Nitric Acid → 4-Nitro-2,3,5-trimethylpyridine, 1-oxide

HRID 979852Notes

Reaction equation

HRID 979852 reaction equation
[N+:1]([O-:4])(O)=[O:2].[CH3:5][C:6]1[C:11]([CH3:12])=[CH:10][C:9]([CH3:13])=[CH:8][N+:7]=1[O-:14].[OH-].[Na+]>S(=O)(=O)(O)O>[CH3:5][C:6]1[C:11]([CH3:12])=[C:10]([N+:1]([O-:4])=[O:2])[C:9]([CH3:13])=[CH:8][N+:7]=1[O-:14]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 14798Sodium HydroxideHCID 104869072,3,5-Trimethyl-1-oxidopyridin-1-ium

Product 1

HCID 112176114-Nitro-2,3,5-trimethylpyridine, 1-oxide

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

65 ml of fuming nitric acid (d=1.5) were added dropwise while cooling to 210 ml of concentrated sulfuric acid. 96.5 g of 2,3,5-trimethylpyridine 1-oxide were subsequently added portionwise at 0°-5°, whereupon the mixture was stirred at room temperature for 1 hour, then heated to 90° within 3 hours and left at this temperature overnight. After cooling the solution was poured on to 1.5 kg of ice, whereupon the mixture was adjusted to pH 3 with concentrated sodium hydroxide solution and extracted three times with 500 ml of methylene chloride. The combined organic phases were washed with 1 l of water, dried over sodium sulfate and evaporated in vacuo. The residue was crystallized from ether/petroleum ether and there was obtained 2,3,5-trimethyl-4-nitropyridine 1-oxide of melting point 76°-78°.

Workup

  1. temperatureheated to 90° within 3 hours
  2. waitleft at this temperature overnight
  3. temperatureAfter cooling the solution
  4. extractionextracted three times with 500 ml of methylene chloride
  5. washThe combined organic phases were washed with 1 l of water
  6. dry with materialdried over sodium sulfate
  7. customevaporated in vacuo
  8. customThe residue was crystallized from ether/petroleum ether

Sources & evidence

ORD record
ord-dae219d7c9014da3baec7b8b1c22d5af
Source dataset
uspto-grants-1987_01
Patent number
US04634710

Reaction notes

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