Methyl acetoacetate → HCID 54125930, compound

HRID 974508

Reaction equation

HRID 974508 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].C([N-]C(C)C)(C)C.[Li+].[CH:17](=[O:23])[CH:18]=[CH:19][CH:20]=[CH:21][CH3:22]>C1COCC1>[OH:4][CH:3]([CH2:5][C:17](=[O:23])[CH:18]=[CH:19][CH:20]=[CH:21][CH3:22])[CH2:2][C:1]([O:7][CH3:8])=[O:6]

Participants

5

Reactant 3

HCID 7757Methyl acetoacetateHCID 8901Hexa-2,4-dienalHCID 2724682Lithium diisopropylamide

Product 1

HCID 54125930HCID 54125930, compoundYield 24.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a cold (-30° C.) solution of methyl acetoacetate (41.5 g, 357 mmol) in THF (500 mL) was added lithium diisopropylamide (476 mL, 1.5M solution in cyclohexane, 714 mmol). The resultant solution was stirred for 15 minutes at -30° C. After cooling to -78° C., 2,4-hexadienal (34.3 g, 357 mmol) was added and the solution stirred for 10 minutes at -78° C. and for 16 hours at ambient temperature. The solution was concentrated under reduced pressure and the residual syrup was partitioned between 1N HCl and ethyl acetate. The organic layer was washed with brine (2x), dried (Na2SO4), and concentrated. The residue was purified by chromatography on silica gel (diethyl ether:hexane/2:1) to afford 18.5 g (24.4%) of the title compound as an oil.

Workup

  1. concentrationThe solution was concentrated under reduced pressure
  2. customthe residual syrup was partitioned between 1N HCl and ethyl acetate
  3. washThe organic layer was washed with brine (2x)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography on silica gel (diethyl ether:hexane/2:1)

Sources & evidence

ORD record
ord-d13487c2d22b426ab9dbcc433187123e
Source dataset
uspto-grants-1991_11
Patent number
US05068346

Linked notes

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