4-(2,5-Difluoro-4-nitrophenoxy)-3-iodo-2-[bis[(1,1-dimethylethoxy)-carbonyl]amino]pyridine → 4-(2,5-Difluoro-4-aminophenoxy)-3-iodo-2-[bis[(1,1-dimethylethoxy)carbonyl]amino]pyridine

HRID 1046013Notes

Reaction equation

HRID 1046013 reaction equation
[F:1][C:2]1[CH:30]=[C:29]([N+:31]([O-])=O)[C:28]([F:34])=[CH:27][C:3]=1[O:4][C:5]1[CH:10]=[CH:9][N:8]=[C:7]([N:11]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:6]=1[I:26]>CCOC(C)=O.[OH-].[OH-].[Pd+2]>[F:1][C:2]1[CH:30]=[C:29]([NH2:31])[C:28]([F:34])=[CH:27][C:3]=1[O:4][C:5]1[CH:10]=[CH:9][N:8]=[C:7]([N:11]([C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])[C:19]([O:21][C:22]([CH3:23])([CH3:24])[CH3:25])=[O:20])[C:6]=1[I:26]

Participants

4

Reactant 1

HCID 680094134-(2,5-Difluoro-4-nitrophenoxy)-3-iodo-2-[bis[(1,1-dimethylethoxy)-carbonyl]amino]pyridine

Product 1

HCID 680094164-(2,5-Difluoro-4-aminophenoxy)-3-iodo-2-[bis[(1,1-dimethylethoxy)carbonyl]amino]pyridineYield 97%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Palladium hydroxide on carbon (0.193 g, 0.275 mmol) (contains 60% water) was added to a solution of 4-(2,5-difluoro-4-nitrophenoxy)-3-iodo-2-[bis[(1,1-dimethylethoxy)-carbonyl]amino]pyridine (1.63 g, 2.75 mmol) in EtOAc (20 mL) and the mixture was hydrogenated (50) psi for 16 h. The completed reaction mixture was filtered through Celite® rinsing forward with EtOAc (2×10 mL). The combined filtrate was concentrated to afford 4-(2,5-difluoro-4-aminophenoxy)-3-iodo-2-[bis[(1,1-dimethylethoxy)carbonyl]amino]pyridine as colorless foam (1.5 g, 97% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.21 (dd, J=7.6 Hz, 5.6 Hz, 1H), 7.24 (dd, J=11.0 Hz, 7.4 Hz, 1H), 6.71 (m, 1H), 6.57 (d, J=5.6 Hz, 1H), 5.55 (s, 2H), 1.35 (s, 18H); MS (ESI) m/z: 564.1 (M+H+).

Workup

  1. customfor 16 h
  2. customThe completed reaction mixture
  3. filtrationwas filtered through Celite®
  4. washrinsing forward with EtOAc (2×10 mL)
  5. concentrationThe combined filtrate was concentrated

Sources & evidence

ORD record
ord-b7c533ee4c244cac854005d9fd6d209a
Source dataset
uspto-grants-2013_10
Patent number
US08569319B2

Reaction notes

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