Carbonic acid-guanidine (1:1) → 2-Amino-4-phenylpyrimidine-5-carbonitrile

HRID 1355697Notes

Reaction equation

HRID 1355697 reaction equation
[C:1]([C:9](=[CH:12]N(C)C)[C:10]#[N:11])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)(O)O.[NH2:20][C:21]([NH2:23])=[NH:22].C[O-].[Na+]>CO>[NH2:22][C:21]1[N:23]=[CH:12][C:9]([C:10]#[N:11])=[C:1]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[N:20]=1

Participants

5

Reactant 3

HCID 286947Carbonic acid-guanidine (1:1)HCID 38455902-[(Dimethylamino)methylene]-3-oxo-3-phenylpropanenitrileHCID 10942334Sodium Methoxide

Product 1

HCID 7236882-Amino-4-phenylpyrimidine-5-carbonitrileYield 41.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Following the method of Earley et al. (J. Het. Chem. 1983, 20, 1195), to a stirred solution of 6.9 g (34.4 mmol) 2-benzoyl-3-dimethylaminoacrylonitrile and 20.6 g (114 mmol) guanidine carbonate in 50 ml methanol was added 43 ml (232 mmol) sodium methylate (5.4 M in methanol) and the mixture stirred at room temperature for 2 h. The reaction mixture was then concentrated in vacuo. The residue was resuspended in ethyl acetate and water, and the aqueous phase acidified to pH 8 by addition of hydrochloric acid. The phases were separated and the aqueous phase extracted twice more with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated in vacuo. The residue was triturated in a mixture of ethyl acetate, ether, dichloromethane and ethanol, and the resulting crystals were then additionally recrystallised from ethanol/ether to afford 2.83 g (41%) 2-amino-5-cyano-6-phenylpyrimidine as a light yellow crystalline solid. EI-MS m/e (%): 196 (M+, 100), 195 ([M—H]+, 40), 170 ([M—CN]+, 36).

Workup

  1. concentrationThe reaction mixture was then concentrated in vacuo
  2. additionwater, and the aqueous phase acidified to pH 8 by addition of hydrochloric acid
  3. customThe phases were separated
  4. extractionthe aqueous phase extracted twice more with ethyl acetate
  5. dry with materialThe combined organic phases were dried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was triturated in a mixture of ethyl acetate, ether, dichloromethane and ethanol
  8. customthe resulting crystals were then additionally recrystallised from ethanol/ether

Sources & evidence

ORD record
ord-df36b1ec673943dcbc16bb90bfc073ef
Source dataset
uspto-grants-2003_07
Patent number
US06586441B2

Reaction notes

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