Hydrochloric Acid → 2-Methyl-5-nitropyridine

HRID 231634Notes

Reaction equation

HRID 231634 reaction equation
[C:1](OCC)(=O)[CH2:2][C:3](OCC)=O.[OH-].[Na+].[N+:14]([C:17]1[CH:18]=CC(Cl)=[N:21][CH:22]=1)([O-:16])=[O:15].Cl>CN(C)C=O>[N+:14]([C:17]1[CH:18]=[CH:3][C:2]([CH3:1])=[N:21][CH:22]=1)([O-:16])=[O:15]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 14798Sodium HydroxideHCID 783082-Chloro-5-nitropyridine

Product 1

HCID 27945522-Methyl-5-nitropyridine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

206 g (1.29 mol) of diethyl malonate are added to 600 ml of dimethylformamide, and 51.2 g (1.28 mol) of freshly powdered NaOH are introduced, with cooling. The mixture is subsequently stirred after 15 minutes and a solution of 94.8 g (0.6 mol) of 5-nitro-2-chloropyridine in 600 ml of dimethylformamide is then added dropwise at room temperature. The deep red solution formed is stirred until the reaction is complete, 36% strength HCl is then added dropwise until the color changes to orange and the mixture is evaporated to dryness in vacuo. The residue is taken up in 400 ml of CHCl3, washed with 500 ml of water and evaporated again. The residue is now dissolved in a mixture of 1,200 ml of 36% strength HCl and 870 ml of water and the solution is boiled under reflux until the evolution of gas has ended. Thereafter, it is evaporated in vacuo, the residue is dissolved in 500 ml of water, the solution is extracted with methylene chloride and the organic phase is washed again with water. After the solvent has been stripped off, 72 g (87%) of 5-nitro-2-picoline remain.

Workup

  1. additionare introduced
  2. temperaturewith cooling
  3. customThe deep red solution formed
  4. stirringis stirred until the reaction
  5. customis evaporated to dryness in vacuo
  6. washwashed with 500 ml of water
  7. customevaporated again
  8. dissolutionThe residue is now dissolved in a mixture of 1,200 ml of 36% strength HCl and 870 ml of water
  9. temperatureunder reflux until the evolution of gas
  10. customThereafter, it is evaporated in vacuo
  11. dissolutionthe residue is dissolved in 500 ml of water
  12. extractionthe solution is extracted with methylene chloride
  13. washthe organic phase is washed again with water

Sources & evidence

ORD record
ord-ad23d5c7686a4c32a01a7095e4b8648a
Source dataset
uspto-grants-1989_07
Patent number
US04847382

Reaction notes

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