Bromine → 4-Amino-3-bromo-5-nitropyridine

HRID 68922

Reaction equation

HRID 68922 reaction equation
[N+:1]([C:4]1[CH:5]=[N:6][CH:7]=[CH:8][C:9]=1[NH2:10])([O-:3])=[O:2].CC([O-])=O.[Na+].[Br:16]Br.C([O-])(O)=O.[Na+]>O.C(O)(=O)C>[Br:16][C:8]1[CH:7]=[N:6][CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[C:9]=1[NH2:10]

Participants

7

Reactant 4

HCID 24408BromineHCID 516892Sodium BicarbonateHCID 517045Sodium AcetateHCID 5488034-Amino-3-nitropyridine

Product 1

HCID 49975884-Amino-3-bromo-5-nitropyridineYield 77%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 3-nitropyridin-4-amine (XII) (10 g, 71.94 mmol) and acetic acid (120 ml) was added to a sealed tube followed by addition of NaOAc (29.50 g, 93.52 mmol) and dropwise addition of bromine (4.7 ml 359.7 mmol) under stirring. The sealed tube was heated at 100° C. for 28 h until TLC showed consumption of starting material. The reaction mixture was concentrated to obtain a solid which was dissolved in water, basified with NaHCO3 and extracted with ethyl acetate. The combined organic extracts were dried and concentrated to produce 3-bromo-5-nitropyridin-4-amine (XIII) as a yellow solid (12 g, 55 mmol, 77% yield). 1H NMR (DMSO-d6) δ ppm 9.19 (s, 1H), 8.58 (s, 1H); ESIMS found for C5H4BrN3O2 m/z 217, 219 (M+, M+2).

Workup

  1. additionwas added to a sealed tube
  2. customconsumption of starting material
  3. concentrationThe reaction mixture was concentrated
  4. customto obtain a solid which
  5. extractionextracted with ethyl acetate
  6. customThe combined organic extracts were dried
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-af6d8cfa091e44d3b644922f7ca636d7
Source dataset
uspto-grants-2014_09
Patent number
US08822478B2

Linked notes

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