Hydrochloric Acid → 2,4-Diamino-5-[1-(p-chlorophenyl)-4-piperidinyl]pyrimidine

HRID 623199Notes

Reaction equation

HRID 623199 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([CH:9]2[CH2:14][CH2:13][N:12]([C:15]3[CH:20]=[CH:19][C:18]([N+]([O-])=O)=[CH:17][CH:16]=3)[CH2:11][CH2:10]2)=[CH:4][N:3]=1.[ClH:24]>O.[Fe]>[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([CH:9]2[CH2:14][CH2:13][N:12]([C:15]3[CH:20]=[CH:19][C:18]([Cl:24])=[CH:17][CH:16]=3)[CH2:11][CH2:10]2)=[CH:4][N:3]=1

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 212906212,4-Diamino-5-[1-(p-nitrophenyl)-4-piperidinyl]pyrimidine

Product 1

HCID 212906232,4-Diamino-5-[1-(p-chlorophenyl)-4-piperidinyl]pyrimidine

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

1 g of 2,4-diamino-5-[1-(p-nitrophenyl)-4-piperidinyl]pyrimidine was dissolved in 50 ml of water and 10 ml of conc. hydrochloric acid, treated with 700 mg of iron powder and stirred at 80° C. for 45 minutes. The mixture was filtered over a filter aid, the filtrate was cooled to 0°-5° C., diazotized with 210 mg of sodium nitrite in 2 ml of water and the resulting diazonium solution was added dropwise at 0°-5° C. to a solution of copper (I) chloride (prepared from 250 mg of copper (II) sulfate pentahydrate, 80 mg of sodium chloride and 70 mg of sodium bisulfite) in 0.8 ml of hydrochloric acid. Thereafter, the reaction mixture was heated at 90° C. for 1 hour, treated with active carbon, filtered and concentrated to 50 ml. The residue was neutralized with ammonium hydroxide, filtered off and the product obtained after distilling off the water was chromatographed on silica gel with CHCl3 /EtOH (9:1). Recrystallization from ethanol yielded 2,4-diamino-5-[1-(p-chlorophenyl)-4-piperidinyl]pyrimidine of melting point 254°-255° C.

Workup

  1. filtrationThe mixture was filtered over a filter aid
  2. temperaturethe filtrate was cooled to 0°-5° C.
  3. additionthe resulting diazonium solution was added dropwise at 0°-5° C. to a solution of copper (I) chloride (prepared from 250 mg of copper (II) sulfate pentahydrate, 80 mg of sodium chloride and 70 mg of sodium bisulfite) in 0.8 ml of hydrochloric acid
  4. temperatureThereafter, the reaction mixture was heated at 90° C. for 1 hour
  5. additiontreated with active carbon
  6. filtrationfiltered
  7. concentrationconcentrated to 50 ml
  8. filtrationfiltered off
  9. customthe product obtained
  10. distillationafter distilling off the water
  11. customwas chromatographed on silica gel with CHCl3 /EtOH (9:1)
  12. customRecrystallization from ethanol

Sources & evidence

ORD record
ord-f50ecda9c0d14780b3e2404a1086f0ba
Source dataset
uspto-grants-1988_09
Patent number
US04774249

Reaction notes

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