1-Iodo-3-nitrobenzene → Tert-butyl 4-(3-nitrophenyl)piperazine-1-carboxylate

HRID 1267113Notes

Reaction equation

HRID 1267113 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.[C:11]([O:15][C:16]([N:18]1[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].CC(C)([O-])C.[Na+].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>O1CCOCC1.CCOCC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:11]([O:15][C:16]([N:18]1[CH2:23][CH2:22][N:21]([C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=2)[CH2:20][CH2:19]1)=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

8

Reactant 4

HCID 125741-Iodo-3-nitrobenzeneHCID 80271Tri-o-tolylphosphineHCID 143452tert-Butyl piperazine-1-carboxylateHCID 23676156Sodium t-butoxide

Product 1

HCID 22330126Tert-butyl 4-(3-nitrophenyl)piperazine-1-carboxylateYield 54%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 1-iodo-3-nitro-benzene (9 g), piperazine-1-carboxylic acid tert-butyl ester (13.5 g) and sodium tert-butoxide (9.7 g) in dioxane (150 mL) was added tris(dibenzylideneacetone)dipalladium (2 g) and tri-o-tolylphosphine (2.2 g) and the mixture was heated at reflux for 24 hours. The solution was then cooled to room temperature, taken in Et2O and washed with brine. The organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure. The crude residue was recrystallized from diisopropyl ether to give the title compound (6 g) as a yellow solid.

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 24 hours
  3. washwashed with brine
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude residue was recrystallized from diisopropyl ether

Sources & evidence

ORD record
ord-3e6f4f4adc4544aa9e6884a8a24e610d
Source dataset
uspto-grants-2003_04
Patent number
US06552022B1

Reaction notes

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