Water → 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-propanoylpyrazole

HRID 377657Notes

Reaction equation

HRID 377657 reaction equation
[C:1]([C:3]1[C:7](I)=[CH:6][N:5]([C:9]2[C:14]([Cl:15])=[CH:13][C:12]([C:16]([F:19])([F:18])[F:17])=[CH:11][C:10]=2[Cl:20])[N:4]=1)#[N:2].C([Li])CCC.[C:26](OC)(=[O:29])[CH2:27][CH3:28].O>O1CCCC1>[C:1]([C:3]1[C:7]([C:26](=[O:29])[CH2:27][CH3:28])=[CH:6][N:5]([C:9]2[C:14]([Cl:15])=[CH:13][C:12]([C:16]([F:19])([F:18])[F:17])=[CH:11][C:10]=2[Cl:20])[N:4]=1)#[N:2]

Participants

6

Reactant 4

HCID 962WaterHCID 11124Methyl propionateHCID 211881263-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-iodopyrazoleHCID 178418339Butyllithium

Product 1

HCID 186994653-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-propanoylpyrazole

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-72 °C

Procedure

To a stirred solution of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-iodopyrazole (7.2 g) in tetrahydrofuran (80 ml) at -78° C. under an atmosphere of nitrogen was added, at such a rate that the temperature of the reaction mixture did not exceed -71° C., n-butyllithium (8 ml of a 2.5M solution in hexanes). A solution of methyl propionate (3.2 ml) in tetrahydrofuran (10 ml) was then added at such a rate that the temperature of the reaction mixture did not exceed -72° C. Upon completion of the addition the mixture was stirred at -72° C. and then allowed to warm to room temperature over a period of 1.5 hours. After stirring overnight at room temperature water (100 ml) was added and the mixture extracted twice with ethyl acetate (200 ml). The combined organic layers were dried (Na2SO4) and evaporated to give a brown gum which was purified by column chromatography on silica gel (500 g) eluted with dichloromethane. Combination and evaporation of suitable fractions gave a brown solid which was further purified by column chromatography on silica gel (60 g) eluted with dichloromethane. Combination and evaporation of suitable fractions gave the title compound as a pale yellow solid, m.p. 143° C.

Workup

  1. customdid not exceed -71° C.
  2. customdid not exceed -72° C
  3. additionUpon completion of the addition the mixture
  4. temperatureto warm to room temperature over a period of 1.5 hours
  5. additionwas added
  6. extractionthe mixture extracted twice with ethyl acetate (200 ml)
  7. dry with materialThe combined organic layers were dried (Na2SO4)
  8. customevaporated
  9. customto give a brown gum which
  10. customwas purified by column chromatography on silica gel (500 g)
  11. washeluted with dichloromethane
  12. customCombination and evaporation of suitable fractions
  13. customgave a brown solid which
  14. customwas further purified by column chromatography on silica gel (60 g)
  15. washeluted with dichloromethane
  16. customCombination and evaporation of suitable fractions

Sources & evidence

ORD record
ord-2b586c226a2d40f792eceaa41d5cb9ed
Source dataset
uspto-grants-2000_02
Patent number
US06028096

Reaction notes

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