Nitric Acid → 2-Chloro-5-methoxy-3-methyl-4-nitropyridine 1-oxide

HRID 69315Notes

Reaction equation

HRID 69315 reaction equation
[N+:1]([O-:4])(O)=[O:2].[Cl:5][C:6]1[C:11]([CH3:12])=[CH:10][C:9]([O:13][CH3:14])=[CH:8][N+:7]=1[O-:15].C(=O)([O-])[O-].[Na+].[Na+]>S(=O)(=O)(O)O>[Cl:5][C:6]1[C:11]([CH3:12])=[C:10]([N+:1]([O-:4])=[O:2])[C:9]([O:13][CH3:14])=[CH:8][N+:7]=1[O-:15]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 10340Sodium CarbonateHCID 867178152-Chloro-5-methoxy-3-methylpyridine 1-oxide

Product 1

HCID 867178162-Chloro-5-methoxy-3-methyl-4-nitropyridine 1-oxide

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
90 °C

Procedure

Concentrated nitric acid (2.5 mL) was added drop-wise to a 0° C. solution of C2 (350 mg, 2.02 mmol) in concentrated sulfuric acid (2.5 mL). The reaction mixture was heated at 90° C. for 1 hour, then cooled to room temperature and poured onto crushed ice. The resulting mixture was neutralized to pH 6-7 with saturated aqueous sodium carbonate solution, and extracted with ethyl acetate. The combined organic layers were washed with water, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated in vacuo to provide the product as a light yellow solid. Yield: 370 mg, 1.69 mmol, 84%. LCMS m/z 219.0, 221.1 [M+H+]. 1H NMR (400 MHz, DMSO-d6) δ 8.65 (s, 1H), 3.94 (s, 3H), 2.31 (s, 3H).

Workup

  1. temperaturecooled to room temperature
  2. additionpoured
  3. customonto crushed ice
  4. extractionextracted with ethyl acetate
  5. washThe combined organic layers were washed with water
  6. washwashed with saturated aqueous sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-638a42ae056845ba92bf5d870e224a00
Source dataset
uspto-grants-2014_09
Patent number
US08822494B2

Reaction notes

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