2-Chloro-4-(2,5-difluoro-4-nitrophenoxy)pyridine → Benzenamine, 4-[(2-chloro-4-pyridinyl)oxy]-2,5-difluoro-

HRID 2060689Notes

Reaction equation

HRID 2060689 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([O:8][C:9]2[CH:14]=[C:13]([F:15])[C:12]([N+:16]([O-])=O)=[CH:11][C:10]=2[F:19])[CH:5]=[CH:4][N:3]=1>[Ni].CO>[Cl:1][C:2]1[CH:7]=[C:6]([O:8][C:9]2[C:10]([F:19])=[CH:11][C:12]([NH2:16])=[C:13]([F:15])[CH:14]=2)[CH:5]=[CH:4][N:3]=1

Participants

4

Reactant 1

HCID 552369312-Chloro-4-(2,5-difluoro-4-nitrophenoxy)pyridine

Product 1

HCID 78358387Benzenamine, 4-[(2-chloro-4-pyridinyl)oxy]-2,5-difluoro-Yield 78.3%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

In a Parr Shaker flask was combined 2-chloro-4-(2,5-difluoro-4-nitrophenoxy)pyridine (11.68 g, 40.8 mmol) and MeOH (200 ml) under argon. Raney Ni (50% wet, 0.955 g, 8.15 mmol) was added. The argon atmosphere was removed and replaced with hydrogen (10-20 psi) and the reaction mixture shaken under hydrogen for 4 hours. The completed reaction mixture was filtered through a pad of Celite® and the filtrate was concentrated to dryness to provide 4-(2-chloropyridin-4-yloxy)-2,5-difluoroaniline (8.2 g, 72% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.28 (d, J=5.9 Hz, 1H), 7.25 (dd, J=11.2, 7.5 Hz, 1H), 7.02 (dd, J=2.2 Hz, 1H), 6.95 (dd, J=5.8, 2.0 Hz, 1H), 6.74 (dd, J=12.3, 8.3 Hz, 1H), 5.57 (s, 2H); MS (ESI): m/z 257.0 [M+H]+

Workup

  1. customThe argon atmosphere was removed
  2. customThe completed reaction mixture
  3. filtrationwas filtered through a pad of Celite®
  4. concentrationthe filtrate was concentrated to dryness

Sources & evidence

ORD record
ord-9c5c978b0d5e491099a931017e76b4cf
Source dataset
uspto-grants-2012_10
Patent number
US08278331B2

Reaction notes

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