Trifluoroacetic acid → HCID 67026662, compound

HRID 2113417Notes

Reaction equation

HRID 2113417 reaction equation
[Cl:1][C:2]([C:17]1[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([C:24]([O:26][CH3:27])=[O:25])[N+:18]=1[O-:28])(C(OC(C)(C)C)=O)C(OC(C)(C)C)=O.FC(F)(F)C(O)=O>ClCCl>[Cl:23][C:20]1[CH:21]=[CH:22][C:17]([CH2:2][Cl:1])=[N+:18]([O-:28])[C:19]=1[C:24]([O:26][CH3:27])=[O:25]

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 67026716HCID 67026716, compound

Product 1

HCID 67026662HCID 67026662, compoundYield 66.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of di-tert-butyl chloro[5-chloro-6-(methoxycarbonyl)-1-oxidopyridin-2-yl]malonate (19.65 g, 45.0 mmol), trifluoroacetic acid (41 mL) and dichloromethane (82 mL) was refluxed for 2.5 hours, cooled and then concentrated to dryness. The crude residue was taken up in xylene and the mixture heated at reflux until carbon dioxide was no longer given off. The reaction mixture was then cooled to room temperature and ethyl ether added followed by a small amount of saturated NaHCO3 solution. The organic was separated and the aqueous layer was saturated with brine and extracted with ethyl acetate. The organic layers were combined, dried (MgSO4), filtered and concentrated to dryness. The crude product was purified by column chromatography (20-50% ethyl acetate in hexane) to give methyl 3-chloro-6-(chloromethyl)pyridine-2-carboxylate 1-oxide (7.11 g, 30.1 mmol) as a brown solid; 1H NMR (CDCl3): δ 7.60 (d, 2H), 7.40 (d, 2H), 4.80 (s, 2H), 4.00 (s, 3H).

Workup

  1. temperaturewas refluxed for 2.5 hours
  2. temperaturecooled
  3. concentrationconcentrated to dryness
  4. temperaturethe mixture heated
  5. temperatureat reflux until carbon dioxide
  6. additionethyl ether added
  7. customThe organic was separated
  8. extractionextracted with ethyl acetate
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. concentrationconcentrated to dryness
  12. customThe crude product was purified by column chromatography (20-50% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-257f9431d2374338933ce2c8e9f868cd
Source dataset
uspto-grants-2008_10
Patent number
US07432227B2

Reaction notes

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