Ethyl Acetoacetate → HCID 67360478, compound

HRID 238947Notes

Reaction equation

HRID 238947 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[O-]CC.[Na+].C(O)C.[CH2:17]([O:24][C@@H:25]([CH3:31])[CH2:26][C:27](=[O:30])[CH2:28]Br)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C(O)C>[CH2:8]([O:7][C:1](=[O:6])[CH:2]([C:3](=[O:4])[CH3:5])[CH2:28][C:27](=[O:30])[CH2:26][C@@H:25]([O:24][CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[CH3:31])[CH3:9]

Participants

5

Reactant 3

HCID 8868Ethyl AcetoacetateHCID 23706232Ethanol sodium ethoxideHCID 86658652HCID 86658652, compound

Product 1

HCID 67360478HCID 67360478, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

Under a nitrogen atmosphere, to a solution of ethyl acetoacetate (1.0 g, 7.7 mmol) in ethanol (30 mL), 20% sodium ethoxide/ethanol solution (3.1 mL, 7.7 mmol) was gradually added under ice-cooling, and the mixture was stirred at room temperature for 30 minutes. Thereafter, under ice-cooling, a solution of the above (4S)-4-(benzyloxy)-1-bromopentan-2-one (2.1 g, 7.7 mmol) in ethanol (6.0 mL) was gradually added, and the mixture was stirred at room temperature for 3 hours. After the reaction, ethanol was distilled off under reduced pressure and 1N hydrochloric acid (0.20 L) was added to acidify it. After it was extracted with ethyl acetate and successively washed with water, a saturated aqueous sodium hydrogencarbonate solution and saturated brine, it was dried with sodium sulfate and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography (ethyl acetate/hexane, 1:3, v/v) to give the title compound (1.6 g, 65%) as an oil.

Workup

  1. temperaturecooling
  2. temperatureThereafter, under ice-cooling
  3. stirringthe mixture was stirred at room temperature for 3 hours
  4. distillationwas distilled off under reduced pressure and 1N hydrochloric acid (0.20 L)
  5. additionwas added
  6. extractionAfter it was extracted with ethyl acetate
  7. washsuccessively washed with water
  8. dry with materiala saturated aqueous sodium hydrogencarbonate solution and saturated brine, it was dried with sodium sulfate
  9. distillationthe solvent was distilled off under reduced pressure
  10. customIt was purified by silica gel column chromatography (ethyl acetate/hexane, 1:3

Sources & evidence

ORD record
ord-14a4792f9bb7408dadf271a4957fdede
Source dataset
uspto-grants-2014_02
Patent number
US08642640B2

Reaction notes

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