Hydrazine → 4-[[5-Amino4-[(2,4,6-trimethylphenyl)amino]-2-pyrimidinyl]amino]benzonitrile

HRID 2357967Notes

Reaction equation

HRID 2357967 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([CH3:9])[C:3]=1[NH:10][C:11]1[C:16]([N+:17]([O-])=O)=[CH:15][N:14]=[C:13]([NH:20][C:21]2[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=2)[N:12]=1.NN>[Pd].C(O)C>[NH2:17][C:16]1[C:11]([NH:10][C:3]2[C:2]([CH3:1])=[CH:7][C:6]([CH3:8])=[CH:5][C:4]=2[CH3:9])=[N:12][C:13]([NH:20][C:21]2[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=2)=[N:14][CH:15]=1

Participants

5

Reactant 2

HCID 9321HydrazineHCID 221700954-[[4-[(2,4,6-Trimethylphenyl)amino]-5-nitro-2-pyrimidinyl]amino]benzonitrile

Product 1

HCID 221700874-[[5-Amino4-[(2,4,6-trimethylphenyl)amino]-2-pyrimidinyl]amino]benzonitrileYield 70%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

4-[[4-[(2,4,6-trimethylphenyl)amino]-5-nitro-2-pyrimidinyl]amino]benzonitrile (0.001 mol), Pd/C 10% (0.025 g), ethanol (20 ml), and hydrazine (0.030 mol) were combined to form a slurry and stirred at room temperature for 16 hours. The solvent was removed by rotary evaporation. The residue was taken up in tetrahydrofuran (20 ml) and methanol (1 ml). A second portion of hydrazine (0.5 g) was added, and the reaction was stirred for 16 hours at room temperature. A third portion of hydrazine (0.5 ml) was added and the reaction was stirred for an additional 16 hours at room temperature. The sample was concentrated by rotary evaporation onto silica gel (1 g) and purified by flash chromatography (eluent: 0.5, 1.2% 10% (NH4OH in CH3OH) in CH2Cl2). The desired fractions were purified by preparatory HPLC to yield 0.24 g of 4-[[5-amino-4-[(2,4,6-trimethylphenyl)amino]-2-pyrimidinyl]amino]benzonitrile (70%); mp. 224-225° C. (interm. 36).

Workup

  1. customto form a slurry
  2. customThe solvent was removed by rotary evaporation
  3. additionA second portion of hydrazine (0.5 g) was added
  4. stirringthe reaction was stirred for 16 hours at room temperature
  5. additionA third portion of hydrazine (0.5 ml) was added
  6. stirringthe reaction was stirred for an additional 16 hours at room temperature
  7. concentrationThe sample was concentrated by rotary evaporation onto silica gel (1 g)
  8. custompurified by flash chromatography (eluent: 0.5, 1.2% 10% (NH4OH in CH3OH) in CH2Cl2)
  9. customThe desired fractions were purified by preparatory HPLC

Sources & evidence

ORD record
ord-199419cfa57a4ebe806f6dbebd36ccac
Source dataset
uspto-grants-2010_07
Patent number
US07763631B2

Reaction notes

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