Hydrochloric Acid → HCID 54485817, compound

HRID 1196485Notes

Reaction equation

HRID 1196485 reaction equation
C(O)(=O)C(O)=O.[CH2:7]([O:11][C:12](=[O:27])[CH2:13][C:14]1[C:15]([NH2:26])=[N:16][NH:17][C:18]=1[C:19]1[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=1)[CH2:8]CC.Cl.CO[CH:31](OC)[CH2:32][CH:33](OC)OC.C(=O)([O-])[O-].[K+].[K+]>C(O)C.O>[CH2:7]([O:11][C:12](=[O:27])[CH2:13][C:14]1[C:18]([C:19]2[CH:20]=[CH:21][C:22]([CH3:25])=[CH:23][CH:24]=2)=[N:17][N:16]2[CH:33]=[CH:32][CH:31]=[N:26][C:15]=12)[CH3:8]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 66019TetramethoxypropaneHCID 131717372HCID 131717372, compound

Product 1

HCID 54485817HCID 54485817, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

A stirred slurry of 50.2 g (0.133 mole) of 3-amino-5-(4-methylphenyl)-1H-pyrazole-4-acetic acid butyl ester ethanedioate (1:1) in 500 mL of 190 ethanol was treated first with 5 mL of hydrochloric acid (37%) and then with 21.8 g (0.133 mole) of malonaldehyde bis(dimethyl acetal). After stirring for 24 hours at ambient temperature, the reaction mixture was concentrated in vacuo. The residue was dissolved in 500 mL of methylene chloride and washed with saturated sodium bicarbonate solution. The combined aqueous layers were extracted with methylene chloride then the methylene chloride solutions were combined and washed with water. After drying the methylene chloride solution was concentrated in vacuo. The residue was dissolved in 500 mL of 200 ethanol, treated with 1 mL of concentrated sulfuric acid, and heated on a steam bath for 24 hours. The ethanol solution was treated with 50 g of potassium carbonate and 5 mL of H2O. After stirring for 30 minutes, the inorganic material was removed by filtration and the filtrate concentrated in vacuo to a black tar-like residue. The residue was dissolved in 2-propyl ether, filtered, and treated with ethereal hydrogen chloride. The salt which precipitated was collected by filtration, yielding 44 g of crude yellow-green product. The crude product was dissolved in 190 ethanol, diluted with water, then treated with 20 g of potassium carbonate. The precipitated product was collected by filtration in 2 batches to yield 33.4 g (85%) of tan product, mp 69°-71.5° C. An analytical sample was recrystallized from ethanol-water with charcoal treatment yielding a pale yellow crystalline powder, mp 71°-73° C.

Workup

  1. concentrationthe reaction mixture was concentrated in vacuo
  2. dissolutionThe residue was dissolved in 500 mL of methylene chloride
  3. washwashed with saturated sodium bicarbonate solution
  4. extractionThe combined aqueous layers were extracted with methylene chloride
  5. washwashed with water
  6. dry with materialAfter drying the methylene chloride solution
  7. concentrationwas concentrated in vacuo
  8. dissolutionThe residue was dissolved in 500 mL of 200 ethanol
  9. additiontreated with 1 mL of concentrated sulfuric acid
  10. temperatureheated on a steam bath for 24 hours
  11. additionThe ethanol solution was treated with 50 g of potassium carbonate and 5 mL of H2O
  12. stirringAfter stirring for 30 minutes
  13. customthe inorganic material was removed by filtration
  14. concentrationthe filtrate concentrated in vacuo to a black tar-like residue
  15. dissolutionThe residue was dissolved in 2-propyl ether
  16. filtrationfiltered
  17. additiontreated with ethereal hydrogen chloride
  18. customThe salt which precipitated
  19. filtrationwas collected by filtration
  20. customyielding 44 g of crude yellow-green product
  21. filtrationThe precipitated product was collected by filtration in 2 batches

Sources & evidence

ORD record
ord-b0693c2b36334dd497780764ddde4c65
Source dataset
uspto-grants-1992_05
Patent number
US05114944

Reaction notes

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