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

HRID 53441

Reaction equation

HRID 53441 reaction equation
Br[C:2]1[C:3]([CH3:17])=[C:4]([N+:14]([O-:16])=[O:15])[C:5]([NH:8][C:9]([CH:11]2[CH2:13][CH2:12]2)=[O:10])=[N:6][CH:7]=1.C(N(CC)CC)C.C(O)=O>[Pd].C1(C)C=CC=CC=1>[CH:11]1([C:9]([NH:8][C:5]2[C:4]([N+:14]([O-:16])=[O:15])=[C:3]([CH3:17])[CH:2]=[CH:7][N:6]=2)=[O:10])[CH2:12][CH2:13]1

Participants

6

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 1140TolueneSolvent

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 (a n-hexane/ethyl acetate system)

Sources & evidence

ORD record
ord-868eab46688c4b149fd7a79c0d17fd8d
Source dataset
uspto-grants-1997_04
Patent number
US05618969

Linked notes

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