Acetic Acid → 4-(Difluoromethoxy)-3-methylaniline

HRID 2110137Notes

Reaction equation

HRID 2110137 reaction equation
[F:1][CH:2]([F:14])[O:3][C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-])=O)=[CH:6][C:5]=1[CH3:13].C(O)(=O)C>C(O)C.O.[Fe]>[NH2:10][C:7]1[CH:8]=[CH:9][C:4]([O:3][CH:2]([F:1])[F:14])=[C:5]([CH3:13])[CH:6]=1

Participants

6

Reactant 2

HCID 176Acetic AcidHCID 133147061-(Difluoromethoxy)-2-methyl-4-nitrobenzene

Product 1

HCID 132950334-(Difluoromethoxy)-3-methylanilineYield 95.7%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a solution of 1-(difluoromethoxy)-2-methyl-4-nitrobenzene (10 g, 48.28 mmol) in ethanol (150 mL) and water (150 mL) was added iron powder (12 g, 214.29 mmol). Acetic acid (cat. amount) was added dropwise with stirring and the reaction mixture was heated at reflux for 20 minutes. The mixture was cooled to room temperature and solids were removed by filtration. Volatiles were removed in vacuo and the aqueous solution was extracted with EtOAc (3×150 mL). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to provide 8 g (95%) of 4-amino-1-difluoromethoxy-2-methyl-benzene.

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureat reflux for 20 minutes
  3. customsolids were removed by filtration
  4. customVolatiles were removed in vacuo
  5. extractionthe aqueous solution was extracted with EtOAc (3×150 mL)
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-404ac5aaa61e42d2aa3d39d5e86fc0b9
Source dataset
uspto-grants-2009_04
Patent number
US07517884B2

Reaction notes

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