Pyridine → HCID 178521706, compound

HRID 491392Notes

Reaction equation

HRID 491392 reaction equation
C(Cl)(=O)C(Cl)=O.[N+:7]([C:10]1[CH:14]=[C:13]([C:15]([OH:17])=O)[NH:12][N:11]=1)([O-:9])=[O:8].[CH:18]1([NH2:21])[CH2:20][CH2:19]1.N1C=CC=CC=1>ClCCl.C1COCC1.CN(C=O)C.C(OCC)(=O)C>[CH:18]1([NH:21][C:15]([C:13]2[NH:12][N:11]=[C:10]([N+:7]([O-:9])=[O:8])[CH:14]=2)=[O:17])[CH2:20][CH2:19]1

Participants

9

Reactant 4

HCID 1049PyridineHCID 65578Oxalyl chlorideHCID 69828CyclopropylamineHCID 178524578HCID 178524578, compound

Product 1

HCID 178521706HCID 178521706, compoundYield 93.4%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Oxalyl chloride (8.75 mL, 100 mmol) was added to a suspension of 3-nitro-1H-pyrazole-5-carboxylic acid (7.85 g, 50 mmol) in dichloromethane (100 mL) and THF (5.00 mL) at 0° C. and one drop of DMF was then added to the reaction mixture. The reaction mixture was stirred at room temperature for 3 hours. The solvent was evaporated and the residue was redissolved in dichloromethane (100 mL). To the reaction mixture was added a solution of cyclopropanamine (4.16 mL, 60.0 mmol) and pyridine (8.09 mL, 100 mmol) in dichloromethane (10 mL) over a period of 10 minutes. The reaction mixture was stirred overnight and then diluted with ethyl acetate (50 mL), washed with water, dried over MgSO4 and concentrated in vacuo. The crude was purified by silica gel column chromatography (0-5% 2N NH3/CD3ODichloromethane) to give 9.16 g of N-cyclopropyl-3-nitro-1H-pyrazole-5-carboxamide. MS (ESI) m/z 197.1 (M+H). 1H NMR (CD3OD) δ ppm 7.38 (s, 1H), 2.81-2.86 (m, 1H), 0.82 (td, J=7.08, 5.36 Hz, 2H), 0.62-0.68 (m, 2H).

Workup

  1. customThe solvent was evaporated
  2. dissolutionthe residue was redissolved in dichloromethane (100 mL)
  3. stirringThe reaction mixture was stirred overnight
  4. washwashed with water
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe crude was purified by silica gel column chromatography (0-5% 2N NH3/CD3ODichloromethane)

Sources & evidence

ORD record
ord-4eff50b9e5c5458c81c60a8090dfdd26
Source dataset
uspto-grants-2009_05
Patent number
US07531539B2

Reaction notes

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