Carbon Dioxide → 5-Ethyl-6-cyclopropyl-pyridine-2,3-dicarboxylic acid

HRID 358847Notes

Reaction equation

HRID 358847 reaction equation
S(=O)(=O)(O)O.C([O:8][C:9]([C:11]1[C:16]([C:17]([O:19]CC)=[O:18])=[CH:15][C:14]([CH2:22][CH3:23])=[CH:13][N:12]=1)=[O:10])C.[CH:24]1(C(O)=O)[CH2:26][CH2:25]1.C(=O)=O>O.[N+]([O-])([O-])=O.[Ag+]>[CH2:22]([C:14]1[CH:15]=[C:16]([C:17]([OH:19])=[O:18])[C:11]([C:9]([OH:8])=[O:10])=[N:12][C:13]=1[CH:24]1[CH2:26][CH2:25]1)[CH3:23]

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 1118Sulfuric AcidHCID 15655Cyclopropanecarboxylic acidHCID 10857926Diethyl 5-ethylpyridine-2,3-dicarboxylate

Product 1

HCID 200671725-Ethyl-6-cyclopropyl-pyridine-2,3-dicarboxylic acidYield 42.7%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent

Procedure

There is added to a solution of 32 ml of concentrated sulphuric acid and 6.8 g of silver nitrate (AgNO3) in 400 ml of water first of all 50 g of 5-ethylpyridine-2,3-dicarboxylic acid diethyl ester and, when a homogeneous solution has been obtained, 25.8 g of cyclopropanecarboxylic acid. The solution is then heated to 70° and a solution of 68.2 g of ammonium peroxydisulphate (NH4)2S2O8 is added dropwise thereto while stirring vigorously. When the evolution of CO2 has ceased, the reaction mixture is stirred for a further 20 minutes, then cooled to 15° and extracted twice with 200 ml of methylene chloride each time. The methylene chloride extract is dried over magnesium sulphate, filtered and concentrated. The oily residue is purified by chromatography over a column of silica gel using ether/hexane 1:1. Evaporation of the solvent yields 20 g of 5-ethyl-6-cyclopropyl-pyridine-2,3-dicarboxylic acid in the form of a yellow oil.

Workup

  1. customhas been obtained
  2. temperatureThe solution is then heated to 70°
  3. stirringthe reaction mixture is stirred for a further 20 minutes
  4. temperaturecooled to 15°
  5. extractionextracted twice with 200 ml of methylene chloride each time
  6. extractionThe methylene chloride extract
  7. dry with materialis dried over magnesium sulphate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe oily residue is purified by chromatography over a column of silica gel
  11. customEvaporation of the solvent

Sources & evidence

ORD record
ord-8b16d12fa2e147f78b230a93275aa80d
Source dataset
uspto-grants-1991_03
Patent number
US04997947

Reaction notes

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