Acetic Acid → 2-[(4-Nitrophenyl)methylamino]pyridine

HRID 566149Notes

Reaction equation

HRID 566149 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH:8]=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].[NH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=1.C(O)(=O)C>ClCCCl>[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH2:8][NH:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=2)=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 5414-NitrobenzaldehydeHCID 104392-Aminopyridine

Product 1

HCID 184725022-[(4-Nitrophenyl)methylamino]pyridineYield 35.6%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a solution of 4-nitrobenzaldehyde (3.02 g) and 2-aminopyridine (1.88 g) in 1,2-dichloroethane (70 ml) were added triacetoxy sodium boro hydride (5.93 g) and acetic acid (1.14 ml), and the mixture was stirred under nitrogen atmosphere at room temperature for 2 hours and concentrated. To the residue was added sodium bicarbonate solution, and the mixture was extracted with ethyl acetate, washed with brine, dried (anhydrous magnesium sulfate) and concentrated. The residue was purified with silica gel column chromatography (ethyl acetate/hexane=1/1), and to the purified materials were added ethyl acetate/diethylether and 1N hydrochloric acid. The aqueous layer was extracted and washed with diethylether, and to the mixture was added sodium carbonate. The mixture was extracted with ethyl acetate, and the extract was dried (anhydrous magnesium sulfate), concentrated and recrystallized from ethyl acetate/hexane to give 2-[(4-nitrophenyl)methylamino]pyridine (1.63 g) as pale yellow crystals.

Workup

  1. concentrationconcentrated
  2. additionTo the residue was added sodium bicarbonate solution
  3. extractionthe mixture was extracted with ethyl acetate
  4. washwashed with brine
  5. dry with materialdried (anhydrous magnesium sulfate)
  6. concentrationconcentrated
  7. customThe residue was purified with silica gel column chromatography (ethyl acetate/hexane=1/1)
  8. additionto the purified materials were added ethyl acetate/diethylether and 1N hydrochloric acid
  9. extractionThe aqueous layer was extracted
  10. washwashed with diethylether
  11. additionto the mixture was added sodium carbonate
  12. extractionThe mixture was extracted with ethyl acetate
  13. dry with materialthe extract was dried (anhydrous magnesium sulfate)
  14. concentrationconcentrated
  15. customrecrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-58baa9e73e2b453083e9f2227816560a
Source dataset
uspto-grants-2001_01
Patent number
US06172061B2

Reaction notes

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