Ammonia → 14-Methoxydihydromorphinone

HRID 1482744Notes

Reaction equation

HRID 1482744 reaction equation
C([O:8][C:9]1[C:14]2[O:15][C@H:16]3[C:25]4(OCC[O:26]4)[CH2:24][CH2:23][C@:22]4([O:30][CH3:31])[C@@:17]53[CH2:18][CH2:19][N:20]([CH3:33])[C@@H:21]4[CH2:32][C:12]([C:13]=25)=[CH:11][CH:10]=1)C1C=CC=CC=1.Cl.N>CO>[OH:8][C:9]1[C:14]2[O:15][C@H:16]3[C:25](=[O:26])[CH2:24][CH2:23][C@:22]4([O:30][CH3:31])[C@@:17]53[CH2:18][CH2:19][N:20]([CH3:33])[C@@H:21]4[CH2:32][C:12]([C:13]=25)=[CH:11][CH:10]=1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 71150051HCID 71150051, compound

Product 1

HCID 1355932514-Methoxydihydromorphinone

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of (4R,4aS,7aR,12bS)-9-(benzyloxy)-4a-methoxy-3-methyl-1,2,3,4,4a,5,6,7a-octahydrospiro[4,12-methanobenzofuro[3,2-e]isoquinoline-7,2′-[1,3]dioxolane] (7.3 g, 16.2 mmol) in MeOH (75 mL) was added conc. HCl (50 mL). The mixture was refluxed for 5 hours then cooled with an ice bath. Concentrated ammonia (25%) was added until pH 8 was reached. The mixture was concentrated and the residues stirred with 10% MeOH/DCM (1 L) overnight. The mixture was filtered and the liquors concentrated to give (4R,4aS,7aR,12bS)-9-hydroxy-4a-methoxy-3-methyl-2,3,4,4a,5,6-hexahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-7(7aH)-one as a dark red oil (5.3 g, quantitative yields).

Workup

  1. temperatureThe mixture was refluxed for 5 hours
  2. temperaturethen cooled with an ice bath
  3. concentrationThe mixture was concentrated
  4. filtrationThe mixture was filtered
  5. concentrationthe liquors concentrated
  6. customto give

Sources & evidence

ORD record
ord-d67e3ca7d3fe40749f514c139d6e32cf
Source dataset
uspto-grants-2016_08
Patent number
US09415045B2

Reaction notes

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