Triethylamine → 5-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-trimethylsilylethynylpyrazole

HRID 377661Notes

Reaction equation

HRID 377661 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]=1I.[CH3:23][Si:24]([C:27]#[CH:28])([CH3:26])[CH3:25].C(N(CC)CC)C>CN(C)C=O.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[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:28]#[C:27][Si:24]([CH3:26])([CH3:25])[CH3:23]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 66111Trimethylsilylacetylene2×HCID 211881115-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-iodopyrazole

Product 1

HCID 211881085-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-trimethylsilylethynylpyrazole

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalyst2×HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a stirred solution of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethoxyphenyl)-4-iodopyrazole (5.489 g) in dimethylformamide (4 ml) at room temperature was added trimethylsilylacetylene (3.35 ml), cuprous iodide (0.116 g), bis(triphenylphosphine)palladium(II) chloride (0.228 g) and triethylamine (1 ml). The mixture was heated at 60° C. for 2.5 hours. Trimethylsilylacetylene (1.675 ml), cuprous iodide (0.058 g) and bis(triphenylphosphine)palladium(II) chloride (0.114 g) were then added and stirring and heating was continued for a further period of one hour. The cooled reaction mixture was diluted with water and extracted with ether. The ether extract was dried (MgSO4) and evaporated to give the crude product which was purified by column chromatography on silica gel eluted with dichloromethane/hexane. Combination and evaporation of suitable fractions followed by recrystallisation of their residue from dichloromethane/hexane provided the title compound as a pale yellow solid, m.p. 151.5-152.1° C.

Workup

  1. temperatureheating
  2. customThe cooled reaction mixture
  3. extractionextracted with ether
  4. extractionThe ether extract
  5. dry with materialwas dried (MgSO4)
  6. customevaporated
  7. customto give the crude product which
  8. customwas purified by column chromatography on silica gel
  9. washeluted with dichloromethane/hexane
  10. customCombination and evaporation of suitable fractions
  11. customfollowed by recrystallisation of their residue from dichloromethane/hexane

Sources & evidence

ORD record
ord-bc2c561ea9724ff38b1675faca0e4166
Source dataset
uspto-grants-2000_02
Patent number
US06028096

Reaction notes

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