Acetic Acid → 14-Hydroxydihydrocodeine

HRID 1406628Notes

Reaction equation

HRID 1406628 reaction equation
[CH3:1][N:2]1[C@@H:12]2[CH2:13][C:14]3[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]4[O:22][CH: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].C(O)C.C(O)(=O)C.[H][H]>[Pd].O>[CH3:1][N:2]1[C@@H:12]2[CH2:13][C:14]3[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]4[O:22][C@H:6]5[C@@H:7]([OH:8])[CH2:9][CH2:10][C@:11]2([OH:23])[C@:5]5([C:15]=34)[CH2:4][CH2:3]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 702EthanolHCID 5359420(4R,4aS,12bS)-4a-hydroxy-9-methoxy-3-methyl-2,4,7a,13-tetrahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-7-oneHCID 178418361HCID 178418361, compound

Product 1

HCID 536024114-HydroxydihydrocodeineYield 84%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 962WaterSolvent2×

Procedure

14-Hydroxycodeinone (4.5 g) was warmed with ethanol (2.17 g/g 14-hydroxycodeinone) to 60-65° C. and acetic acid was added in portions until all solid dissolved. Following the addition of 10% Pd/C (dry, 0.01 g/g 14-hydroxycodeinone) and water (0.01 g/g 14-hydroxycodeinone) to compensate for the water in the dry Pd/C catalyst, the hydrogenation was performed with hydrogen being introduced at 80° C. The reaction was sampled after 22 h and was determined to be complete. This reaction resulted in low levels of 6α-oxycodol. After isolation (84% yield by LOD), the level of 6α-oxycodol was also determined to be low by analysis.

Workup

  1. dissolutiondissolved
  2. additionintroduced at 80° C
  3. aliquotThe reaction was sampled after 22 h

Sources & evidence

ORD record
ord-7a925e4519d342a7a53e9765dd023172
Source dataset
uspto-grants-2014_12
Patent number
US08916707B2

Reaction notes

Loading…