Triethylamine → N-(4-cyano-1-isopropyl-1H-pyrazol-5-yl)-4-nitrobenzamide

HRID 1093183Notes

Reaction equation

HRID 1093183 reaction equation
[NH2:1][C:2]1[N:6]([CH:7]([CH3:9])[CH3:8])[N:5]=[CH:4][C:3]=1[C:10]#[N:11].[N+:12]([C:15]1[CH:23]=[CH:22][C:18]([C:19](Cl)=[O:20])=[CH:17][CH:16]=1)([O-:14])=[O:13].C(N(CC)CC)C>ClCCl>[C:10]([C:3]1[CH:4]=[N:5][N:6]([CH:7]([CH3:9])[CH3:8])[C:2]=1[NH:1][C:19](=[O:20])[C:18]1[CH:17]=[CH:16][C:15]([N+:12]([O-:14])=[O:13])=[CH:23][CH:22]=1)#[N:11]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 85024-Nitrobenzoyl chlorideHCID 179620285-amino-1-isopropyl-1H-pyrazole-4-carbonitrile

Product 1

HCID 66589126N-(4-cyano-1-isopropyl-1H-pyrazol-5-yl)-4-nitrobenzamideYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of crude 5-amino-1-isopropyl-1H-pyrazole-4-carbonitrile (0.72 g, 4.5 mmol maximum) and 4-nitrobenzoylchloride (1.3 g, 6.8 mmol) in dichloromethane (20 mL) was treated successively with triethylamine (1.8 mL, 14 mmol) and 4-N,N-dimethylaminoaniline (DMAP, 55 mg, 10 mol %). The mixture was heated to reflux (oil bath) for one hour and then allowed to cool to room temperature. The mixture was then concentrated to dryness under reduced pressure. The residue was dissolved in pyridine (20 mL). Water was added, followed by concentrated aqueous ammonium hydroxide (5 mL). The reaction vessel was swirled manually and then left overnight at room temperature. The mixture was concentrated to dryness under reduced pressure. The residue was partitioned between ethyl acetate and water. The aqueous phase was extracted three times with ethyl acetate. The combined extracts were washed twice with saturated aqueous sodium hydrogen carbonate solution and once each with 0.25 M aqueous hydrochloric acid and saturated aqueous sodium chloride solution. Drying over anhydrous magnesium sulfate was followed by filtration and then concentration under reduced pressure to provide N-(4-cyano-1-isopropyl-1H-pyrazol-5-yl)-4-nitrobenzamide as a dark yellow solid (1.3 g, 100%). MS (ES+): 299.6, 299.9 (M+H)+

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux (oil bath) for one hour
  3. concentrationThe mixture was then concentrated to dryness under reduced pressure
  4. dissolutionThe residue was dissolved in pyridine (20 mL)
  5. additionWater was added
  6. concentrationThe mixture was concentrated to dryness under reduced pressure
  7. customThe residue was partitioned between ethyl acetate and water
  8. extractionThe aqueous phase was extracted three times with ethyl acetate
  9. washThe combined extracts were washed twice with saturated aqueous sodium hydrogen carbonate solution
  10. dry with materialDrying over anhydrous magnesium sulfate
  11. filtrationwas followed by filtration
  12. concentrationconcentration under reduced pressure

Sources & evidence

ORD record
ord-4b3d0d6ab5824fceb1426dc5523555e1
Source dataset
uspto-grants-2012_03
Patent number
US08129371B2

Reaction notes

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