2-Butene, 1-bromo-3-methyl- → (-)-1-[17-(3-Methyl-2-butenyl)morphinan-3-yl]ethanone

HRID 1758508Notes

Reaction equation

HRID 1758508 reaction equation
[CH:1]1[C:14]2[CH2:13][C@H:12]3[NH:15][CH2:16][CH2:17][C@:6]4([C@H:11]3[CH2:10][CH2:9][CH2:8][CH2:7]4)[C:5]=2[CH:4]=[C:3]([C:18](=[O:20])[CH3:19])[CH:2]=1.C(=O)(O)[O-].[Na+].[CH3:26][C:27]([CH3:31])=[CH:28][CH2:29]Br>CN(C)C=O>[CH3:26][C:27]([CH3:31])=[CH:28][CH2:29][N:15]1[CH2:16][CH2:17][C@@:6]23[C:5]4[CH:4]=[C:3]([C:18](=[O:20])[CH3:19])[CH:2]=[CH:1][C:14]=4[CH2:13][C@@H:12]1[C@@H:11]2[CH2:10][CH2:9][CH2:8][CH2:7]3

Participants

5

Reactant 3

HCID 700922-Butene, 1-bromo-3-methyl-HCID 516892Sodium BicarbonateHCID 13100586HCID 13100586, compound

Product 1

HCID 13100605(-)-1-[17-(3-Methyl-2-butenyl)morphinan-3-yl]ethanoneYield 93.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a mixture of 1.8 g of (-)-1-(morphinan-3-yl)ethanone, 0.6 g of sodium bicarbonate and 25 ml of dimethylformamide, was added 1.0 g of dimethylallyl bromide. After the mixture had been heated at 50° for 16 hours, it was cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure and the residue was partitioned between 50 ml of methylene chloride and 30 ml of water. The methylene chloride solution was washed with water and dried over magnesium sulfate. Removal of the solvent gave 2.1 g (93%) of crude (-)-1-[17-(3-methyl-2-butenyl)morphinan-3-yl]ethanone. For analysis, a sample of this compound was distilled, bp 185°-195° (0.05 mm), [α]25D-76.53° (c 0.98, MeOH).

Workup

  1. temperatureAfter the mixture had been heated at 50° for 16 hours
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customthe residue was partitioned between 50 ml of methylene chloride and 30 ml of water
  5. washThe methylene chloride solution was washed with water
  6. dry with materialdried over magnesium sulfate
  7. customRemoval of the solvent

Sources & evidence

ORD record
ord-7dd742878f7a437b8fa4a841a19ef86a
Source dataset
uspto-grants-1983_02
Patent number
US04374139

Reaction notes

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