Nitric Acid → 5-Bromo-2-methyl-4-nitropyridine 1-oxide

HRID 2196406Notes

Reaction equation

HRID 2196406 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:9])=[N+:6]([O-:8])[CH:7]=1.[N+:10]([O-])([OH:12])=[O:11].[OH-].[Na+]>S(=O)(=O)(O)O>[Br:1][C:2]1[C:3]([N+:10]([O-:12])=[O:11])=[CH:4][C:5]([CH3:9])=[N+:6]([O-:8])[CH:7]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 14798Sodium HydroxideHCID 8171645-Bromo-2-methylpyridin-1-ium-1-olate

Product 1

HCID 123329085-Bromo-2-methyl-4-nitropyridine 1-oxideYield 81%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
25 °C

Procedure

To a solution of 5-bromo-2-methylpyridine N-oxide (660 mg, 3.51 mmol) in sulfuric acid (1.6 mL) at 0° C. was added a premixed solution of nitric acid (1.5 mL) in sulfuric acid (2.5 mL). The resulting reaction was warmed to 25° C. then heated to 80° C. After 12 h, the solution was poured into ice then, neutralized with 6N NaOH and extracted several times with DCM. The combined organic fractions were dried over Na2SO4, concentrated and purified via column chromatography (silica, 1% MeOH in DCM) yielding the title compound (558 mg, 81%) as a yellow solid: LCMS (ES) m/z=235 (M+H)+.

Workup

  1. customThe resulting reaction
  2. temperaturethen heated to 80° C
  3. additionthe solution was poured into ice
  4. extractionextracted several times with DCM
  5. dry with materialThe combined organic fractions were dried over Na2SO4
  6. concentrationconcentrated
  7. custompurified via column chromatography (silica, 1% MeOH in DCM)

Sources & evidence

ORD record
ord-bdc4a2d1cc704ac6915bb262af9b0138
Source dataset
uspto-grants-2012_12
Patent number
US08338434B2

Reaction notes

Loading…