Oxalic Acid → (4R,4aS,12bS)-4a-hydroxy-9-methoxy-3-methyl-2,4,7a,13-tetrahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-7-one

HRID 1436849Notes

Reaction equation

HRID 1436849 reaction equation
C(O)(=O)C(O)=[O:3].[CH3:7][N:8]1[C@@H:24]2[CH2:25][C:13]3[CH:14]=[CH:15][C:16]([O:28][CH3:29])=[C:17]4[O:18][C@H:19]5[C:20]([O:26]C)=[CH:21][CH:22]=[C:23]2[C@:11]5([C:12]=34)[CH2:10][CH2:9]1.[OH-].[Na+]>O.C(O)(=O)C.OO>[CH3:7][N:8]1[C@@H:24]2[CH2:25][C:13]3[CH:14]=[CH:15][C:16]([O:28][CH3:29])=[C:17]4[O:18][CH:19]5[C:20]([CH:21]=[CH:22][C@:23]2([OH:3])[C@:11]5([C:12]=34)[CH2:10][CH2:9]1)=[O:26]

Participants

7

Reactant 3

HCID 971Oxalic AcidHCID 14798Sodium HydroxideHCID 5324289Thebaine

Product 1

HCID 5359420(4R,4aS,12bS)-4a-hydroxy-9-methoxy-3-methyl-2,4,7a,13-tetrahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-7-oneYield 82%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 784Hydrogen PeroxideSolventHCID 962WaterSolvent

Conditions

Temperature
2 °C

Procedure

6-Benzyloxy-4,5α-epoxy-3-methoxy-17-methylmorfina-6,8(14)-diene (52.5 g) is dissolved in a solution prepared by dissolving 9.8 g of oxalic acid in 35 ml of water, 10 ml of acetic acid and 21.2 ml of 30% hydrogen peroxide are added. The reaction mixture is stirred at 20° C. until total conversion of the benzyl analogue of thebaine, the reaction mixture is cooled down to 2° C., 8% aqueous solution of NaOH is added with stirring until pH of 9.2. Precipitated crystals of 14-hydroxycodeinone are filtered off, washed with water and dried. The procedure yields ca. 37 g of 14-hydroxycodeinone (82%). Further procedure of preparation of Oxycodone hydrochloride is the same as in Example Ib) and Ic).

Workup

  1. customprepared
  2. additionare added
  3. customPrecipitated crystals of 14-hydroxycodeinone
  4. filtrationare filtered off
  5. washwashed with water
  6. customdried

Sources & evidence

ORD record
ord-74dd04d089184e75bd039d8d62d100e2
Source dataset
uspto-grants-2009_11
Patent number
US07619087B2

Reaction notes

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