Ethyl 4-chloroacetoacetate → S-[(3,4-Dihydro-2-(1-methylethyl)-4-oxo-6-pyrimidinyl)methyl] O,O-dimethyl phosphorodithioate

HRID 1075295Notes

Reaction equation

HRID 1075295 reaction equation
Cl[CH2:2][C:3]1[NH:8][C:7]([CH:9]([CH3:11])[CH3:10])=[N:6][C:5](=[O:12])[CH:4]=1.ClCC(=O)CC(OCC)=O.C(N)(=N)C(C)C.[P:29]([S-:35])(=[S:34])([O:32][CH3:33])[O:30][CH3:31].[NH4+]>CO.ClCCl>[P:29]([S:35][CH2:2][C:3]1[N:8]=[C:7]([CH:9]([CH3:11])[CH3:10])[NH:6][C:5](=[O:12])[CH:4]=1)(=[S:34])([O:32][CH3:33])[O:30][CH3:31]

Participants

7

Reactant 4

HCID 69484Ethyl 4-chloroacetoacetateHCID 4151182-MethylpropanimidamideHCID 6451175Ammonium O,O-dimethyl dithiophosphateHCID 178440240HCID 178440240, compound

Product 1

HCID 135665134S-[(3,4-Dihydro-2-(1-methylethyl)-4-oxo-6-pyrimidinyl)methyl] O,O-dimethyl phosphorodithioate

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 6344DichloromethaneSolvent

Procedure

The intermediate, 6-(chloromethyl)-2-(1-methylethyl)-4(1H)pyrimidinone, was prepared according to Swiss patent 524617 from ethyl 4-chloroacetoacetate and isobutyramidine. m.p. 123°-125°. The intermediate chloromethyl compound (25 g) was stirred with 50 ml methanol at room temperature. To this mixture was added, dropwise, a solution of 25 g ammonium dimethyl phosphorodithioate dissolved in 500 ml methanol. The mixture was then heated to reflux for 6 hours, then the solvent was evaporated under reduced pressure yielding a solid. The solid was dissolved in dichloromethane and washed with water, separated, dried, and the solvent was evaporated. The remaining solid was recrystallized from toluene; yield: 15.9 g, m.p. 89°-93°.

Workup

  1. additionTo this mixture was added
  2. temperatureThe mixture was then heated
  3. temperatureto reflux for 6 hours
  4. customthe solvent was evaporated under reduced pressure
  5. customyielding a solid
  6. washwashed with water
  7. customseparated
  8. customdried
  9. customthe solvent was evaporated
  10. customThe remaining solid was recrystallized from toluene

Sources & evidence

ORD record
ord-921e6e77ba944dc38469bfcabd59faa0
Source dataset
uspto-grants-1983_07
Patent number
US04395551

Reaction notes

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