p-Toluenesulfonic acid → 4-Acetyl-5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)pyrazole

HRID 377663Notes

Reaction equation

HRID 377663 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([O:14][C:15]([F:18])([F:17])[F:16])=[CH:9][C:8]=2[Cl:19])[N:5]=[C:4]([C:20]#[N:21])[C:3]=1[C:22]#[CH:23].C1(C)C=CC(S(O)(=O)=[O:31])=CC=1>C(#N)C>[C:22]([C:3]1[C:4]([C:20]#[N:21])=[N:5][N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([O:14][C:15]([F:17])([F:16])[F:18])=[CH:9][C:8]=2[Cl:19])[C:2]=1[NH2:1])(=[O:31])[CH3:23]

Participants

4

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 211880625-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-ethynylpyrazole

Product 1

HCID 193564804-Acetyl-5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)pyrazole

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-ethynylpyrazole (0.318 g) in acetonitrile (10 ml) was added p-toluenesulphonic acid (0.455 g) and the mixture was stirred at room temperature for 1.5 hours and then evaporated to dryness. The residue was taken up in ether and washed with saturated aqueous sodium hydrogen carbonate solution (5 ml). The aqueous layer was twice extracted with ether. The combined organic layers were dried (Na2SO4) and evaporated. The residue was purified by column chromatography on silica gel eluted with hexane:ether (1:1). Combination and evaporation of suitable fractions gave a yellow solid which was further purified by reverse phase high performance chromatography on C18 silica eluted with acetonitrile:water:methanol (60:30:10). Appropriate fractions were combined and evaporated to give, after recrystallisation from propan-2-ol, the title compound as a white solid, m.p. 192.3-192.7° C.

Workup

  1. customevaporated to dryness
  2. washwashed with saturated aqueous sodium hydrogen carbonate solution (5 ml)
  3. extractionThe aqueous layer was twice extracted with ether
  4. dry with materialThe combined organic layers were dried (Na2SO4)
  5. customevaporated
  6. customThe residue was purified by column chromatography on silica gel
  7. washeluted with hexane:ether (1:1)
  8. customCombination and evaporation of suitable fractions
  9. customgave a yellow solid which
  10. customwas further purified by reverse phase high performance chromatography on C18 silica
  11. washeluted with acetonitrile:water:methanol (60:30:10)
  12. customevaporated
  13. customto give
  14. customafter recrystallisation from propan-2-ol

Sources & evidence

ORD record
ord-2153b914a08b47138691b94003502cc6
Source dataset
uspto-grants-2000_02
Patent number
US06028096

Reaction notes

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