Water → HCID 13370513, compound

HRID 2412925Notes

Reaction equation

HRID 2412925 reaction equation
[F:1][C:2]([F:20])([F:19])[C:3]1[CH:4]=[C:5]([CH:16]=[CH:17][CH:18]=1)[C:6]([CH2:8][C:9](=O)[C:10]([O:12]CC)=[O:11])=O.[CH3:21][NH:22][NH2:23].O>C(O)C>[CH3:21][N:22]1[C:9]([C:10]([OH:12])=[O:11])=[CH:8][C:6]([C:5]2[CH:16]=[CH:17][CH:18]=[C:3]([C:2]([F:20])([F:19])[F:1])[CH:4]=2)=[N:23]1

Participants

5

Reactant 3

HCID 962WaterHCID 6061MethylhydrazineHCID 13370511Ethyl α,γ-dioxo-3-(trifluoromethyl)benzenebutanoate

Product 1

HCID 13370513HCID 13370513, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Following the procedure of Example 1, 5.8 g. of ethyl 3-trifluoromethylbenzoylpyruvate and 0.92 g. of methyl hydrazine were heated in ethanol solution for about one hour at about 80° C. The reaction mixture was cooled and water added. The aqueous mixture was extracted with two 100 ml. portions of ether followed by one 100 ml. portion of chloroform. The combined extracts were dried with phase separation paper. The solvents were removed from the filtrate. NMR indicated that the residue comprised the isomeric pair ethyl 1-methyl-3-(3-trifluoromethylphenyl)pyrazole-5-carboxylate and ethyl 1-methyl-5-(3-trifluoromethylphenyl)pyrazole-3-carboxylate in about a 60-40 mixture. Following the procedure of Example 2, the isomers were separated by chromatography over silica gel using dichloromethane. The faster moving fraction, comprising the desired ethyl 1-methyl-3-(3-trifluoromethylphenyl)pyrazole-5-carboxylate, was collected and the solvent removed therefrom; weight=2.0 g. The desired ethyl ester was hydrolyzed without further purification according to the following procedure. A solution of 2.0 g. of ethyl 1-methyl-3-(3-trifluoromethylphenyl)pyrazole-5-carboxylate in 40 ml. of ethanol was refluxed with a solution of 0.3 g. of sodium hydroxide in 120 ml. of water for about 2 hours. The hydrolysis mixture was cooled and then acidified with 1N aqueous hydrochloric acid. The free acid, being insoluble in the acidic aqueous solution, precipitated and was collected by filtration. Recrystallization of the filer cake yielded 1-methyl-3-(3-trifluoromethylphenyl)pyrazole-5-carboxylic acid melting at 198°-9° C. after recrystallization from ethanol.

Workup

  1. temperatureThe reaction mixture was cooled
  2. extractionThe aqueous mixture was extracted with two 100 ml
  3. customThe combined extracts were dried with phase separation paper
  4. customThe solvents were removed from the filtrate
  5. customthe isomers were separated by chromatography over silica gel
  6. customwas collected
  7. customthe solvent removed
  8. customThe desired ethyl ester was hydrolyzed without further purification
  9. temperatureof ethanol was refluxed with a solution of 0.3 g
  10. temperatureThe hydrolysis mixture was cooled
  11. customprecipitated
  12. filtrationwas collected by filtration
  13. customRecrystallization of the filer cake

Sources & evidence

ORD record
ord-ae05da81aa2a4026af8f3e012911f63f
Source dataset
uspto-grants-1985_01
Patent number
US04495195

Reaction notes

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