Allyl bromide → 1,3,4,5-Tetrahydro-3-(methoxycarbonyl)-1-(methoxymethyl)-4-(methoxyphenyl)-3-(2-propenyl)-7-(trifluoromethyl)-2H-1-benzazepin-2-one

HRID 580398Notes

Reaction equation

HRID 580398 reaction equation
[H-].[Na+].[CH3:3][O:4][C:5]([CH:7]1[CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[O:20][CH3:21])[CH2:12][C:11]2[CH:22]=[C:23]([C:26]([F:29])([F:28])[F:27])[CH:24]=[CH:25][C:10]=2[N:9]([CH2:30][O:31][CH3:32])[C:8]1=[O:33])=[O:6].[CH2:34](Br)[CH:35]=[CH2:36].[H-]>CN(C)C=O>[CH3:3][O:4][C:5]([C:7]1([CH2:36][CH:35]=[CH2:34])[CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[O:20][CH3:21])[CH2:12][C:11]2[CH:22]=[C:23]([C:26]([F:27])([F:28])[F:29])[CH:24]=[CH:25][C:10]=2[N:9]([CH2:30][O:31][CH3:32])[C:8]1=[O:33])=[O:6]

Participants

6

Reactant 4

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 166653HydrideHCID 201350811,3,4,5-Tetrahydro-3-(methoxycarbonyl)-1-(methoxymethyl)-4-(methoxyphenyl)-7-(trifluoromethyl)-2H-1-benzazepin-2-one

Product 1

HCID 201350941,3,4,5-Tetrahydro-3-(methoxycarbonyl)-1-(methoxymethyl)-4-(methoxyphenyl)-3-(2-propenyl)-7-(trifluoromethyl)-2H-1-benzazepin-2-one

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a suspension of sodium hydride (384 mg; 8 mmole; 50% oil dispersion) in dry dimethylformamide (35 ml), cooled in an ice water bath, was added a solution of 1,3,4,5-tetrahydro-3-(methoxycarbonyl)-1-(methoxymethyl)-4-(methoxyphenyl)-7-(trifluoromethyl)-2H-1-benzazepin-2-one (917 mg; 21 mmole) in dimethylformamide (8 ml) with stirring. After stirring at 0°-5° C. for 30 minutes, allyl bromide (1.5 ml) was added in one portion, the mixture was allowed to stand at 0°-5° C. for three additional hours, whereupon excess hydride was destroyed by the addition of water. The mixture was diluted with ether and washed with water. The aqueous layer was extracted with ether (three times), and the combined ether extracts were dried (magnesium sulfate) and concentrated. The crude residue was flash chromatographed (silica gel/5-20% ethyl acetate:hexane) to obtain 905 mg of the title compound in crystalline form.

Workup

  1. temperaturecooled in an ice water bath
  2. stirringAfter stirring at 0°-5° C. for 30 minutes
  3. customwas destroyed by the addition of water
  4. additionThe mixture was diluted with ether
  5. washwashed with water
  6. extractionThe aqueous layer was extracted with ether (three times)
  7. dry with materialthe combined ether extracts were dried (magnesium sulfate)
  8. concentrationconcentrated
  9. customchromatographed (silica gel/5-20% ethyl acetate:hexane)

Sources & evidence

ORD record
ord-28236b5386d142ff8f92b114579f289a
Source dataset
uspto-grants-1988_06
Patent number
US04752645

Reaction notes

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