Formic Acid → Cyclopropanecarboxamido-4-methyl-3-nitropyridine

HRID 1940951Notes

Reaction equation

HRID 1940951 reaction equation
C1(C)C=CC=CC=1.Br[C:9]1[C:10]([CH3:24])=[C:11]([N+:21]([O-:23])=[O:22])[C:12]([NH:15][C:16]([CH:18]2[CH2:20][CH2:19]2)=[O:17])=[N:13][CH:14]=1.C(N(CC)CC)C.C(O)=O>CCCCCC.C(OCC)(=O)C>[CH:18]1([C:16]([NH:15][C:12]2[C:11]([N+:21]([O-:23])=[O:22])=[C:10]([CH3:24])[CH:9]=[CH:14][N:13]=2)=[O:17])[CH2:19][CH2:20]1

Participants

6

Reactant 4

HCID 284Formic AcidHCID 1140TolueneHCID 8471TriethylamineHCID 109794822-cyclopropanecarboxamido-5-Bromo-4-Methyl-3-nitropyridine

Product 1

HCID 15380885Cyclopropanecarboxamido-4-methyl-3-nitropyridineYield 72.3%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

Toluene (60 ml) was added to 3.0 g (10.0 mmol) of 5-bromo-2-cyclopropanecarboxamido-4-methyl-3-nitropyridine, 10% Pd--C (100 mg) and 2.9 g (28.6 mmol) of triethylamine, followed by stirring and heating under reflux. 1.9 g (41.3 mmol) of formic acid was dropwise added to this solution, followed by stirring for 5 hours. The reaction liquid was brought to room temperature and filtered to remove the catalyst. The filtrate was subjected to vacuum concentration. Chloroform (100 ml) and water (100 ml) were added to the residue and the obtained mixture was caused liquid-liquid separation. The aqueous phase was further extracted with chloroform (50 ml) once. The organic phases were combined, dried over anhydrous magnesium sulfate and subjected to vacuum concentration. The residue was purified by silica gel column chromatography: (a n-hexane/ethyl acetate system) to give 1.6 g of the title compound (yield 72%).

Workup

  1. temperatureheating
  2. temperatureunder reflux
  3. stirringby stirring for 5 hours
  4. customThe reaction liquid
  5. customwas brought to room temperature
  6. filtrationfiltered
  7. customto remove the catalyst
  8. concentrationThe filtrate was subjected to vacuum concentration
  9. additionChloroform (100 ml) and water (100 ml) were added to the residue
  10. customliquid-liquid separation
  11. extractionThe aqueous phase was further extracted with chloroform (50 ml) once
  12. dry with materialdried over anhydrous magnesium sulfate
  13. concentrationsubjected to vacuum concentration
  14. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-6674975646bc4c31bf37297af960c901
Source dataset
uspto-grants-1997_12
Patent number
US05700938

Reaction notes

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