Dimethyl 2-(3-nitropyridin-2-yl)malonate → 2-Methyl-3-nitropyridine

HRID 2201401Notes

Reaction equation

HRID 2201401 reaction equation
COC(=O)[CH:4]([C:9]1[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][CH:12]=[CH:11][N:10]=1)C(OC)=O>Cl>[CH3:4][C:9]1[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][CH:12]=[CH:11][N:10]=1

Participants

3

Reactant 1

HCID 2782199Dimethyl 2-(3-nitropyridin-2-yl)malonate

Product 1

HCID 3293602-Methyl-3-nitropyridineYield 92.7%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

A modified procedure of Cash et al. (Org. Biomol. Chem. 2005, 3. 3701-3706) was used. Dimethyl-2-(3-nitropyridin-2-yl)malonate (1.4 g, 5.5 mmol) was dissolved in 70 ml 6 M HCl and refluxed for 8 h. After neutralization with saturated Na2CO3 solution the solution was extracted three times with dichloromethane. The combined organic layers were dried over Na2SO4, filtered, concentrated and purified by bulb tube distillation (0.35 mbar; 70-80° C.). 2-Methyl-3-nitropyridine (0.7 g, 5.1 mmol, 92%) was obtained as a pale yellow oil. 1H NMR (300 MHz, CDCl3) 8.72 (pdd; 3J=1.2 Hz; 3J=4.7 Hz; 1H; H-6); 8.27 (pdd; 3J=1.2 Hz; 3J=8.2 Hz; 1H; H-4); 7.35 (pdd; 3J=4.7 Hz; 3J=8.2 Hz; 1H; H-5); 2.86 (s; 3H; CH3).

Workup

  1. temperaturerefluxed for 8 h
  2. extractionAfter neutralization with saturated Na2CO3 solution the solution was extracted three times with dichloromethane
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified by bulb tube
  7. distillationdistillation (0.35 mbar; 70-80° C.)

Sources & evidence

ORD record
ord-e12327c3bb024bcd89e22da162dd200e
Source dataset
uspto-grants-2016_06
Patent number
US09364459B2

Reaction notes

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