Hydrogen Peroxide → Picolinic acid

HRID 1954447Notes

Reaction equation

HRID 1954447 reaction equation
[C:1]([O:6]CC)(=[O:5])[C:2]([CH3:4])=O.OO.Cl[C:12]1C=C[N:15]=[CH:14][CH:13]=1.OS(O)(=O)=O>O.C1(C)C=CC=CC=1.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Fe+2]>[N:15]1[CH:14]=[CH:13][CH:12]=[CH:4][C:2]=1[C:1]([OH:6])=[O:5]

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 1118Sulfuric AcidHCID 12041Ethyl pyruvateHCID 122884-Chloropyridine

Product 1

HCID 1018Picolinic acidYield 90%

Reagents, catalysts & solvents 3

HCID 62662Ferrous sulfate heptahydrateCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent2×

Procedure

Ethyl pyruvate (0.9-3 eq.) was stirred and cooled (-20-+0° C.) and hydrogen peroxide (30-35%, 0.9-3 eq) was added dropwise. This solution and a solution of Iron sulfate heptahydrate (0.9-3 eq.) in water (1-5 vol.) were then slowly and simultaneously added dropwise into a stirred solution of 4-Chloropyridine (1 eq) in water (1-5 vol.) and conc. H2SO4 (1-4 eq.) and Toluene (0-20 vol.), keeping the temperature below 25° C. The mixture was then stirred at room temperature until the reaction is judged complete. The mixture was poured into ice cold NaOH (10%) solution. Toluene (2-5 vol.) was added (If not already present), the layers were separated. The toluene layer was washed with 0.5 N HCl solution and evaporated to yield the crude 2-Pyridinecarboxylic acid, 4-chloro-3,5-dimethyl-, ethyl ester in over 90% yield based on the consumed starting material and over 50% isolated yield.

Workup

  1. additionwas added dropwise
  2. customthe temperature below 25° C
  3. customwere separated
  4. washThe toluene layer was washed with 0.5 N HCl solution
  5. customevaporated

Sources & evidence

ORD record
ord-b81822cebc874ba5a6b07c0bd81f8555
Source dataset
uspto-grants-2000_09
Patent number
US06121454

Reaction notes

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