Hydrogen Peroxide → 3-Bromo-2-ethyl-6-nitropyridine

HRID 2278895Notes

Reaction equation

HRID 2278895 reaction equation
OO.[Br:3][C:4]1[CH:5]=[CH:6][C:7]([NH2:12])=[N:8][C:9]=1[CH2:10][CH3:11].C(Cl)Cl.[OH-:16].[Na+].[OH:18]S(O)(=O)=O>>[Br:3][C:4]1[C:9]([CH2:10][CH3:11])=[N:8][C:7]([N+:12]([O-:18])=[O:16])=[CH:6][CH:5]=1

Participants

6

Reactant 5

HCID 784Hydrogen PeroxideHCID 1118Sulfuric Acid2×HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 217103385-Bromo-6-ethylpyridin-2-amine

Product 1

HCID 904030533-Bromo-2-ethyl-6-nitropyridineYield 71%

Procedure

A 0° C. solution of H2SO4 (11 mL) was slowly treated with H2O2 (30%, 5.5 mL), in an open flask, stirred for 5 min, treated drop-wise with a solution of 5-bromo-6-ethylpyridin-2-amine (3.79 g, 18.85 mmol) in H2SO4 (10 mL) warmed to RT as the cooling bath expired and stirred overnight. The solution was poured into ice water (200 mL), treated with DCM, cooled to 0° C. and treated slowly with 50% NaOH until pH=10. The layers were separated, the aqueous layer extracted with additional DCM (1×) and the combined organics were washed with brine, dried over Na2SO4 and concentrated to dryness to afford crude 3-bromo-2-ethyl-6-nitropyridine (3.168 g, 71%) which was used without further purification. 1H NMR (400 MHz, DMSO-d6): δ 8.44 (d, J=8.5 Hz, 1 H), 8.05 (d, J=8.5 Hz, 1 H), 2.97 (q, J=7.5 Hz, 2 H), 1.24 (t, J=7.5 Hz, 3 H); MS (ESI) m/z: 231.0 (M+H+).

Workup

  1. stirringstirred overnight
  2. temperaturecooled to 0° C.
  3. customThe layers were separated
  4. extractionthe aqueous layer extracted with additional DCM (1×)
  5. washthe combined organics were washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-8f3118101cba4f29abe32bee2e4fced7
Source dataset
uspto-grants-2015_09
Patent number
US09133183B2

Reaction notes

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