Sodium hydride → HCID 19896206, compound

HRID 1196774Notes

Reaction equation

HRID 1196774 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]([C:22]([F:25])([F:24])[F:23])[CH:19]=[C:18]([Cl:26])[C:17]=1[N:27]=[C:28]=[O:29]>CN(C)C=O>[Cl:15][C:16]1[CH:21]=[C:20]([C:22]([F:24])([F:23])[F:25])[CH:19]=[C:18]([Cl:26])[C:17]=1[N:27]1[C:4](=[O:6])[CH:3]=[C:2]([C:9]([F:10])([F:11])[F:12])[NH:1][C:28]1=[O:29]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 5702529Ethyl 3-amino-4,4,4-trifluorocrotonateHCID 19896197HCID 19896197, compound

Product 1

HCID 19896206HCID 19896206, compoundYield 28.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
0 °C

Procedure

A 20 ml dimethylformamide solution of 2.7 g of ethyl 3-amino-4,4,4-trifluorocrotonate was added dropwise to a 20 ml dimethylformamide solution of 0.78 g of sodium hydride (purity: 55%) with stirring at 0° C. After heated to room temperature under stirring for 15 minutes, the mixed solution was cooled to -30° C. and then added dropwise with 20 ml of a dimethylformamide solution of 3.8 g of 2,6-dichloro-4-trifluoromethylphenyl isocyanate. The resulting solution was again heated to room temperature and stirred at 80° C. for 30 minutes. Then the solvent was distilled away under reduced pressure and the residue was dissolved by adding 100 ml of water. This aqueous solution was washed twice with diethyl ether, then added to a mixed solution of 50 g of ice and 20 ml of concentrated hydrochloric acid, and extracted with ethyl acetate. The obtained organic layer was washed with water and dried, and the solvent was distilled away under reduced pressure to obtain 3.75 g of a crude product. This crude product was recrystallized from a mixed solvent of diisopropyl ether and isopropyl alcohol to obtain 1.65 g of the objective compound.

Workup

  1. temperatureAfter heated to room temperature
  2. stirringunder stirring for 15 minutes
  3. temperaturethe mixed solution was cooled to -30° C.
  4. temperatureThe resulting solution was again heated to room temperature
  5. stirringstirred at 80° C. for 30 minutes
  6. distillationThen the solvent was distilled away under reduced pressure
  7. dissolutionthe residue was dissolved
  8. additionby adding 100 ml of water
  9. washThis aqueous solution was washed twice with diethyl ether
  10. additionadded to a mixed solution of 50 g of ice and 20 ml of concentrated hydrochloric acid
  11. extractionextracted with ethyl acetate
  12. washThe obtained organic layer was washed with water
  13. customdried
  14. distillationthe solvent was distilled away under reduced pressure
  15. customto obtain 3.75 g of a crude product
  16. customThis crude product was recrystallized from a mixed solvent of diisopropyl ether and isopropyl alcohol

Sources & evidence

ORD record
ord-2d2aadd70ea444bfbf7503ae6f41b466
Source dataset
uspto-grants-1992_05
Patent number
US05116404

Reaction notes

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