4-Fluoroiodobenzene → ethyl 1-(4-fluorophenyl)-1H-pyrazole-3-carboxylate

HRID 1755258Notes

Reaction equation

HRID 1755258 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[NH:9]1[CH:13]=[CH:12][C:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[N:10]1.CN(C)[C@@H]1CCCC[C@H]1N.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.[Cu]I>[F:1][C:2]1[CH:7]=[CH:6][C:5]([N:9]2[CH:13]=[CH:12][C:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[N:10]2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 96054-FluoroiodobenzeneHCID 11430Potassium CarbonateHCID 11275066(1R,2R)-N1,N1-Dimethylcyclohexane-1,2-diamineHCID 178469268HCID 178469268, compound

Product 1

HCID 14129372ethyl 1-(4-fluorophenyl)-1H-pyrazole-3-carboxylateYield 77%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

To a solution of 1-fluoro-4-iodo-benzene (1.47 g, 6.6 mmol, 1.3 eq) and ethyl 1H-pyrazole-3-carboxylate (0.71 g, 5.1 mmol, 1 eq) in 15 mL of toluene was added CuI (0.19 g, 1.0 mmol, 0.2 eq), trans-N,—N-dimethylcyclohexane 1,2-diamine (0.4 mL, 2.5 mmol, 0.2 eq), and potassium carbonate (1.4 g, 10 mmol, 2 eq). The reaction mixture was heated at 110° C. for 2 d then filtered and concentrated. The residue was purified by silica gel column chromatography (hex:EtoAc 4:1) to afford ethyl 1-(4-fluorophenyl)pyrazole-3-carboxylate (0.92 g, 3.9 mmol, 77%).

Workup

  1. filtrationthen filtered
  2. concentrationconcentrated
  3. customThe residue was purified by silica gel column chromatography (hex:EtoAc 4:1)

Sources & evidence

ORD record
ord-93b9b36478ca492e93f8d10589d8a529
Source dataset
uspto-grants-2015_10
Patent number
US09169261B2

Reaction notes

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