Ethanol → 5-Bromo-2,4-bis(2,4-difluorophenoxy)aniline

HRID 633526Notes

Reaction equation

HRID 633526 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[C:5]([O:11][C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][C:13]=2[F:19])=[CH:4][C:3]=1[O:20][C:21]1[CH:26]=[CH:25][C:24]([F:27])=[CH:23][C:22]=1[F:28].[Cl-].[NH4+].C(O)C.O>O1CCCC1.[Fe]>[Br:1][C:2]1[C:3]([O:20][C:21]2[CH:26]=[CH:25][C:24]([F:27])=[CH:23][C:22]=2[F:28])=[CH:4][C:5]([O:11][C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][C:13]=2[F:19])=[C:6]([CH:7]=1)[NH2:8]

Participants

7

Reactant 4

HCID 702EthanolHCID 962WaterHCID 25517Ammonium ChlorideHCID 904167304,4'-(4-Bromo-6-nitro-1,3-phenylene)bis(oxy)bis(1,3-difluorobenzene)

Product 1

HCID 904177805-Bromo-2,4-bis(2,4-difluorophenoxy)anilineYield 96.4%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
90 °C

Procedure

The product from Example 13A (0.578 g, 1.26 mmol), iron (0.352 g, 6.31 mmol), and ammonium chloride (0.101 g, 1.89 mmol) were combined in a mixture of tetrahydrofuran (9 mL), ethanol (9 mL), water (3 mL) and heated at 90° C. for 2 hours. The mixture was cooled, filtered through Celite and the Celite pad was washed repeatedly with methanol. The filtrate was concentrated and the residue was partitioned between ethyl acetate and water. The organic layer was washed with saturated aqueous sodium chloride, dried (anhydrous Na2SO4), filtered, and concentrated to afford the title compound (0.52 g, 96%).

Workup

  1. temperatureThe mixture was cooled
  2. filtrationfiltered through Celite
  3. washthe Celite pad was washed repeatedly with methanol
  4. concentrationThe filtrate was concentrated
  5. customthe residue was partitioned between ethyl acetate and water
  6. washThe organic layer was washed with saturated aqueous sodium chloride
  7. dry with materialdried (anhydrous Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-c71d956e61b649e890567f96dac1b692
Source dataset
uspto-grants-2016_04
Patent number
US09321764B2

Reaction notes

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