3-Butyn-2-ol → HCID 10421814, compound

HRID 233661Notes

Reaction equation

HRID 233661 reaction equation
[CH3:1][CH:2]([OH:5])[C:3]#[CH:4].C([Li])CCC.[CH2:11]([O:13][C:14]([N:16]1[CH2:21][CH2:20][C:19](=[O:22])[CH2:18][CH2:17]1)=[O:15])[CH3:12].[NH4+].[Cl-]>C1COCC1.CCCCCC>[OH:5][CH:2]([CH3:1])[C:3]#[C:4][C:19]1([OH:22])[CH2:18][CH2:17][N:16]([C:14]([O:13][CH2:11][CH3:12])=[O:15])[CH2:21][CH2:20]1

Participants

7

Reactant 4

HCID 162393-Butyn-2-olHCID 25517Ammonium ChlorideHCID 34767Ethyl 4-oxo-1-piperidinecarboxylateHCID 178418339Butyllithium

Product 1

HCID 10421814HCID 10421814, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent4×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 3-butyn-2-ol (42 g, 0.6 mol) in dry THF (800 ml) under nitrogen was cooled with a dry-ice/acetone bath. n-Butyl lithium (390 ml of 2.5M and 230 ml of 1.5M) in hexane was added rapidly, dropwise. The suspension became gelatinous and another 800 mls of dry THF was added. The reaction was stirred at approximately -78° C. for 1 hour and then at 0° C. for 20 minutes. The reaction was cooled to -78° C. and 1-ethoxycarbonyl-4-piperidinone (104 g, 0.607 mol) in 300 ml of dry THF was added rapidly dropwise. The reaction mixture was allowed to warm to room temperature and then stirred overnight. The reaction mixture was cooled in an ice-bath, diluted with THF (1.51 ), decomposed with saturated NH4Cl, and the THF layer was washed three times with 200 ml of saturated ammonium chloride. The aqueous layers were back-washed with THF (200 ml×3). The organic layers were combined and dried over MgSO4 and evaporated to give an oil. A one-fifth portion of the oil was purified by flash chromatography on silica gel and elution with 30% ethyl acetate/ether afforded the desired product diol (19.7 g).

Workup

  1. waitat 0° C. for 20 minutes
  2. temperatureThe reaction was cooled to -78° C.
  3. temperatureto warm to room temperature
  4. stirringstirred overnight
  5. temperatureThe reaction mixture was cooled in an ice-bath
  6. washthe THF layer was washed three times with 200 ml of saturated ammonium chloride
  7. washThe aqueous layers were back-washed with THF (200 ml×3)
  8. dry with materialdried over MgSO4
  9. customevaporated
  10. customto give an oil
  11. customA one-fifth portion of the oil was purified by flash chromatography on silica gel and elution with 30% ethyl acetate/ether

Sources & evidence

ORD record
ord-5f5ed05fec0942f4b4df42ce19e1e4d6
Source dataset
uspto-grants-1997_01
Patent number
US05594000

Reaction notes

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