Aniline → 3,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)aniline

HRID 2394491Notes

Reaction equation

HRID 2394491 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([NH2:8])[CH:5]=[C:4]([Cl:9])[C:3]=1[OH:10].[OH-].[K+].[F:13][C:14]([F:21])([F:20])[C:15]([F:19])=[C:16]([F:18])[F:17].NC1C=CC=CC=1>O1CCCC1>[Cl:1][C:2]1[CH:7]=[C:6]([CH:5]=[C:4]([Cl:9])[C:3]=1[O:10][C:16]([F:18])([F:17])[CH:15]([F:19])[C:14]([F:21])([F:20])[F:13])[NH2:8].[Cl:1][C:2]1[CH:7]=[C:6]([CH:5]=[C:4]([Cl:9])[C:3]=1[O:10][C:16]([F:17])=[C:15]([F:19])[C:14]([F:21])([F:20])[F:13])[NH2:8]

Participants

7

Reactant 4

HCID 6115AnilineHCID 8302HexafluoropropyleneHCID 14797Potassium HydroxideHCID 800374-Amino-2,6-dichlorophenol

Product 2

HCID 98838783,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)anilineHCID 544918163,5-Dichloro-4-[(1,2,3,3,3-pentafluoro-1-propen-1-yl)oxy]benzenamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 1.1 liters of tetrahydrofuran containing 44.5 g of 2,6-dichloro-4-aminophenol and 3.2 g potassium hydroxide, was added subsurface 38.7 g of hexafluoropropene. The addition was complete in 25 minutes at a temperature of 8°-11° C. Analysis by liquid chromatography indicates no starting aniline present. Most of the THF was removed under vacuum, 500 mL water was added and the resulting mixture was extracted 3×500 mL ethyl ether. The combined extracts were washed with 2×100 mL 1N NaOH, 2×200 mL brine, dried over anhydrous sodium sulfate, filtered and the solvent removed under vacuum to give a mixture. This mixture was separated by prep LC to give 46.8 g of 3,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)aniline and ~4 g of 3,5-dichloro-4-(1 ,2,3,3,3-pentafluoropropenoxy) aniline . Proton and 19F nmr and mass spectra were consistent with the proposed structures.

Workup

  1. additionThe addition
  2. customMost of the THF was removed under vacuum, 500 mL water
  3. additionwas added
  4. extractionthe resulting mixture was extracted 3×500 mL ethyl ether
  5. washThe combined extracts were washed with 2×100 mL 1N NaOH, 2×200 mL brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customthe solvent removed under vacuum
  9. customto give a mixture
  10. customThis mixture was separated by prep LC

Sources & evidence

ORD record
ord-c75ea8e381164e50b68d49dfa1d420fa
Source dataset
uspto-grants-1998_09
Patent number
US05811461

Reaction notes

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