m-Chloroperbenzoic acid → 14-Hydroxymorphinone

HRID 1521552Notes

Reaction equation

HRID 1521552 reaction equation
[CH3:1][N:2]1[C@@H:12]2[CH2:13][C:14]3[CH:19]=[CH:18][C:17]([O:20]C)=[C:16]4[O:22][C@H:6]5[C:7]([CH2:9][CH2:10][C@:11]2([OH:23])[C@:5]5([C:15]=34)[CH2:4][CH2:3]1)=[O:8].C1C=C(Cl)C=C(C(OO)=O)C=1>CC(O)=O.C(O)(C(F)(F)F)=O>[CH3:1][N:2]1[C@H:12]2[CH2:13][C:14]3[CH:19]=[CH:18][C:17]([OH:20])=[C:16]4[O:22][C@H:6]5[C:7]([CH:9]=[CH:10][C@:11]2([OH:23])[C@:5]5([C:15]=34)[CH2:4][CH2:3]1)=[O:8]

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 5284603Oxycodone

Product 1

HCID 7175141914-Hydroxymorphinone

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

According to literature methods for the preparation of oxycodeinone from thebaine,[16] oripavine (1.00 g of 78% w/w, 2.62 mmol) was treated with two portions of m-CPBA (0.82 g in total of max 77% reagent, approx. 3.66 mmol) in HOAc (4.5 mL) and TFA (0.35 mL). When the reaction was complete, the mixture was poured into ice-water (20 mL). After stirring for 30 min, the solid was removed by filtration. The filtrate was extracted with CHCl3 (5 mL×2), made basic to pH 9 with conc. NH4OH, and extracted with CHCl3/i-PrOH (5:1; 20 mL×4). The latter extracts were combined, dried (Na2SO4), filtered and concentrated to give oxymorphinone (B1) as an off-white solid, 670 mg (85%).

Workup

  1. customthe solid was removed by filtration
  2. extractionThe filtrate was extracted with CHCl3 (5 mL×2)
  3. extractionextracted with CHCl3/i-PrOH (5:1; 20 mL×4)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-03083153e95c4f1a9c6eb90f9cd63db0
Source dataset
uspto-grants-2015_07
Patent number
US09073934B2

Reaction notes

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