3-Nitroaniline → 4-iodo-N-(3-nitrophenyl)pyridine-2-amine

HRID 593281Notes

Reaction equation

HRID 593281 reaction equation
F[C:2]1[CH:7]=[C:6]([I:8])[CH:5]=[CH:4][N:3]=1.[N+:9]([C:12]1[CH:13]=[C:14]([CH:16]=[CH:17][CH:18]=1)[NH2:15])([O-:11])=[O:10].C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C.CCOC(C)=O>[I:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([NH:15][C:14]2[CH:16]=[CH:17][CH:18]=[C:12]([N+:9]([O-:11])=[O:10])[CH:13]=2)[CH:7]=1

Participants

6

Reactant 3

HCID 74233-NitroanilineHCID 10796Cesium carbonateHCID 70235702-Fluoro-4-iodopyridine

Product 1

HCID 682872994-iodo-N-(3-nitrophenyl)pyridine-2-amineYield 16%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
130 °C

Procedure

A mixture of 2-fluoro-4-iodopyridine (500 mg, 2.24 mmol), 3-nitroaniline (620 mg, 4.49 mmol), and Cs2CO3 (1460 mg, 4.48 mmol) in dry DMF (12.5 mL) was heated for 1 h at 130° C. in a microwave oven. The mixture was diluted with EtOAc and washed twice with brine. The organic layer was dried over MgSO4 and concentrated under reduced pressure, and the residue was purified by flash chromatography on silica gel (DCM/MeOH 100:0 to 95:5) to yield the desired product A5 as a white solid (122 mg, 16%). 1H NMR (400 MHz, d6-DMSO, 300K) δ 7.21 (d, J=5.4 Hz, 1H), 7.29 (s, 1H), 7.52 (t, J=8.1 Hz, 1H), 7.71 (d, J=8.1 Hz, 1H), 7.93 (m, 2H), 8.74 (t, J=2.1 Hz, 1H), 9.62 (s, 1H). MS (ES) C11H8IN3O2 requires: 341. found: 342 (M+H)+.

Workup

  1. washwashed twice with brine
  2. dry with materialThe organic layer was dried over MgSO4
  3. concentrationconcentrated under reduced pressure
  4. customthe residue was purified by flash chromatography on silica gel (DCM/MeOH 100:0 to 95:5)

Sources & evidence

ORD record
ord-3da0d17d63744d6cbf13d76bd131d5ec
Source dataset
uspto-grants-2016_01
Patent number
US09242937B2

Reaction notes

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