Dimethylformamide → Dimethyl 4-chloropyridine-3,5-dicarboxylate

HRID 6893Notes

Reaction equation

HRID 6893 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10](=O)[C:9]([C:12]([O:14][CH3:15])=[O:13])=[CH:8][NH:7][CH:6]=1)=[O:4].CN(C=O)C.S(Cl)([Cl:23])=O>>[CH3:1][O:2][C:3](=[O:4])[C:5]1[C:10]([Cl:23])=[C:9]([C:12]([O:14][CH3:15])=[O:13])[CH:8]=[N:7][CH:6]=1

Participants

4

Reactant 3

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 113901994-Oxo-1,4-dihydro-pyridine-3,5-dicarboxylic acid dimethyl ester

Product 1

HCID 22019198Dimethyl 4-chloropyridine-3,5-dicarboxylateYield 41%

Procedure

A mixture of 16.38 g (77.6 mmol) of 4-oxo-1,4-dihydro-pyridine-3,5-dicarboxylic acid dimethyl ester (prepared according to the method described in S. Zupancic, Heterocycles; 2000; 2033–2042) and 0.5 ml of DMF in 150 ml of thionyl chloride is heated at reflux for 2 hours. Excess thionyl chloride is removed under vacuum and the residue is added to aqueous NaHCO3, and extracted in ethyl acetate. The phases are separated and the organic layer is dried and evaporated. The residue is washed with aqueous K2CO3 and water, and dried. There is obtained 7.35 g (41% yield) of white solid (M+1=230).

Workup

  1. customprepared
  2. temperatureat reflux for 2 hours
  3. customExcess thionyl chloride is removed under vacuum
  4. additionthe residue is added to aqueous NaHCO3
  5. extractionextracted in ethyl acetate
  6. customThe phases are separated
  7. customthe organic layer is dried
  8. customevaporated
  9. washThe residue is washed with aqueous K2CO3 and water
  10. customdried

Sources & evidence

ORD record
ord-e4a9dca21e40463ab3e70a50648798e9
Source dataset
uspto-grants-2006_08
Patent number
US07084163B2

Reaction notes

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