Methyl Isocyanate → 2,4(1H,3H)-Pyrimidinedione, dihydro-1-(2,4-dichlorophenyl)-3-methyl-

HRID 280106Notes

Reaction equation

HRID 280106 reaction equation
CO[C:3](=[O:15])[CH2:4][CH2:5][NH:6][C:7]1[CH:12]=[CH:11][C:10]([Cl:13])=[CH:9][C:8]=1[Cl:14].C([Li])CCC.[CH3:21][N:22]=[C:23]=[O:24].[Cl-].[NH4+]>O1CCCC1>[Cl:14][C:8]1[CH:9]=[C:10]([Cl:13])[CH:11]=[CH:12][C:7]=1[N:6]1[CH2:5][CH2:4][C:3](=[O:15])[N:22]([CH3:21])[C:23]1=[O:24]

Participants

6

Reactant 4

HCID 12228Methyl IsocyanateHCID 25517Ammonium ChlorideHCID 12999022HCID 12999022, compoundHCID 178418339Butyllithium

Product 1

HCID 30636712,4(1H,3H)-Pyrimidinedione, dihydro-1-(2,4-dichlorophenyl)-3-methyl-Yield 16.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

At first, 7.44 g (0.03 moles) of N-(2,4-dichlorophenyl)-β-alanine methyl ester was dissolved in 150 ml of tetrahydrofuran (THF), and 19.2 ml (0.03 moles) of n-butyl lithium was added thereto at -78° C. Several minutes thereafter, 5.4 ml (0.045 moles) of methyl isocyanate was added thereto. The mixture was stirred at the same temperature for one hour, a saturated aqueous ammonium chloride solution was added thereto, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and with a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography and recrystallized from toluene, whereby 1.32 g of the desired compound was obtained as colorless prism crystals having a melting point of 154°-157° C. (yield: 16.1%).

Workup

  1. customat -78° C
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe ethyl acetate layer was washed with water and with a saturated aqueous sodium chloride solution
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationthe solvent was distilled off under reduced pressure
  6. customrecrystallized from toluene

Sources & evidence

ORD record
ord-0957dba095f748499982221f01d62bfd
Source dataset
uspto-grants-1986_05
Patent number
US04588729

Reaction notes

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