p-Toluenesulfonic acid → 2,6-Difluoro-4-iodoaniline

HRID 2266030Notes

Reaction equation

HRID 2266030 reaction equation
[F:1][C:2]1[CH:8]=[CH:7][CH:6]=[C:5]([F:9])[C:3]=1[NH2:4].C1(C)C=CC(S(O)(=O)=O)=CC=1.[I:21]N1C(=O)CCC1=O>CN(C=O)C>[F:1][C:2]1[CH:8]=[C:7]([I:21])[CH:6]=[C:5]([F:9])[C:3]=1[NH2:4]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 796472,6-DifluoroanilineHCID 120273N-Iodosuccinimide

Product 1

HCID 2789432,6-Difluoro-4-iodoanilineYield 92.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a solution of 2,6-difluoroaniline (5.0 g, 38.7 mmol) and p-toluenesulfonic acid (1.45 g, 7.62 mmol) in DMF (70 mL) was added dropwise N-iodosuccinimide (9.6 g, 42.7 mmol) dissolved in DMF (50 mL) at 5° C. The mixture was stirred for 2.5 hours at room temperature. The mixture was concentrated under reduced pressure, and then diluted with EtOAc and water. The organic layer was washed with saturated aqueous sodium thiosulfate and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by crystallization from EtOAc and hexane to give 2,6-difluoro-4-iodoaniline (9.12 g, 92.4%).

Workup

  1. concentrationThe mixture was concentrated under reduced pressure
  2. additiondiluted with EtOAc and water
  3. washThe organic layer was washed with saturated aqueous sodium thiosulfate and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude residue was purified by crystallization from EtOAc and hexane

Sources & evidence

ORD record
ord-043c9a3135624896bd504189a1daf0c0
Source dataset
uspto-grants-2010_12
Patent number
US07858621B2

Reaction notes

Loading…