Oxalyl chloride → methyl 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylate

HRID 2359668Notes

Reaction equation

HRID 2359668 reaction equation
[CH3:1][N:2]1[C:6]([CH3:7])=[C:5]([C:8]([OH:10])=[O:9])[C:4](=[O:11])[N:3]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[C:18](Cl)(=O)C(Cl)=O>ClCCl>[CH3:1][N:2]1[C:6]([CH3:7])=[C:5]([C:8]([O:10][CH3:18])=[O:9])[C:4](=[O:11])[N:3]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

4

Reactant 2

HCID 65578Oxalyl chlorideHCID 246564Antipyric acid

Product 1

HCID 20294053methyl 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylateYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2,3-dimethyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazole-4-carboxylic acid (7.55 g, 33 mmol) was dissolved in dichlormethane (145 ml) and oxalyl chloride (4.1 ml, 46 mmol) was added via syringe over about 10 minutes, resulting in vigorous bubbling. After stirring at room temperature for about 30 minutes, the reaction was cautiously quenched with MeOH (100 ml). The methanol was added slowly at first as vigorous gas evolution was observed. The reaction was stirred at room temperature for 1 hour, concentrated, and then partitioned between dichlormethane (125 ml) and saturated sodium bicarbonate (125 ml). More dichlormethane and saturated sodium bicarbonate were added, and the layers of the biphasic, homogeneous solution were separated. The aqueous phase was extracted with dichlormethane (3×100 ml), and the organic phases were collected, dried over sodium sulfate, filtered, and concentrated to give desired methyl 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazole-4-carboxylate (7.82 g, 79% purity by HPLC, 25 mmol, 77% yield). MS (ESI pos. ion) m/z: 247 (MH+). Calc'd exact mass for C13H14N2O3: 246.

Workup

  1. customresulting in vigorous bubbling
  2. customthe reaction was cautiously quenched with MeOH (100 ml)
  3. additionThe methanol was added slowly at first as vigorous gas evolution
  4. stirringThe reaction was stirred at room temperature for 1 hour
  5. concentrationconcentrated
  6. custompartitioned between dichlormethane (125 ml) and saturated sodium bicarbonate (125 ml)
  7. additionMore dichlormethane and saturated sodium bicarbonate were added
  8. customthe layers of the biphasic, homogeneous solution were separated
  9. extractionThe aqueous phase was extracted with dichlormethane (3×100 ml)
  10. customthe organic phases were collected
  11. dry with materialdried over sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-f3992177a40e4576a3d6514fcfeaaf15
Source dataset
uspto-grants-2014_04
Patent number
US08685983B2

Reaction notes

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