Potassium Carbonate → 3-nitro-1-(3-(trifluoromethyl)phenyl)-1H-pyrazole

HRID 926863Notes

Reaction equation

HRID 926863 reaction equation
[N+:1]([C:4]1[CH:8]=[CH:7][NH:6][N:5]=1)([O-:3])=[O:2].I[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([F:19])([F:18])[F:17])[CH:11]=1.C(=O)([O-])[O-].[K+].[K+].N1CCC[C@H]1C(O)=O>CS(C)=O.O.[Cu]I>[N+:1]([C:4]1[CH:8]=[CH:7][N:6]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([C:16]([F:19])([F:18])[F:17])[CH:11]=2)[N:5]=1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 67868Benzene, 1-iodo-3-(trifluoromethyl)-HCID 145742L-ProlineHCID 178526745HCID 178526745, compound

Product 1

HCID 665874833-nitro-1-(3-(trifluoromethyl)phenyl)-1H-pyrazoleYield 62%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
85 °C

Procedure

Into a 250-mL round-bottom flask, was placed a solution of 3-nitro-1H-pyrazole (10 g, 88.50 mmol, 1.00 equiv) in DMSO (100 mL), 1-iodo-3-(trifluoromethyl)benzene (29 g, 106.62 mmol, 1.20 equiv), potassium carbonate (24 g, 173.91 mmol, 1.97 equiv), copper(I) iodide (2.6 g, 13.68 mmol, 0.15 equiv), and L-proline (2.5 g, 21.74 mmol, 0.25 equiv). The resulting solution was stirred overnight at 85° C. in an oil bath. The reaction progress was monitored by LCMS. The resulting solution was diluted with 500 mL of water, extracted with 7×200 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 3×200 mL of water and 2×200 mL of brine. The mixture was dried over sodium sulfate. The solids were filtered out. The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column and eluted with petroleum ether/ethyl acetate (10:1-5:1) to give 14 g (62%) of 3-nitro-1-(3-(trifluoromethyl)phenyl)-1H-pyrazole as a light yellow solid.

Workup

  1. customInto a 250-mL round-bottom flask, was placed
  2. extractionextracted with 7×200 mL of ethyl acetate
  3. washThe resulting mixture was washed with 3×200 mL of water and 2×200 mL of brine
  4. dry with materialThe mixture was dried over sodium sulfate
  5. filtrationThe solids were filtered out
  6. concentrationThe resulting mixture was concentrated under vacuum
  7. washeluted with petroleum ether/ethyl acetate (10:1-5:1)

Sources & evidence

ORD record
ord-e51e91c1f0894c1aa9f6c9994be09dcb
Source dataset
uspto-grants-2016_03
Patent number
US09289430B2

Reaction notes

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