Ethyl 2,4-dioxovalerate → HCID 86650585, compound

HRID 1257313Notes

Reaction equation

HRID 1257313 reaction equation
O=[C:2]([CH2:8][C:9](=O)[CH3:10])[C:3]([O:5][CH2:6][CH3:7])=[O:4].C([O-])(=O)C.[NH4+].Cl.[NH:18]([CH2:20][C:21]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22])[NH2:19]>C(O)C>[CH2:6]([O:5][C:3]([C:2]1[CH:8]=[C:9]([CH3:10])[N:18]([CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])[N:19]=1)=[O:4])[CH3:7].[CH2:6]([O:5][C:3]([C:2]1[N:18]([CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])[N:19]=[C:9]([CH3:10])[CH:8]=1)=[O:4])[CH3:7]

Participants

6

Reactant 3

HCID 69208Ethyl 2,4-dioxovalerateHCID 517165Ammonium AcetateHCID 66939210HCID 66939210, compound

Product 2

HCID 86650584HCID 86650584, compoundYield 31%HCID 86650585HCID 86650585, compoundYield 51%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of ethyl 2,4-dioxopentanoate (1.74 g, 11.0 mmol), ammonium acetate (1.16 g, 15.0 mmol) and ethanol (20 mL) was added benzyl hydrazinoacetate hydrochloride (2.17 g, 10.0 mmol), and the mixture was stirred at room temperature for 1 hr and at 80° C. for 3 hr. The reaction mixture was concentrated under reduced pressure, and the residue was diluted with water, extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, eluent: hexane-ethyl acetate) to give benzyl [3-(ethoxycarbonyl)-5-methyl-1H-pyrazol-1-yl]acetate (0.95 g, 31%) and benzyl [5-(ethoxycarbonyl)-3-methyl-1H-pyrazol-1-yl]acetate (1.56 g, 51%). To a solution of benzyl [3-(ethoxycarbonyl)-5-methyl-1H-pyrazol-1-yl]acetate (0.95 g, 3.14 mmol) in ethanol (10 mL) was added 5% palladium/carbon (0.30 g), and the mixture was stirred under a hydrogen stream for 21 hr. The insoluble material was filtered off, and the filtrate was concentrated. The residue was recrystallized from ethyl acetate-hexane to give the title compound (0.59 g, 88%).

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. additionthe residue was diluted with water
  3. extractionextracted with ethyl acetate
  4. washwashed with saturated brine
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography (carrier: silica gel, eluent: hexane-ethyl acetate)

Sources & evidence

ORD record
ord-5ce21259aad740da94adb5a3e014c109
Source dataset
uspto-grants-2013_06
Patent number
US08461348B2

Reaction notes

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