Carbon Dioxide → 6-Cyclopropylpyridine-2,3-dicarboxylic acid diethyl ester

HRID 358845Notes

Reaction equation

HRID 358845 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:10][CH:9]=[CH:8][N:7]=1)=[O:5])[CH3:2].[CH:17]1(C(O)=O)[CH2:19][CH2:18]1.C(=O)=O>O.S(=O)(=O)(O)O.[N+]([O-])([O-])=O.[Ag+]>[CH2:1]([O:3][C:4]([C:6]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:10][CH:9]=[C:8]([CH:17]2[CH2:19][CH2:18]2)[N:7]=1)=[O:5])[CH3:2]

Participants

7

Reactant 3

HCID 280Carbon DioxideHCID 15655Cyclopropanecarboxylic acidHCID 108895172,3-Diethyl 2,3-pyridinedicarboxylate

Product 1

HCID 142803436-Cyclopropylpyridine-2,3-dicarboxylic acid diethyl ester

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Procedure

40 g of pyridine-2,3-dicarboxylic acid diethyl ester are dissolved in a mixture of 400 g of water and 36 g of concentrated sulphuric acid and 6.1 g of silver nitrate (AgNO3). Subsequently, 32 g of cyclopropanecarboxylic acid are added and the reaction mixture is heated to 70°. A solution of 82.1 g of ammonium peroxydisulphate (NH4)2S2O8 in 300 ml of water is added dropwise thereto while stirring vigorously. When the evolution of CO2 has ceased, the reaction mixture is stirred for a further 20 minutes. It is then cooled to 15° and extracted twice with 200 ml of methylene chloride each time. The organic phase is collected, dried over magnesium sulphate, filtered and concentrated by evaporation. The residue is distilled at 13 millibars and the distillate is chromatographed over a column of silica gel with hexane/methylene chloride/ether. After the solvent has been evaporated 11.2 g of the above diester remain behind in the form of a colourless oil.

Workup

  1. temperaturethe reaction mixture is heated to 70°
  2. stirringthe reaction mixture is stirred for a further 20 minutes
  3. temperatureIt is then cooled to 15°
  4. extractionextracted twice with 200 ml of methylene chloride each time
  5. customThe organic phase is collected
  6. dry with materialdried over magnesium sulphate
  7. filtrationfiltered
  8. concentrationconcentrated by evaporation
  9. distillationThe residue is distilled at 13 millibars
  10. distillationthe distillate is chromatographed over a column of silica gel with hexane/methylene chloride/ether
  11. customAfter the solvent has been evaporated 11.2 g of the above diester

Sources & evidence

ORD record
ord-61cddb36b2914d6ca7c820944a07ee2f
Source dataset
uspto-grants-1991_03
Patent number
US04997947

Reaction notes

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