Ammonia → tert-butyl 4-(6-amino-5-nitropyrimidin-4-yl)piperazine-1-carboxylate

HRID 2230102Notes

Reaction equation

HRID 2230102 reaction equation
N.Cl[C:3]1[C:8]([N+:9]([O-:11])=[O:10])=[C:7](Cl)[N:6]=[CH:5][N:4]=1.[C:13]([O:17][C:18]([N:20]1[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]1)=[O:19])([CH3:16])([CH3:15])[CH3:14].C([N:28](CC)CC)C.[Cl-].[Na+]>O.C(Cl)Cl>[C:13]([O:17][C:18]([N:20]1[CH2:25][CH2:24][N:23]([C:3]2[C:8]([N+:9]([O-:11])=[O:10])=[C:7]([NH2:28])[N:6]=[CH:5][N:4]=2)[CH2:22][CH2:21]1)=[O:19])([CH3:16])([CH3:14])[CH3:15]

Participants

8

Reactant 5

HCID 222AmmoniaHCID 5234Sodium ChlorideHCID 8471TriethylamineHCID 203124,6-Dichloro-5-nitropyrimidineHCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 11484147tert-butyl 4-(6-amino-5-nitropyrimidin-4-yl)piperazine-1-carboxylateYield 50.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a methylene chloride solution (50 mL) saturated with ammonia, commercially available 4,6-dichloro-5-nitropyrimidine (1.00 g, 5.44 mmol) was added, followed by stirring at room temperature for 1 hour. The reaction solution was concentrated, the resulting residue was dissolved in dimethylformamide (10 mL), and then N-tert-butoxycarbonylpiperazine (1.15 g, 6.17 mmol) and triethylamine (3.59 mL, 25.8 mmol) were added thereto, followed by stirring under heating at 80° C. for 4 hours. After the reaction solution was allowed to stand for cooling, it was poured into water, sodium chloride was added thereto, and the precipitated crystals were recovered by filtration, washed with water, and dried to give 4-(6-amino-5-nitro-4-pyrimidinyl)-1-piperazinecarboxylic acid tert-butyl ester (888 mg, 2.74 mmol).

Workup

  1. concentrationThe reaction solution was concentrated
  2. dissolutionthe resulting residue was dissolved in dimethylformamide (10 mL)
  3. stirringby stirring
  4. temperatureunder heating at 80° C. for 4 hours
  5. temperaturefor cooling
  6. additionwas added
  7. filtrationthe precipitated crystals were recovered by filtration
  8. washwashed with water
  9. customdried

Sources & evidence

ORD record
ord-c1809119a5d34dcb8ac577f7331d0ed3
Source dataset
uspto-grants-2002_07
Patent number
US06423716B1

Reaction notes

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