Benzyl 2-nitrophenyl ether → 2-Benzyloxyaniline

HRID 354337

Reaction equation

HRID 354337 reaction equation
[CH2:1]([O: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.[BH4-].[Na+]>CO.Cl[Ni]Cl>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[NH2:15])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 736266Benzyl 2-nitrophenyl etherHCID 4311764Sodium borohydride

Product 1

HCID 2405482-BenzyloxyanilineYield 100%

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 887MethanolSolvent

Procedure

To a stirred solution of 2-benzyloxynitrobenzene (9.92 g, 43.3 mmol) and NiCl2 (20.3 g, 157 mmol) in MeOH (350 mL) was added portionwise NaBH4 (8.09 g, 214 mmol) at 0° C. After disappearing of the starting material (monitored by TLC), the mixture was evaporated off. The black precipitate was dissolved in 1N HCl, then acidic solution was alkalified by the addition of 1N NaOH and extracted with EtOAc. The extracts were washed brine, dried over Na2SO4, and concentrated to dryness. Chromatography of the residue with CHCl3 as eluent gave 2-benzyloxy aniline (8.60 g, 100%) as a reddish oil. 1H-NMR (CDCl3) δ3.71 (broad s, 2H), 5.06 (s, 2H), 6.68-6.86 (m, 4H), 7.32-7.44 (m, 5H); FAB-MS m/z 200 (M++1).

Workup

  1. customthe mixture was evaporated off
  2. dissolutionThe black precipitate was dissolved in 1N HCl
  3. additionacidic solution was alkalified by the addition of 1N NaOH
  4. extractionextracted with EtOAc
  5. washThe extracts were washed brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-50a53959db354bfd9338cafbe55baa10
Source dataset
uspto-grants-2004_06
Patent number
US06756378B2

Linked notes

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