Bromobenzene → HCID 70568455, compound

HRID 1680228Notes

Reaction equation

HRID 1680228 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[CH2:7][C@H:8]3[N:20]([CH3:21])[CH2:19][CH2:18][C@@:14]4([C:15]=2[C:16]=1[OH:17])[C@@:9]3([O:24][CH3:25])[C@H:10]([CH3:23])[CH2:11][C:12](=[O:22])[CH2:13]4.Br[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.C([O-])([O-])=O.[K+].[K+]>N1C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[CH2:7][C@H:8]3[N:20]([CH3:21])[CH2:19][CH2:18][C@@:14]4([C:15]=2[C:16]=1[O:17][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C@@:9]3([O:24][CH3:25])[C@H:10]([CH3:23])[CH2:11][C:12](=[O:22])[CH2:13]4

Participants

5

Reactant 3

HCID 7961BromobenzeneHCID 11430Potassium CarbonateHCID 86737786HCID 86737786, compound

Product 1

HCID 70568455HCID 70568455, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a solution of 3,14-dimethoxy-[α,17-dimethyl-4-hydroxymorphinan-6-one (21) (0.4 g, 1.159 mmol) in dry pyridine (1 ml) was added bromobenzene (0.205 g, 1.35 mmol) and 0.216 g (1.565 mmol) of K2CO3 (freshly dried at 110° C. for 2 hours in a vacuum oven and quickly ground and sieved to 200 mesh). More pyridine (0.5 ml) followed by copper powder (20 mg, 10 micron) was added and the mixture was refluxed (oil bath temperature 130°-140°) for 24 hours under a nitrogen atmosphere with stirring. The mixture was filtered while hot and the residue was washed with hot pyridine (2 ml). After adding 10 ml of toluene, the solution was concentrated under reduced pressure to give (22) as a foamy solid. Thin layer chromatography on a silica gel plate (solvent system: CHCl3 :MeOH, 80:20) showed a single spot. The compound was quickly chromatographed on a silica gel column and eluted with graded methanol/chloroform mixtures to give 0.45 g (92% theory) of 3,14-dimethoxy-8α,17-dimethyl-4-phenoxymorphinan-6-one (22) as a foamy solid.

Workup

  1. customfreshly dried at 110° C. for 2 hours in a vacuum oven and quickly ground
  2. filtrationsieved to 200 mesh)
  3. additionwas added
  4. temperaturethe mixture was refluxed (oil bath temperature 130°-140°) for 24 hours under a nitrogen atmosphere
  5. filtrationThe mixture was filtered while hot and the residue
  6. washwas washed with hot pyridine (2 ml)
  7. additionAfter adding 10 ml of toluene
  8. concentrationthe solution was concentrated under reduced pressure

Sources & evidence

ORD record
ord-199ad999dc0244118b4a6e19723133fa
Source dataset
uspto-grants-1981_06
Patent number
US04272540

Reaction notes

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