N-benzyl-2-nitroaniline → N1-Benzylbenzene-1,2-diamine

HRID 1993399Notes

Reaction equation

HRID 1993399 reaction equation
[CH2:1]([NH:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[N+:15]([O-])=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>C(O)C.O.Cl.[Fe]>[CH2:1]([NH:8][C:9]1[C:10]([NH2:15])=[CH:11][CH:12]=[CH:13][CH:14]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 1

HCID 521800N-benzyl-2-nitroaniline

Product 1

HCID 2735482N1-Benzylbenzene-1,2-diamineYield 57.1%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidCatalystHCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a solution of benzyl-(2-nitro-phenyl)-amine (1068) (2.5 g, 10.43 mmol) in ethanol (150 mL) and water (10 mL) was added iron (8.7 g, 155.7 mmol) followed by 30 drops of concentrated HCl, and the resulting mixture was heated overnight at reflux. The reaction mixture was quenched with water, diluted with DCM and the layers were separated. The organic layer was washed with saturated sodium bicarbonate solution, brine, dried over sodium sulfate and concentrated to give a brown oily residue. Further purification by column chromatography (SiO2, 20% ethyl acetate/hexanes) afforded N-benzyl-benzene-1,2-diamine (1069) as a dark yellow oil (1.18 g, 57%). 1H NMR (400 MHz, CDCl3)  7.41-7.24 (m, 5H), 6.82-6.67 (m, 4H), 4.32 (s, 2H), 3.56 (b, 3H, NH).

Workup

  1. temperaturethe resulting mixture was heated overnight
  2. temperatureat reflux
  3. customThe reaction mixture was quenched with water
  4. additiondiluted with DCM
  5. customthe layers were separated
  6. washThe organic layer was washed with saturated sodium bicarbonate solution, brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated
  9. customto give a brown oily residue
  10. customFurther purification by column chromatography (SiO2, 20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-5d3527c8e8514ba38a595c771e843ddb
Source dataset
uspto-grants-2010_01
Patent number
US07652020B2

Reaction notes

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