Triethylamine → HCID 20784956, compound

HRID 709323Notes

Reaction equation

HRID 709323 reaction equation
[N+:1]([C:4]1[CH:5]=[N:6][NH:7][CH:8]=1)([O-])=O.C(N(CC)CC)C.Cl.[N:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:23](Cl)=[O:24]>C(O)C.[Pd]>[NH:6]1[CH:5]=[C:4]([NH:1][C:23](=[O:24])[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][N:17]=2)[CH:8]=[N:7]1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 163764-nitro-1H-pyrazoleHCID 135033Picolinoyl Chloride Hydrochloride

Product 1

HCID 20784956HCID 20784956, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

A solution of 4-nitro-1H-pyrazole (2.5 g, 22 mmol) in ethanol (80 mL) was added to a Parr vessel under an argon atmosphere. Carefully into the vessel, 10% Pd/C (0.2 g) was added. The vessel was sealed and H2 was added to a pressure of 40 psi. The vessel was shaken for 3 hours and then the catalyst removed by filtration. The catalyst was washed with ethanol and the combined filtrates where evaporated to dryness under reduced pressure. The residue was dissolved in THF (350 mL), treated with triethyl amine (6.9 mL, 49 mmol) and cooled on an ice bath under an argon atmosphere. Picolinoyl chloride hydrochloride (3.94 g, 22.3 mmol) was added in one portion. When the reaction was complete, the solvent was removed under reduced pressure and the residue dissolved in dichloromethane. The solution was extracted with water, NaHCO3 sat, dried, and the solvent removed under reduced pressure. The crude residue was re-crystallized from ethyl acetate to afford N-(1H-pyrazol-4-yl)picolinamide. (2.19 g, 52%). 1H NMR (DMSO-d6) δ 10.88 (s, 1 H), 8.7 (s, 1 H), 8.12 (m, 2 H), 8.04 (m, 1 H,), 7.96 (s, 1 H), 7.65 (m, 1 H). MS: m/z=189[M+1]+.

Workup

  1. customThe vessel was sealed
  2. additionH2 was added to a pressure of 40 psi
  3. customthe catalyst removed by filtration
  4. washThe catalyst was washed with ethanol
  5. customthe combined filtrates where evaporated to dryness under reduced pressure
  6. dissolutionThe residue was dissolved in THF (350 mL)
  7. temperaturecooled on an ice bath under an argon atmosphere
  8. customthe solvent was removed under reduced pressure
  9. dissolutionthe residue dissolved in dichloromethane
  10. extractionThe solution was extracted with water, NaHCO3
  11. customdried
  12. customthe solvent removed under reduced pressure
  13. customThe crude residue was re-crystallized from ethyl acetate

Sources & evidence

ORD record
ord-3d8a79189bb44633870f818afd2b311b
Source dataset
uspto-grants-2015_11
Patent number
US09180192B2

Reaction notes

Loading…