Perfluorobutyl iodide → 2-Fluoro-4-(nonafluorobutyl)aniline

HRID 917755Notes

Reaction equation

HRID 917755 reaction equation
[F:1][C:2]([F:14])([F:13])[C:3]([F:12])([F:11])[C:4]([F:10])([F:9])[C:5]([F:8])([F:7])I.[F:15][C:16]1[CH:22]=[C:21](I)[CH:20]=[CH:19][C:17]=1[NH2:18]>CS(C)=O.[Cu]>[F:15][C:16]1[CH:22]=[C:21]([C:5]([F:8])([F:7])[C:4]([F:10])([F:9])[C:3]([F:12])([F:11])[C:2]([F:14])([F:13])[F:1])[CH:20]=[CH:19][C:17]=1[NH2:18]

Participants

5

Reactant 2

HCID 67917Perfluorobutyl iodideHCID 1856942-Fluoro-4-iodoaniline

Product 1

HCID 236309102-Fluoro-4-(nonafluorobutyl)anilineYield 61.1%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

A dispersion of 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane (3.50 9, 10.1 mmol), 2-fluoro-4-iodoaniline (2.00 g, 8.4 mmol) and copper bronze (1.93 g, 30.4 mmol) in DMSO (10 ml) was stirred at 120° C. for 15 h. Copper(I) iodide was removed by filtration through Celite®. Et2O (100 ml) was used to wash the Celite® plug. Water (100 ml) was then added to the filtrate and the mixture stirred at RT for 5 min. The organic layer was separated and washed 5× with water to remove DMSO, dried (Na2SO4) and concentrated. Flash chromatography on silica gel (10% EtOAc/Hexane) afforded 2-fluoro-4-(1,1,2,2,3,3,4,4,4-nonafluorobutyl) aniline (1.69 g, 61%). 1H NMR [300 MHz, CDCl3] δ 7.25-7.14 (m, 2H), 6.86-6.74 (m, 1H), 4.07 (br s, 1H). LCMS (ACPI−) 328 (100%).

Workup

  1. customCopper(I) iodide was removed by filtration through Celite®
  2. washto wash the Celite® plug
  3. additionWater (100 ml) was then added to the filtrate
  4. customThe organic layer was separated
  5. washwashed 5× with water
  6. customto remove DMSO
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-6a7e6e87ab014dbf9b81fdd48cdef75e
Source dataset
uspto-grants-2007_09
Patent number
US07273877B2

Reaction notes

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