HCID 86650584, compound → HCID 66938796, compound

HRID 1257314Notes

Reaction equation

HRID 1257314 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([CH3:11])[N:8]([CH2:12][C:13]([O:15]CC2C=CC=CC=2)=[O:14])[N:7]=1)=[O:5])[CH3:2]>C(O)C.[Pd]>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([CH3:11])[N:8]([CH2:12][C:13]([OH:15])=[O:14])[N:7]=1)=[O:5])[CH3:2]

Participants

4

Reactant 1

HCID 86650584HCID 86650584, compound

Product 1

HCID 66938796HCID 66938796, compoundYield 88.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

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. filtrationThe insoluble material was filtered off
  2. concentrationthe filtrate was concentrated
  3. customThe residue was recrystallized from ethyl acetate-hexane

Sources & evidence

ORD record
ord-204efb4668694c8999dd561ff5f152fc
Source dataset
uspto-grants-2013_06
Patent number
US08461348B2

Reaction notes

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