Nitric Acid → Methyl 2-amino-5-nitropyridine-3-carboxylate

HRID 2079938Notes

Reaction equation

HRID 2079938 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][CH:7]=[N:6][C:5]=1[NH2:10].C(=O)(O)[O-].[Na+].[N+:17]([O-])([OH:19])=[O:18]>S(=O)(=O)(O)O>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[C:8]([N+:17]([O-:19])=[O:18])[CH:7]=[N:6][C:5]=1[NH2:10]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 351633Methyl 2-aminopyridine-3-carboxylateHCID 516892Sodium Bicarbonate

Product 1

HCID 13063488Methyl 2-amino-5-nitropyridine-3-carboxylateYield 35%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
0 °C

Procedure

2-Amino-nicotinic acid methyl ester (1.00 g, 6.57 mmol) described in Preparation Example A-2 was dissolved at 0° C. in a mixed solution of nitric acid (0.7 mL) and sulfuric acid (2.6 mL), which was stirred at 0° C. for 40 minute and at room temperature for 19 hours, then, further stirred at 70° C. for 4 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution at 0° C., which was extracted with ethyl acetate and tetrahydrofuran, the organic layer was washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated in vacuo. Methanol was added to the residue, the precipitated solid was filtered to obtain the title compound (459 mg, 2.33 mmol, 35%) as a white solid.

Workup

  1. stirringfurther stirred at 70° C. for 4 hours
  2. extractionwhich was extracted with ethyl acetate and tetrahydrofuran
  3. washthe organic layer was washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customThe solvent was evaporated in vacuo
  6. additionMethanol was added to the residue
  7. filtrationthe precipitated solid was filtered

Sources & evidence

ORD record
ord-e8a9ec757a2742cbbfa77f9f6d3650ea
Source dataset
uspto-grants-2011_04
Patent number
US07932272B2

Reaction notes

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