Hydrochloric Acid → HCID 57259370, compound

HRID 1650293Notes

Reaction equation

HRID 1650293 reaction equation
[CH2:1]([O:4][C:5]([N:7]1[CH2:12][CH2:11][CH2:10][CH2:9][CH:8]1[C:13](OC)=O)=[O:6])[CH:2]=[CH2:3].[H-].C([Al+]CC(C)C)C(C)C.Cl.[OH2:28].[C:29]1([CH3:35])C=CC=[CH:31][CH:30]=1>C(OCC)(=O)C>[CH2:1]([O:4][C:5]([N:7]1[CH2:12][CH2:11][CH2:10][CH2:9][CH:8]1[CH:13]=[C:30]([CH3:31])[C:29](=[O:28])[CH3:35])=[O:6])[CH:2]=[CH2:3]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 962WaterHCID 1140TolueneHCID 19914928HCID 19914928, compoundHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 57259370HCID 57259370, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-70 °C

Procedure

To a solution of 1-allyloxycarbonyl-2-methoxycarbonylpiperidine (10 g) in toluene (60 ml) was added dropwise diisobutylaluminum hydride (1M solution in toluene) (57 ml) at -70° C. After stirring at -70° C. for 30 minutes, the reaction mixture was poured into a mixture of concentrated hydrochloric acid (25 ml) and water (100 ml) at 5° C. After stirring at 5° C. for 15 minutes, the organic layer was separated, washed in turn with 1N hydrochloric acid (20 ml), 25% potassium sodium tartrate (20 ml) and brine (20 ml), dried over magncsium sulfate and filtered. The filtrate was concentrated to a volume of 40 ml. To this solution was added 3-triphenylphosphoranylidenebutan-2-one (16.1 g) and the mixture was stirred at 70° C. for 5 hours. After cooling to ambient temperature, the resulting precipitate was removed by filtration. The filtrate was evaporated to give a residue, which was taken up into ethyl acetate. The resulting precipitate was removed by filtration and the filtrate was evaporated in vacuo. The residue was chromatographed on silica gel (300 ml) eluting with a mixture of n-hexane and ethyl acetate (10:1-5:1 V/V) to give 1-allyloxycarbonyl-2-(2-methyl-3-oxo-1-butenyl)piperidine (10.9 g).

Workup

  1. stirringAfter stirring at 5° C. for 15 minutes
  2. customthe organic layer was separated
  3. washwashed in turn with 1N hydrochloric acid (20 ml), 25% potassium sodium tartrate (20 ml) and brine (20 ml)
  4. dry with materialdried over magncsium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated to a volume of 40 ml
  7. additionTo this solution was added 3-triphenylphosphoranylidenebutan-2-one (16.1 g)
  8. stirringthe mixture was stirred at 70° C. for 5 hours
  9. temperatureAfter cooling to ambient temperature
  10. customthe resulting precipitate was removed by filtration
  11. customThe filtrate was evaporated
  12. customto give a residue, which
  13. customThe resulting precipitate was removed by filtration
  14. customthe filtrate was evaporated in vacuo
  15. customThe residue was chromatographed on silica gel (300 ml)
  16. washeluting with a mixture of n-hexane and ethyl acetate (10:1-5:1 V/V)

Sources & evidence

ORD record
ord-ef6c706872004ead86f6f53aea6e42b1
Source dataset
uspto-grants-1990_05
Patent number
US04923857

Reaction notes

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