1-Bromo-4-nitrobenzene → 1-Ethyl-4-(4-nitrophenyl)piperazine

HRID 2176866Notes

Reaction equation

HRID 2176866 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[CH2:11]([N:13]1[CH2:18][CH2:17][NH:16][CH2:15][CH2:14]1)[CH3:12]>O.C(Cl)Cl.CO>[CH2:11]([N:13]1[CH2:18][CH2:17][N:16]([C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=2)[CH2:15][CH2:14]1)[CH3:12]

Participants

5

Reactant 2

HCID 114661-Bromo-4-nitrobenzeneHCID 791961-Ethylpiperazine

Product 1

HCID 28575491-Ethyl-4-(4-nitrophenyl)piperazineYield 88.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 21226129Dichloromethane methanolSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1-bromo-4-nitrobenzene (6 g, 29.7 mmol) and 1-ethylpiperazine (7.6 ml, 59.4 mmol, 2 eq.) is heated to 80° C. for 15 h. After cooling to RT, the reaction mixture is diluted with water and DCM/MeOH, 9:1. The aqueous layer is separated and extracted with DCM/MeOH, 9:1. The organic phase is washed with brine, dried (sodium sulfate), filtered and concentrated. Purification of the residue by silica gel column chromatography (DCM/MeOH+1% NH3aq, 9:1) affords 6.2 g of the title compound as a yellow solid: ESI-MS: 236.0 [MH]+; tR=2.35 min (purity: 100%, gradient J); TLC: Rf=0.50 (DCM/MeOH+1% NH3aq, 9:1).

Workup

  1. temperatureAfter cooling to RT
  2. customThe aqueous layer is separated
  3. extractionextracted with DCM/MeOH, 9:1
  4. washThe organic phase is washed with brine
  5. dry with materialdried (sodium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification of the residue by silica gel column chromatography (DCM/MeOH+1% NH3aq, 9:1)

Sources & evidence

ORD record
ord-a788ed81e8804b7eaa758a8050919dcd
Source dataset
uspto-grants-2015_06
Patent number
US09067896B2

Reaction notes

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