Methyl acetoacetate → HCID 14196835, compound

HRID 1886543Notes

Reaction equation

HRID 1886543 reaction equation
[H-].[Na+].[C:3]([O:9][CH3:10])(=[O:8])[CH2:4][C:5]([CH3:7])=[O:6].C([Li])CCC.[C:16]1([C:22]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[CH:23][CH:24]=[CH:25][CH:26]=[O:27])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C1COCC1>[OH:27][CH:26](/[CH:25]=[CH:24]/[CH:23]=[C:22]([C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)[C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[CH2:7][C:5](=[O:6])[CH2:4][C:3]([O:9][CH3:10])=[O:8]

Participants

6

Reactant 4

HCID 7757Methyl acetoacetateHCID 24758Sodium hydride2×HCID 543262575,5-Diphenylpenta-2,4-dienalHCID 178418339Butyllithium

Product 1

HCID 14196835HCID 14196835, compoundYield 99.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

A 60% dispersion of sodium hydride (0.095 g of dispersion, 0.057 g of NaH, 2.4 mmol) was triturated with anhydrous THF (3×20 ml). The pure sodium hydride was then suspended in anhydrous THF (10 ml) and cooled to 0° C. Methyl acetoacetate (0.227 g, 1.95 mmol) was added dropwise. After stirring the resulting colorless solution for 10 minutes at 0° C., butyllithium in hexanes (0.96 ml, 2.5M, 2.4 mmol) was added dropwise via syringe. After stirring the reaction mixture for another 10 minutes at 0° C., a solution of 5,5-diphenyl-2,4-pentadienal (0.410 g, 1.75 mmol) in anhydrous tetrahydrofuran (10 ml) was added slowly via syringe. After completion of the addition, the reaction was stirred for 10 minutes at 0° C. The reaction mixture was then quenched by pouring it into saturated aqueous ammonium chloride. After stirring vigorously for 5 minutes, the phases were separated and the aqueous phase was extracted with ether (3×25 ml). The combined organic phases were washed with saturated aqueous sodium bicarbonate (40 ml) and water (2×40 ml), dried over magnesium sulfate and concentrated in vacuo to give 0.610 g (98% yield) of methyl (E)-5-hydroxy-9,9-diphenyl-3-oxo-6,8-nonadienoate as a viscous liquid. Since this material was quite pure and unstable on silica gel, it was carried onto the next step without purification.

Workup

  1. stirringAfter stirring the reaction mixture for another 10 minutes at 0° C.
  2. additionAfter completion of the addition
  3. stirringthe reaction was stirred for 10 minutes at 0° C
  4. customThe reaction mixture was then quenched
  5. additionby pouring it into saturated aqueous ammonium chloride
  6. stirringAfter stirring vigorously for 5 minutes
  7. customthe phases were separated
  8. extractionthe aqueous phase was extracted with ether (3×25 ml)
  9. washThe combined organic phases were washed with saturated aqueous sodium bicarbonate (40 ml) and water (2×40 ml)
  10. dry with materialdried over magnesium sulfate
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-33c74c798e434b5cb301294bb2ed0723
Source dataset
uspto-grants-1992_09
Patent number
US05151545

Reaction notes

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