Pyrazole → 1H-Pyrazole, 3,5-dimethyl-1-(1-oxo-2-propenyl)-

HRID 1076148Notes

Reaction equation

HRID 1076148 reaction equation
[CH3:1][C:2]1[CH:6]=[C:5]([CH3:7])[NH:4][N:3]=1.[C:8](Cl)(=[O:11])[CH:9]=[CH2:10].C(N(CC)CC)C.N1C=CC=N1>C1C=CC=CC=1>[C:8]([N:3]1[C:2]([CH3:1])=[CH:6][C:5]([CH3:7])=[N:4]1)(=[O:11])[CH:9]=[CH2:10]

Participants

6

Reactant 4

HCID 1048PyrazoleHCID 62103,5-Dimethylpyrazole2×HCID 8471Triethylamine2×HCID 13140Acryloyl chloride3×

Product 1

HCID 115428091H-Pyrazole, 3,5-dimethyl-1-(1-oxo-2-propenyl)-

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Conditions

Temperature
10 °C

Procedure

N-acrylyl-3,5-dimethyl pyrazole was prepared by reacting 3,5-dimethylpyrazole with acrylyl chloride in the presence of triethylamine. 19.2 grams (0.2 mole) of 3,5-dimethylpyrazole and 20.2 grams (0.2 mole) of triethylamine were dissolved in 125 milliliters of benzene and the solution put into a dropping funnel. The acrylyl chloride, 18.1 grams (0.2 mole) was dissolved in 25 milliliters of benzene and this solution put into a flask equipped for stirring and cooled at 10°C. The pyrazole solution was then added to the acrylyl chloride solution over a period of 45 minutes with constant stirring. Temperature of the reaction mix was held at 8°C. to 15°C. throughout the addition. Following the addition, the reaction mix was allowed to warm to room temperature and let stand for 4 hours. The mix was then filtered to remove triethylamine-hydrochloric acid salt which was formed in the reaction. The filtrate was heated to evaporate off volatiles, leaving 24.5 grams of an amber-colored liquid residue. The residue was then cooled to about 0°C. and 12.1 grams of a white crystalline precipitate was filtered out. After standing 16 hours at about 0°C., 2.5 more grams of crystalline solid was filtered out. The solids were combined and twice recrystallized from a solution of 18 milliliters of methanol and 2 milliliters of water to yield 9.4 grams of a crystalline solid having a melting point of 36°-37°C. The nuclear magnetic resonance (NMR) spectra of the solid conformed with that of the expected product.

Workup

  1. customthe solution put into a dropping funnel
  2. customthis solution put into a flask
  3. customequipped
  4. additionTemperature of the reaction mix
  5. additionwas held at 8°C. to 15°C. throughout the addition
  6. additionthe addition
  7. additionthe reaction mix
  8. temperatureto warm to room temperature
  9. filtrationThe mix was then filtered
  10. customto remove triethylamine-hydrochloric acid salt which
  11. customwas formed in the reaction
  12. temperatureThe filtrate was heated
  13. customto evaporate off volatiles

Sources & evidence

ORD record
ord-a3334686e77d48959fa15c858d3d7645
Source dataset
uspto-grants-1976_05
Patent number
US03955041

Reaction notes

Loading…