Toluene → 3-Fluoro-4-phenylmethoxyaniline

HRID 705635Notes

Reaction equation

HRID 705635 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-])=O)=[CH:11][C:10]=1[F:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C)C=CC=CC=1.C([O-])=O.[NH4+]>[Fe].O>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([NH2:15])=[CH:11][C:10]=1[F:18])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 1140TolueneHCID 2723923Ammonium formateHCID 220309121-(Benzyloxy)-2-fluoro-4-nitrobenzene

Product 1

HCID 219518923-Fluoro-4-phenylmethoxyanilineYield 87.2%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Procedure

A mixture of 1-benzyloxy-2-fluoro-4-nitro-benzene (44 g, 178 mmol), toluene (400 ml), ammonium formate (35 g), iron (30 g), and water (400 ml) was heated to reflux with stirring overnight. The reaction mixture was filtered through celite and washed with ethyl acetate (400 ml). The organic layer was separated and washed with brine (300 ml), dried over sodium sulfate and concentrated to give 4-benzyloxy-3-fluoro-phenylamine as an oil (33.7 g, 87%). 1H NMR (400 MHz, CDCl3): δ 7.41-7.29 (m, 5H), 6.79 (t, 1H), 6.45 (dd, 1H), 6.14 (dd, 1H), 5.02 (s, 2H), 3.50 (s, 2H). LC/MS: (M+1) 218.

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. filtrationThe reaction mixture was filtered through celite
  4. washwashed with ethyl acetate (400 ml)
  5. customThe organic layer was separated
  6. washwashed with brine (300 ml)
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-a58a08598c6845e3b9dbc7358a47d98a
Source dataset
uspto-grants-2015_11
Patent number
US09174947B2

Reaction notes

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