Carbamimidic acid, methyl ester, sulfate (1:1) → 1,4-Dihydro-2-methoxy-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, ethyl ester

HRID 1789577Notes

Reaction equation

HRID 1789577 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:10]=[C:11]([C:17](=O)[CH3:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].S(O)(O)(=O)=O.[CH3:25][O:26][C:27](=[NH:29])[NH2:28].C(=O)(O)[O-].[Na+]>CN(C)C=O.C(OCC)(=O)C>[CH3:25][O:26][C:27]1[NH:29][C:17]([CH3:18])=[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:10]([C:6]2[CH:7]=[CH:8][CH:9]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=2)[N:28]=1

Participants

6

Reactant 3

HCID 169039Carbamimidic acid, methyl ester, sulfate (1:1)HCID 367507Ethyl 2-(3-nitrobenzylidene)-3-oxobutanoateHCID 516892Sodium Bicarbonate

Product 1

HCID 139125831,4-Dihydro-2-methoxy-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, ethyl esterYield 75.5%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A reaction mixture containing 2-[(3-nitrophenyl)methylene]-3-oxobutanoic acid, ethyl ester (2.62 g, 10.0 mmole), 2-methylpseudourea sulfate (1.72 g, 10.0 mmole), and sodium bicarbonate (2.52 g, 30.0 mmole) in dimethylformamide (10 ml) was heated at 65°-70° C. for 16 hours. The reaction mixture was allowed to cool to room temperature, diluted with ethyl acetate, and filtered. The filtrate was washed with water and brine, and then dried over anhydrous magnesium sulfate. Evaporation of the solvent gave a yellow oil which was purified by flash chromatography (5% ethyl acetate in dichloromethane). The resulting foam was crystallized from isopropyl ether/hexanes to provide 2.41 g of 1,4-dihydro-2-methoxy-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, ethyl ester as a colorless crystalline product; melting point 103.5°-105° C. TLC (silica gel; ethyl acetate: hexanes 50:50) Rf =0.31

Workup

  1. temperaturewas heated at 65°-70° C. for 16 hours
  2. filtrationfiltered
  3. washThe filtrate was washed with water and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customEvaporation of the solvent
  6. customgave a yellow oil which
  7. customwas purified by flash chromatography (5% ethyl acetate in dichloromethane)
  8. customThe resulting foam was crystallized from isopropyl ether/hexanes

Sources & evidence

ORD record
ord-0a3b14c7b922485e955378c7884aefb2
Source dataset
uspto-grants-1987_08
Patent number
US04689414

Reaction notes

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