N-(1,1-Dimethylethyl)-4-nitrobenzenamine → 2-Bromo-N-tert-butyl-4-nitroaniline

HRID 1847389Notes

Reaction equation

HRID 1847389 reaction equation
[C:1]([NH:5][C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][CH:7]=1)([CH3:4])([CH3:3])[CH3:2].[Br:15]Br>CC(O)=O>[Br:15][C:11]1[CH:10]=[C:9]([N+:12]([O-:14])=[O:13])[CH:8]=[CH:7][C:6]=1[NH:5][C:1]([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 20095N-(1,1-Dimethylethyl)-4-nitrobenzenamineHCID 24408Bromine

Product 1

HCID 467394192-Bromo-N-tert-butyl-4-nitroanilineYield 43.1%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
30 °C

Procedure

To a solution of N-tert-butyl-4-nitroaniline (1 g, 5.1 mmol) in AcOH (5 mL) was added Br2 (0.86 g, 54 mmol) dropwise at 15° C. After addition, the mixture was stirred at 30° C. for 30 min and then filtered. The filter cake was basified to pH 8-9 with aqueous NaHCO3. The aqueous layer was extracted with EtOAc (10 mL×3). The combined organic layers were washed with water, brine, dried over Na2SO4 and concentrated under vacuum to give (2-bromo-4-nitro-phenyl)-tert-butyl-amine (0.6 g, 43%). 1H-NMR (CDCl3, 400 MHz) δ 8.37 (dd, J=2.4 Hz, 1H), 8.07 (dd, J=2.4, 9.2 Hz, 1H), 6.86 (d, J=9.2 Hz, 1H), 5.19 (brs, 1H), 1.48 (s, 9H).

Workup

  1. additionAfter addition
  2. filtrationfiltered
  3. extractionThe aqueous layer was extracted with EtOAc (10 mL×3)
  4. washThe combined organic layers were washed with water, brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-162fb58487f4435b9f9272774d44f726
Source dataset
uspto-grants-2015_02
Patent number
US08952050B2

Reaction notes

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