Cesium fluoride → 3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-fluoro-4-trifluoromethanesulphonylpyrazole

HRID 1078439Notes

Reaction equation

HRID 1078439 reaction equation
S1(CCCC1)(=O)=O.[F-:8].[Cs+].Br[C:11]1[N:15]([C:16]2[C:21]([Cl:22])=[CH:20][C:19]([C:23]([F:26])([F:25])[F:24])=[CH:18][C:17]=2[Cl:27])[N:14]=[C:13]([C:28]#[N:29])[C:12]=1[S:30]([C:33]([F:36])([F:35])[F:34])(=[O:32])=[O:31]>CCOCC>[C:28]([C:13]1[C:12]([S:30]([C:33]([F:36])([F:35])[F:34])(=[O:32])=[O:31])=[C:11]([F:8])[N:15]([C:16]2[C:21]([Cl:22])=[CH:20][C:19]([C:23]([F:26])([F:25])[F:24])=[CH:18][C:17]=2[Cl:27])[N:14]=1)#[N:29]

Participants

5

Reactant 3

HCID 25953Cesium fluorideHCID 31347SulfolaneHCID 167270545-Bromo-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfonylpyrazole

Product 1

HCID 226183773-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-fluoro-4-trifluoromethanesulphonylpyrazoleYield 9.6%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of dry sulpholane (15 ml) and 4 Å molecular sieve (3.0 g) was stirred under nitrogen with caesium fluoride (2.4 g) at 60° C. for 1/2 hour. To this was added 5-bromo-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethanesulphonylpyrazole (2.0 g) and the mixture stirred at 60° C. for 2 hours, and left overnight at room temperature. This was diluted with ether (50 ml), filtered, and washed with water (100 ml). The aqueous layer was re-extracted with ether (3×50 ml) and the combined organic solution re-washed with water (4×50 ml), dried over anhydrous magnesium sulphate, and evaporated in vacuo to give an oil. Purification by chromatography, eluting with ether/hexane (1:4) gave 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-fluoro-4-trifluoromethanesulphonylpyrazole (0.17 g), m.p. 95°-98° C., in the form of a white solid, after recrystallisation from hexane.

Workup

  1. waitleft overnight at room temperature
  2. filtrationfiltered
  3. washwashed with water (100 ml)
  4. extractionThe aqueous layer was re-extracted with ether (3×50 ml)
  5. washthe combined organic solution re-washed with water (4×50 ml)
  6. dry with materialdried over anhydrous magnesium sulphate
  7. customevaporated in vacuo
  8. customto give an oil
  9. customPurification by chromatography
  10. washeluting with ether/hexane (1:4)

Sources & evidence

ORD record
ord-4a088c01ae4c4c92b4377a94cdd255e9
Source dataset
uspto-grants-1996_08
Patent number
US05547974

Reaction notes

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