Sodium hydride → 3-(2,4,6-trichlorophenyl)-6-trifluoromethyl-(1H,3H)-pyrimidine-2-thion-4-one

HRID 1196778Notes

Reaction equation

HRID 1196778 reaction equation
[NH2:1]/[C:2](/[C:9]([F:12])([F:11])[F:10])=[CH:3]\[C:4]([O:6]CC)=O.[H-].[Na+].[Cl:15][C:16]1[CH:21]=[C:20]([Cl:22])[CH:19]=[C:18]([Cl:23])[C:17]=1[N:24]=[C:25]=[S:26]>CN(C)C=O>[Cl:15][C:16]1[CH:21]=[C:20]([Cl:22])[CH:19]=[C:18]([Cl:23])[C:17]=1[N:24]1[C:4](=[O:6])[CH:3]=[C:2]([C:9]([F:10])([F:11])[F:12])[NH:1][C:25]1=[S:26]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 1233992,4,6-Trichlorophenyl isothiocyanateHCID 5702529Ethyl 3-amino-4,4,4-trifluorocrotonate

Product 1

HCID 1317173943-(2,4,6-trichlorophenyl)-6-trifluoromethyl-(1H,3H)-pyrimidine-2-thion-4-oneYield 5.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
5 °C

Procedure

A 5 ml dimethylformamide solution of 3.7 g ethyl 3-amino-4,4,4-trifluorocrotonate was added dropwise to a 30 ml dimethylformamide solution of 1.0 g of sodium hydride (purity: 55%) with stirring at 5° C. The mixed solution was stirred at room temperature for 15 minutes, then cooled to 5° C. and added dropwise with a 10 ml dimethylformamide solution of 5.0 g of 2,4,6-trichlorophenyl isothiocyanate. The resulting solution was heated to room temperature and further stirred at 130° C. for 2 hours. Then the solvent was distilled away under reduced pressure and the residue was dissolved by adding 200 ml of water and washed with diethyl ether. The obtained aqueous layer was added into a mixed solution of 30 ml of concentrated hydrochloric acid and 100 g of ice and extracted with 200 ml of ethyl acetate. The obtained organic layer was washed with a sodium chloride aqueous solution and dried over anhydrous sodium sulfate. Then the solvent was distilled away under reduced pressure to obtain 2.8 g of a crude product. This product was purified by preparative thin-layer chromatography (developing solvent: a mixed solvent of chloroform and ethyl acetate) to obtain 0.43 g of the objective compound.

Workup

  1. stirringThe mixed solution was stirred at room temperature for 15 minutes
  2. temperaturecooled to 5° C.
  3. temperatureThe resulting solution was heated to room temperature
  4. stirringfurther stirred at 130° C. for 2 hours
  5. distillationThen the solvent was distilled away under reduced pressure
  6. dissolutionthe residue was dissolved
  7. additionby adding 200 ml of water
  8. washwashed with diethyl ether
  9. additionThe obtained aqueous layer was added into a mixed solution of 30 ml of concentrated hydrochloric acid and 100 g of ice
  10. extractionextracted with 200 ml of ethyl acetate
  11. washThe obtained organic layer was washed with a sodium chloride aqueous solution
  12. dry with materialdried over anhydrous sodium sulfate
  13. distillationThen the solvent was distilled away under reduced pressure
  14. customto obtain 2.8 g of a crude product
  15. customThis product was purified by preparative thin-layer chromatography (

Sources & evidence

ORD record
ord-9d172b6b98214e38993ef41bb396e8de
Source dataset
uspto-grants-1992_05
Patent number
US05116404

Reaction notes

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