Formic Acid → 2-Amino-4-(methylamino)pyrimidine-5-carbaldehyde

HRID 3162Notes

Reaction equation

HRID 3162 reaction equation
[N:1]([C:4]1[N:9]=[C:8]([NH:10][CH3:11])[C:7]([C:12]#N)=[CH:6][N:5]=1)=[N+]=[N-].[H][H].C(O)=[O:17]>[Ni]>[NH2:1][C:4]1[N:9]=[C:8]([NH:10][CH3:11])[C:7]([CH:12]=[O:17])=[CH:6][N:5]=1

Participants

5

Reactant 3

HCID 284Formic AcidHCID 218527592-Azido-5-cyano-4-methylamino-pyrimidineHCID 178418361HCID 178418361, compound

Product 1

HCID 218527602-Amino-4-(methylamino)pyrimidine-5-carbaldehyde

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst2×

Procedure

To a suspension of 2-azido-5-cyano-4-methylaminopyrimidine (22.24 g) from Example 5 in 400 mL of 50% aqueous formic acid was added Raney Nickel catalyst (5 g). The reaction mixture was shaken under an atmosphere of hydrogen (40.1 psi) in a Parr hydrogenation apparatus. There was a vigorous evolution of gas as the mixture was shaken at room temperature. After 30 minutes the apparatus was vented, additional Raney Nickel (5 g) was added, the apparatus recharged with hydrogen, and the mixture shaken overnight. The catalyst was removed by filtration and the filtrate was evaporated under high vacuum. The residue was suspended in water and filtered. The insoluble material was collected and dissolved in 450 mL of boiling water. The aqueous solution was filtered and the pH of the filtrate was adjusted to 7 with 1N sodium hydroxide. The precipitated product was collected by filtration and recrystallized from ethanol to give 5.0 g of 2-amino-4-methylamino-5-pyrimidinecarboxaldehyde.

Workup

  1. stirringwas shaken at room temperature
  2. stirringthe mixture shaken overnight
  3. customThe catalyst was removed by filtration
  4. customthe filtrate was evaporated under high vacuum
  5. filtrationfiltered
  6. customThe insoluble material was collected
  7. dissolutiondissolved in 450 mL of boiling water
  8. filtrationThe aqueous solution was filtered
  9. filtrationThe precipitated product was collected by filtration
  10. customrecrystallized from ethanol

Sources & evidence

ORD record
ord-30431f184fdc4b00a734c5fabc99cc4f
Source dataset
uspto-grants-1998_03
Patent number
US05733914

Reaction notes

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