Dimethylformamide → HCID 18420210, compound

HRID 1063802Notes

Reaction equation

HRID 1063802 reaction equation
C(Cl)(=O)C(Cl)=O.[C:7]([C:11]1[NH:15][N:14]=[C:13]([C:16](O)=[O:17])[C:12]=1[N+:19]([O-:21])=[O:20])([CH3:10])([CH3:9])[CH3:8].C[N:23](C)C=O>ClCCl>[C:7]([C:11]1[NH:15][N:14]=[C:13]([C:16]([NH2:23])=[O:17])[C:12]=1[N+:19]([O-:21])=[O:20])([CH3:10])([CH3:9])[CH3:8]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 222774295-(1,1-Dimethylethyl)-4-nitro-1H-pyrazole-3-carboxylic acid

Product 1

HCID 18420210HCID 18420210, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Oxalyl chloride (10.2 ml, 117 mmol) was added dropwise to a suspension of 5-tert-butyl-4-nitro-1H-pyrazol-3-carboxylic acid (6 g, 28 mmol) in dichloromethane (55 ml) containing dimethylformamide (0.1 ml) under nitrogen at 0° C. The reaction was stirred at 0° C. for 0.5 hours, allowed to warm to room temperature and stirred for a further 1.5 hours. The solvent was removed under reduced pressure, the residue was azeotroped with dichloromethane (50 ml) and the residue was dissolved in dichloromethane (100 ml). Ammonia gas was bubbled into the solution for 45 minutes and the reaction was stirred under nitrogen at room temperature for 18 hours, concentrated under reduced pressure and the residue was dissolved in ethyl acetate (250 ml). After washing with water (100 ml) and brine (100 ml) the organic phase was filtered, the filtrate was dried over MgSO4 and concentrated under reduced pressure to give 5-tert-butyl-4-nitro-1H-pyrazol-3-carboxylic acid amide (4.0 g) as a light brown solid. 1H NMR (400 MHz, DMSO-D6): δ=12.90-13.08 (1H, brs), 7.78-7.86 (1H, brs), 7.49-7.60 (1H, brs), 1.30 (9H, s) (electrospray): m/z [M+H]+ 213, [M+Na]+ 235, [M−H]+ 211.

Workup

  1. temperatureto warm to room temperature
  2. stirringstirred for a further 1.5 hours
  3. customThe solvent was removed under reduced pressure
  4. customthe residue was azeotroped with dichloromethane (50 ml)
  5. dissolutionthe residue was dissolved in dichloromethane (100 ml)
  6. customAmmonia gas was bubbled into the solution for 45 minutes
  7. stirringthe reaction was stirred under nitrogen at room temperature for 18 hours
  8. concentrationconcentrated under reduced pressure
  9. dissolutionthe residue was dissolved in ethyl acetate (250 ml)
  10. washAfter washing with water (100 ml) and brine (100 ml) the organic phase
  11. filtrationwas filtered
  12. dry with materialthe filtrate was dried over MgSO4
  13. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-cdde89dcd9ec4536aee3af6aac21876e
Source dataset
uspto-grants-2005_11
Patent number
US06967204B2

Reaction notes

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