1-Butanol → HCID 23093706, compound

HRID 1667313Notes

Reaction equation

HRID 1667313 reaction equation
[CH2:1]([OH:5])CCC.[CH2:6]([N:10]([CH2:15][CH2:16][CH2:17][CH3:18])[CH2:11]CCC)[CH2:7][CH2:8][CH3:9].Br[C:20]1[CH:25]=[C:24]([CH3:26])[C:23](/[CH:27]=[CH:28]/[CH:29]2[CH2:34][CH2:33][N:32]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:31][CH2:30]2)=[C:22]([CH3:42])[CH:21]=1.[OH2:43]>>[CH2:6]([O:43][C:1]([C:20]1[CH:25]=[C:24]([CH3:26])[C:23](/[CH:27]=[CH:28]/[CH:29]2[CH2:34][CH2:33][N:32]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:31][CH2:30]2)=[C:22]([CH3:42])[CH:21]=1)=[O:5])[CH2:7][CH2:8][CH3:9].[CH2:6]([N:10]([CH2:15][CH2:16][CH2:17][CH3:18])[C:11]([C:20]1[CH:25]=[C:24]([CH3:26])[C:23](/[CH:27]=[CH:28]/[CH:29]2[CH2:34][CH2:33][N:32]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH2:31][CH2:30]2)=[C:22]([CH3:42])[CH:21]=1)=[O:5])[CH2:7][CH2:8][CH3:9]

Participants

6

Reactant 4

HCID 2631-Butanol2×HCID 962WaterHCID 7622Tributylamine2×HCID 9977921HCID 9977921, compound

Product 2

HCID 23093706HCID 23093706, compoundHCID 58870242HCID 58870242, compound

Conditions

Temperature
100 °C

Procedure

Under carbon monoxide atmosphere, 120 μl of butanol and 265 μl of tributylamine were added to a mixture of 409 mg of tert-butyl 4-[(E)-2-(4-bromo-2,6-dimethylphenyl)vinyl]piperidine-1-carboxylate and 39 mg of dichlorobistriphenylphosphine palladium. The mixture was heated at 100° C. overnight with stirring. Then 87 mg of dichlorobistriphenylphosphine palladium, 120 μl of butanol and 265 μl of tributylamine were added to the reaction mixture and the mixture was heated at 120° C. overnight with stirring. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed sequentially with 0.1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride. After drying over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give 217 mg of tert-butyl 4-{(E)-2-[4-(butoxycarbonyl)-2,6-dimethylphenyl]vinyl}piperidine-1-carboxylate (Example 32-1) and 123 mg of tert-butyl 4-((E)-2-{4-[(dibutylamino)carbonyl]-2,6-dimethylphenyl}vinyl)piperidine-1-carboxylate (Example 32-2).

Workup

  1. temperaturethe mixture was heated at 120° C. overnight
  2. stirringwith stirring
  3. extractionfollowed by extraction with ethyl acetate
  4. washThe organic layer was washed sequentially with 0.1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride
  5. dry with materialAfter drying over anhydrous magnesium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-1fd232cc9c684023b820d2e43685e08b
Source dataset
uspto-grants-2011_10
Patent number
US08044206B2

Reaction notes

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