Bromine → 2-Amino-3-bromo-5-nitropyridine

HRID 1044004Notes

Reaction equation

HRID 1044004 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([NH2:10])=[N:8][CH:9]=1)([O-:3])=[O:2].[Br:11]Br>C(O)(=O)C>[Br:11][C:6]1[C:7]([NH2:10])=[N:8][CH:9]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1

Participants

4

Reactant 2

HCID 24408BromineHCID 778882-Amino-5-nitropyridine

Product 1

HCID 27344122-Amino-3-bromo-5-nitropyridineYield 32%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
20 °C

Procedure

To a solution of 5-nitro-pyridin-2-ylamine (30 g, 0.22 mol) in acetic acid (200 mL) at 10° C. was added Br2 (38 g, 0.24 mol) dropwise. After addition, the mixture was stirred at 20° C. for 30 min. The solid was filtered and then dissolved in ethyl acetate (200 mL). The mixture was basified to pH 8-9 with saturated aqueous NaHCO3. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (100 mL×3). The combined organic layers were washed with water, brine, dried over Na2SO4 and concentrated under vacuum to afford 3-bromo-5-nitropyridin-2-amine (14.8 g, 32%). 1H-NMR (CDCl3, 400 MHz) δ 8.94 (d, J=2.4 Hz, 1H), 8.50 (d, J=2.4 Hz, 1H), 5.67 (brs, 2H).

Workup

  1. additionAfter addition
  2. filtrationThe solid was filtered
  3. dissolutiondissolved in ethyl acetate (200 mL)
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted with ethyl acetate (100 mL×3)
  6. washThe combined organic layers were washed with water, brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-bf64df3423d641cc85246691b025fe73
Source dataset
uspto-grants-2013_10
Patent number
US08563573B2

Reaction notes

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