Sodium hydride → ethyl 3-[4-cyano-1-(2,3,4-trichlorophenyl)-1H-pyrazol-5-yl]acrylate

HRID 1614488Notes

Reaction equation

HRID 1614488 reaction equation
Cl[CH:2]([CH2:8][C:9]1[N:13]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[C:16]([Cl:21])[C:15]=2[Cl:22])[N:12]=[CH:11][C:10]=1[C:23]#[N:24])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+]>CN(C)C=O>[C:23]([C:10]1[CH:11]=[N:12][N:13]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[C:16]([Cl:21])[C:15]=2[Cl:22])[C:9]=1[CH:8]=[CH:2][C:3]([O:5][CH2:6][CH3:7])=[O:4])#[N:24]

Participants

4

Reactant 2

HCID 24758Sodium hydrideHCID 19790770ethyl 2-chloro-3-[4-cyano-1-(2,3,4-trichlorophenyl)-1H-pyrazol-5-yl]propionate

Product 1

HCID 54479989ethyl 3-[4-cyano-1-(2,3,4-trichlorophenyl)-1H-pyrazol-5-yl]acrylateYield 54%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a stirred, slightly warmed solution of 1.4 grams (0.003 mole) of ethyl 2-chloro-3-[4-cyano-1-(2,3,4-trichlorophenyl)-1H-pyrazol-5-yl]propionate in 25 mL of N,N-dimethylformamide was added in one portion 0.1 gram (0.004 mole) of sodium hydride. Upon completion of the addition the reaction mixture was warmed to about 60° C., where it was stirred for 1.75 hours. The reaction mixture was then allowed to cool to ambient temperature, where it was stirred for about 18 hours. The reaction mixture was again warmed to about 60° C., where it was stirred for two hours. The reaction mixture was cooled and concentrated under reduced pressure. The residue remaining was stirred with water for about 40 minutes, giving a solid that was collected by filtration. The solid was recrystallized from ethanol and water, yielding 0.6 gram of ethyl 3-[4-cyano-1-(2,3,4-trichlorophenyl)-1H-pyrazol-5-yl]acrylate, m.p. 131°-134° C. The nmr spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of the addition the reaction mixture
  2. temperatureto cool to ambient temperature
  3. stirringwhere it was stirred for about 18 hours
  4. temperatureThe reaction mixture was again warmed to about 60° C.
  5. stirringwhere it was stirred for two hours
  6. temperatureThe reaction mixture was cooled
  7. concentrationconcentrated under reduced pressure
  8. stirringThe residue remaining was stirred with water for about 40 minutes
  9. customgiving a solid
  10. filtrationthat was collected by filtration
  11. customThe solid was recrystallized from ethanol and water

Sources & evidence

ORD record
ord-177b5298e5a540df8e0b1864201f5425
Source dataset
uspto-grants-1993_03
Patent number
US05198014

Reaction notes

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