Toluene → 3-Fluoro-4-phenylmethoxyaniline

HRID 562994Notes

Reaction equation

HRID 562994 reaction equation
C([O-])=O.[NH4+].[CH2:5]([O:12][C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[CH:15][C:14]=1[F:22])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C1(C)C=CC=CC=1>[Fe].O>[CH2:5]([O:12][C:13]1[CH:18]=[CH:17][C:16]([NH2:19])=[CH:15][C:14]=1[F:22])[C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 3

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

Product 1

HCID 219518923-Fluoro-4-phenylmethoxyanilineYield 101.3%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 962WaterSolvent

Procedure

A mixture of iron powder (45.2 g, 0.809 g atoms), ammonium formate (53.6 g, 0.850 mol), 1-benzyloxy-2-fluoro-4-nitrobenzene (50.0 g, 0.200 mol), toluene (400 mL) and water (400 mL) was heated to reflux overnight. The mixture was filtered through Celite and washed with hot ethyl acetate. The combined organic layers were washed with water and brine, then dried over sodium sulfate and concentrated to afford 4-benzyloxy-3-fluoroaniline (44 g, 100%). 1H NMR (400 MHz, d6-DMSO): δ 7.43-7.26 (m, 5H), 6.90 (dd, 1H), 6.49 (dd, 1H), 6.34 (m, 1H), 4.99 (br s, 2H), 4.98 (s, 2H); 13C NMR (100 MHz, d6-DMSO): δ 171.1, 155.1, 152.7, 144.9, 138.0, 137.2, 129.6, 129.0, 128.5, 118.9, 110.0, 102.9, 72.5; IR (cm−1): 1510, 1454, 1277, 1215, 1126, 1007, 957, 843, 800, 789, 739, 694, 604; LC/MS (M+H=218).

Workup

  1. temperaturewas heated
  2. temperatureto reflux overnight
  3. filtrationThe mixture was filtered through Celite
  4. washwashed with hot ethyl acetate
  5. washThe combined organic layers were washed with water and brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-621de597d0004470b7118a0e7357568b
Source dataset
uspto-grants-2011_11
Patent number
US08067436B2

Reaction notes

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