Hexafluoropropylene → N-(2-Bromo-4-nitrophenyl)-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanamide

HRID 1761394Notes

Reaction equation

HRID 1761394 reaction equation
[F-:1].[K+].[Br:3][C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[N:13]=[C:14]=[O:15].[F:16][C:17]([F:24])([F:23])[C:18]([F:22])=[C:19]([F:21])[F:20]>CN(C=O)C>[Br:3][C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[NH:13][C:14](=[O:15])[C:18]([F:22])([C:19]([F:1])([F:21])[F:20])[C:17]([F:24])([F:23])[F:16]

Participants

5

Reactant 3

HCID 8302HexafluoropropyleneHCID 522689Potassium FluorideHCID 145774932-Bromo-1-isocyanato-4-nitrobenzene

Product 1

HCID 163755N-(2-Bromo-4-nitrophenyl)-2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanamide

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

Potassium fluoride (23 grams; 0.4 mole) which was dried by heating strongly with a bunsen burner in a porcelain crucible and subsequently powdered, was added to 200 ml of a DMF solution of 2-bromo-4-nitrophenyl isocyanate (6 grams; 0.025 mole). The mixture was placed in a pressure vessel, purged with a small stream of hexafluoropropene, and heated to 70° C. while adding hexafluoropropene from a pre-weighed supply cylinder at 10-20 psig. A pressure drop occurred as the gas reacted, and the remaining hexafluoropropene was added intermittently until the supply cylinder was empty; heating was continued at 65°-70° C. for 21/2 hours with pressure stabilized at 5 psig. The reaction vessel was then cooled and the solution poured off and extracted with hexane. The DMF solution was poured into water and filtered. The solid products were taken up in chloroform, dried over sodium sulfate, filtered, evaporated, and chromatographed on silica gel with ethyl acetate/hexane (1:5). The front-running product was collected; H-NMR of this product indicated the desired product. The material was then chromatographed on silica gel with gradient elution from 100% hexane to 100% ethyl acetate.

Workup

  1. temperatureby heating strongly with a bunsen burner in a porcelain crucible
  2. customThe mixture was placed in a pressure vessel
  3. custompurged with a small stream of hexafluoropropene
  4. additionwhile adding hexafluoropropene from a pre-weighed supply cylinder at 10-20 psig
  5. customreacted
  6. temperatureheating
  7. customwas continued at 65°-70° C. for 21
  8. custom2 hours
  9. temperatureThe reaction vessel was then cooled
  10. additionthe solution poured off
  11. extractionextracted with hexane
  12. additionThe DMF solution was poured into water
  13. filtrationfiltered
  14. dry with materialdried over sodium sulfate
  15. filtrationfiltered
  16. customevaporated
  17. customchromatographed on silica gel with ethyl acetate/hexane (1:5)
  18. customThe front-running product was collected
  19. customThe material was then chromatographed on silica gel with gradient elution from 100% hexane to 100% ethyl acetate

Sources & evidence

ORD record
ord-2696f06d690c4b729c71e0762fded551
Source dataset
uspto-grants-1989_05
Patent number
US04826841

Reaction notes

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