Hydrogen Peroxide → (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 2367860Notes

Reaction equation

HRID 2367860 reaction equation
[OH:1]O.[CH3:3][N:4]1[C@@H:20]2[CH2:21][C:9]3[CH:10]=[CH:11][C:12]([O:24][CH3:25])=[C:13]4[O:14][C@H:15]5[C:16]([O:22]C)=[CH:17][CH:18]=[C:19]2[C@:7]5([C:8]=34)[CH2:6][CH2:5]1.[NH4+].[OH-]>C(O)=O.OS(O)(=O)=O.O>[CH3:3][N:4]1[C@@H:20]2[CH2:21][C:9]3[CH:10]=[CH:11][C:12]([O:24][CH3:25])=[C:13]4[O:14][CH:15]5[C:16]([CH:17]=[CH:18][C@:19]2([OH:1])[C@:7]5([C:8]=34)[CH2:6][CH2:5]1)=[O:22]

Participants

7

Reactant 3

HCID 784Hydrogen PeroxideHCID 14923Ammonium 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 86%

Reagents, catalysts & solvents 3

HCID 284Formic AcidSolventHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Conditions

Temperature
40 °C

Procedure

Hydrogen peroxide (30%, 1.3 mL, 13 mmol) is added to a solution of thebaine O-1 (3.11 g, 10 mmol) in a mixture of formic acid (88%, 1.3 mL) and H2SO4 (0.7%, 4.1 mL). The mixture is heated at 40° C. (bath temperature) for 6.5 h, cooled, diluted with water (10 mL), and made basic with concentrated NH4OH. The precipitate is filtered, washed with H2O and dried (MgSO4). The product is recrystallized from EtOH—CHCl3 to yield O-5 (2.70 g, expected yield 86%). See Iijima, I.; Minamikawa, J.; Jacobson, A. E.; Brossi, A.; Rice, K. C.; J. Med. Chem. (1978) 21, 398.

Workup

  1. temperaturecooled
  2. filtrationThe precipitate is filtered
  3. washwashed with H2O
  4. dry with materialdried (MgSO4)
  5. customThe product is recrystallized from EtOH—CHCl3
  6. customto yield O-5 (2.70 g

Sources & evidence

ORD record
ord-3e5dab4cffd54edab1e4ca78bcb9c201
Source dataset
uspto-grants-2014_04
Patent number
US08703099B2

Reaction notes

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