1)C(OO)=O.[CH3:34][N:35]1[C@H:45]2[CH2:46][C:47]3[CH:52]=[CH:51][C:50]([OH:53])=[C:49]4[O:54][C@H:39]5[C:40]([CH:42]=[CH:43][C@:44]2([OH:55])[C@:38]5([C:48]=34)[CH2:37][CH2:36]1)=[O:41].[H][H]>[Pd].C(O)(=O)C>[CH3:34][N:35]1[C@@H:45]2[CH2:46][C:47]3=[CH:52][CH:51]=[C:50]([OH:53])[C:49]4[O:54][C@H:39]5[C:40]([CH2:42][CH2:43][C@:44]2([OH:55])[C@:38]5([C:48]=43)[CH2:37][CH2:36]1)=[O:41]

Participants

7

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 5462306Oripavine2×HCID 7175141914-Hydroxymorphinone2×HCID 178418361HCID 178418361, compound

Product 1

HCID 5284604OxymorphoneYield 95%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolvent

Procedure

A mixture of CPS-O (6.92 g contains 76% (5.26 g, 17.7 mmol) of oripavine), meta-chloroperoxybenzoic acid (MCPBA, 4.30 g) and glacial acetic acid (52 ml) is stirred at room temperature for 5 hours. The amount of oripavine is then expected to be not more than 1% by HPLC analysis. To the resulting 14-hydroxymorphinone mixture is added 5% Pd/C (0.55 g) and hydrogenation proceeds at room temperature at 48 psig of hydrogen for about 18 hours. The amount of unreacted 14-hydroxymorphinone is expected to be not more than 0.5% by HPLC analysis. The mixture is filtered to remove the catalyst and the filtrate is evaporated to almost dryness. The residue is dissolved in water and basified to pH 9 by ammonium hydroxide. The solids are collected by filtration and dried at 90° C. and under 25-inch Hg of vacuum for 3 hours to give crude oxymorphone (approximately 95% yield expected).

Workup

  1. filtrationThe mixture is filtered
  2. customto remove the catalyst
  3. customthe filtrate is evaporated to almost dryness
  4. dissolutionThe residue is dissolved in water and basified to pH 9 by ammonium hydroxide
  5. filtrationThe solids are collected by filtration
  6. customdried at 90° C. and under 25-inch Hg of vacuum for 3 hours

Sources & evidence

ORD record
ord-3ba60a5aa2bc4e939ef2eb95e757bdc3
Source dataset
uspto-grants-2015_08
Patent number
US09108974B2

Reaction notes

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