3-(Benzyloxy)-6-bromo-2-nitropyridine → 3-(Benzyloxy)-6-bromopyridin-2-amine

HRID 1922753Notes

Reaction equation

HRID 1922753 reaction equation
[CH2:1]([O:8][C:9]1[C:10]([N+:16]([O-])=O)=[N:11][C:12]([Br:15])=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>C(O)(=O)C.[Fe]>[CH2:1]([O:8][C:9]1[C:10]([NH2:16])=[N:11][C:12]([Br:15])=[CH:13][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 596057923-(Benzyloxy)-6-bromo-2-nitropyridine

Product 1

HCID 596055123-(Benzyloxy)-6-bromopyridin-2-amineYield 71%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Procedure

A mixture of 3-benzyloxy-6-bromo-2-nitropyridine (1.6 g, 5.2 mmol) and iron powder (2.9 g, 51.8 mmol) in acetic acid (25 mL) and IMS (25 mL) was stirred at reflux for 1 hour, then cooled to room temperature and filtered though a pad of celite. The filtrate was concentrated under reduced pressure to give a residue that was partitioned between an aqueous saturated solution of sodium bicarbonate and EtOAc. The organic layer was separated and washed with water and brine, dried over Na2SO4, filtered and concentrated. The residue was purified by flash chromatography (Si—PPC, EtOAc:cyclohexane, gradient 0:100 to 40:60) to give 3-Benzyloxy-6-bromopyridin-2-ylamine as a pale yellow solid (1.0 g, 71%). 1H NMR (400 MHz, CHCl3-d): δ 7.41-7.34 (m, 5 H); 6.82 (d, J=8.1 Hz, 1 H); 6.71 (d, J=8.1 Hz, 1 H); 5.04 (s, 2 H); 4.80 (s, 2 H).

Workup

  1. temperatureat reflux for 1 hour
  2. filtrationfiltered though a pad of celite
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customto give a residue that
  5. customwas partitioned between an aqueous saturated solution of sodium bicarbonate and EtOAc
  6. customThe organic layer was separated
  7. washwashed with water and brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by flash chromatography (Si—PPC, EtOAc:cyclohexane, gradient 0:100 to 40:60)

Sources & evidence

ORD record
ord-d0fcd4e4f0644d449217d6cf32907cb0
Source dataset
uspto-grants-2012_05
Patent number
US08173650B2

Reaction notes

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