Formic Acid → 4-Amino-2-phenylamino-pyrimidine-5-carboxaldehyde

HRID 3446Notes

Reaction equation

HRID 3446 reaction equation
[NH2:1][C:2]1[C:7]([C:8]#N)=[CH:6][N:5]=[C:4]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:3]=1.C(O)=[O:18]>[Ni].O>[NH2:1][C:2]1[C:7]([CH:8]=[O:18])=[CH:6][N:5]=[C:4]([NH:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:3]=1

Participants

5

Reactant 2

HCID 284Formic AcidHCID 139252174-Amino-2-phenylamino-pyrimidine-5-carbonitrile

Product 1

HCID 183753114-Amino-2-phenylamino-pyrimidine-5-carboxaldehyde

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 962WaterSolvent

Procedure

4-Amino-2-phenylamino-pyrimidine-5-carbonitrile (2.00 g) obtained from Example 71 was combined with wet Raney nickel (2.00 g), 98% formic acid (60 mL) and water (40 mL) in a Parr shaker. The reaction was placed under hydrogen (42 psi) and shaken for 20 minutes. The reaction was filtered, and the filtrate was concentrated in vacuo. The residue was suspended in water, made basic with saturated sodium bicarbonate, and extracted with ethyl acetate three times. The aqueous layer was filtered through a fiberglass filter to disperse the emulsion that was present. The aqueous filtrate was washed with ethyl acetate. The ethyl acetate washes were combined, filtered, washed with saturated sodium chloride, dried with magnesium sulfate and concentrated in vacuo. Chromatography down silica gel, eluting with ethyl acetate:hexane (2:1) gave 0.73 g of the title compound, CIMS (1% NH3 in CH4): 243=M+ +C2H5, 215=M+ +H (Base), 214=M+.

Workup

  1. filtrationThe reaction was filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. extractionextracted with ethyl acetate three times
  4. filtrationThe aqueous layer was filtered through a fiberglass
  5. filtrationfilter
  6. additionto disperse the emulsion that
  7. washThe aqueous filtrate was washed with ethyl acetate
  8. filtrationfiltered
  9. washwashed with saturated sodium chloride
  10. dry with materialdried with magnesium sulfate
  11. concentrationconcentrated in vacuo
  12. washChromatography down silica gel, eluting with ethyl acetate:hexane (2:1)

Sources & evidence

ORD record
ord-748a2d0593d44481a5c135fdf239e33d
Source dataset
uspto-grants-1998_03
Patent number
US05733913

Reaction notes

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