Piperidine → 2-Nitro-5-piperidinoaniline

HRID 272699Notes

Reaction equation

HRID 272699 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7].[NH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C>[N+:9]([C:5]1[CH:4]=[CH:3][C:2]([N:12]2[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]2)=[CH:8][C:6]=1[NH2:7])([O-:11])=[O:10]

Participants

5

Reactant 3

HCID 8082PiperidineHCID 11430Potassium CarbonateHCID 742185-Chloro-2-nitroaniline

Product 1

HCID 70622462-Nitro-5-piperidinoanilineYield 60.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 5-chloro-2-nitroaniline (1.73 g, 10 mmol), piperidine (1.09 mL, 11 mmol), and K2CO3 (1.52 g, 11 mmol) in DMF was heated to 120° C. for 24 hours. Cooled to room temperature. Partitioned between ethyl acetate and water. The organic layer was washed with brine, dried (MgSO4), filtered, and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel with 4:1 hexanes/ethyl acetate to provide 1.33 g (60%) of the desired product. MS (ESI) m/e 222 (M+H)+, 1H NMR (300 MHz, DMSO-d6): □ 7.79 (d, J=9.83 Hz, 1H), 7.22 (s, 2H), 6.37 (dd, J=9.83, 2.71 Hz, 1H), 6.19 (d, J=2.71 Hz, 1H), 3.34-3.38 (m, 4H), 1.53-1.60 (m, 6H).

Workup

  1. temperatureCooled to room temperature
  2. customPartitioned between ethyl acetate and water
  3. washThe organic layer was washed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe residue was purified by flash column chromatography on silica gel with 4:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-65017cb31ba246ceaa4893c401fc9ae0
Source dataset
uspto-grants-2008_11
Patent number
US07456169B2

Reaction notes

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