3-Bromo-4-nitropyridine N-oxide → 1-(4-Nitro-1-oxido-pyridin-1-ium-3-yl)-4-(oxetan-3-yl)piperazine

HRID 1850683Notes

Reaction equation

HRID 1850683 reaction equation
Br[C:2]1[CH:3]=[N+:4]([O-:11])[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].[O:12]1[CH2:15][CH:14]([N:16]2[CH2:21][CH2:20][NH:19][CH2:18][CH2:17]2)[CH2:13]1>CCO>[N+:8]([C:7]1[CH:6]=[CH:5][N+:4]([O-:11])=[CH:3][C:2]=1[N:19]1[CH2:20][CH2:21][N:16]([CH:14]2[CH2:15][O:12][CH2:13]2)[CH2:17][CH2:18]1)([O-:10])=[O:9]

Participants

4

Reactant 2

HCID 5485213-Bromo-4-nitropyridine N-oxideHCID 574162871-(Oxetan-3-yl)piperazine

Product 1

HCID 904113171-(4-Nitro-1-oxido-pyridin-1-ium-3-yl)-4-(oxetan-3-yl)piperazineYield 86.4%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 3-bromo-4-nitro-1-oxido-pyridin-1-ium (500 mg, 2.283 mmol) and 1-(oxetan-3-yl)piperazine (649.3 mg, 4.566 mmol) in EtOH (10 mL) were heated at reflux for 17 hours. The reaction was cooled to ambient temperature and the solvent removed in vacuo. The residue was passed through a 25 g SCX-2 cartridge (pre-wetted with MeOH), eluting with 2M NH3 in MeOH/DCM. The solvents were removed in vacuo and the residue purified by column chromatography (ISCO Companion, 40 g column, eluting with 0 to 10% MeOH/DCM, loaded in DCM) to give 1-(4-nitro-1-oxido-pyridin-1-ium-3-yl)-4-(oxetan-3-yl)piperazine as an orange solid (553 mg, 86% Yield).

Workup

  1. temperaturewere heated
  2. temperatureat reflux for 17 hours
  3. customthe solvent removed in vacuo
  4. washeluting with 2M NH3 in MeOH/DCM
  5. customThe solvents were removed in vacuo
  6. customthe residue purified by column chromatography (ISCO Companion, 40 g column, eluting with 0 to 10% MeOH/DCM, loaded in DCM)

Sources & evidence

ORD record
ord-2b593e8115fd41b28ce11a2f4792a387
Source dataset
uspto-grants-2015_02
Patent number
US08957078B2

Reaction notes

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