Hydrochloric Acid → Methyl [2-(1-(4-chlorophenyl)-3-pyrazolyloxy)pyridin-3-yl]glyoxylate

HRID 279044Notes

Reaction equation

HRID 279044 reaction equation
CC(C)([O-])C.[K+].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([N:14]2[CH:18]=[CH:17][C:16]([OH:19])=[N:15]2)=[CH:10][CH:9]=1.Cl[C:21]1[C:26]([C:27](=[O:32])[C:28]([O:30][CH3:31])=[O:29])=[CH:25][CH:24]=[CH:23][N:22]=1.Cl>C(O)(C)(C)C.CS(C)=O>[Cl:7][C:8]1[CH:9]=[CH:10][C:11]([N:14]2[CH:18]=[CH:17][C:16]([O:19][C:21]3[C:26]([C:27](=[O:32])[C:28]([O:30][CH3:31])=[O:29])=[CH:25][CH:24]=[CH:23][N:22]=3)=[N:15]2)=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 10976475Methyl 2-chloro-alpha-oxo-3-pyridineacetateHCID 23665647Potassium tert-butoxideHCID 178516414HCID 178516414, compound

Product 1

HCID 17888488Methyl [2-(1-(4-chlorophenyl)-3-pyrazolyloxy)pyridin-3-yl]glyoxylateYield 40.4%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6386tert-ButanolSolvent

Procedure

At 60° C., 4.7 g (42 mmol) of potassium tert-butoxide were added a little at a time to a solution of 7.4 g (38.1 mmol) of 1-(4-chlorophenyl)-3-hydroxypyrazole in 15 ml of tert-butanol. The mixture was stirred at this temperature for 1 hour and the solvent was then removed under reduced pressure. The residue was dissolved in 25 ml of abs. dimethyl sulfoxide, and a solution of 8.0 g (38.1 mmol) of methyl (2-chloropyridin-3-yl)glyoxylate in 10 ml of abs. dimethyl sulfoxide was then added at such a rate that the temperature did not exceed 30° C. After 30 minutes at room temperature, 50 ml of 0.5 N HCl were added and the reaction mixture was extracted repeatedly with ethyl acetate. The combined organic phases were washed with water and dried over sodium sulfate. The solvent was subsequently removed under reduced pressure. The resulting residue was purified by silica gel column chromatography using cyclohexane/ethyl acetate (10:1) as eluant. 5.5 g (40%) of the title compound were obtained as a clear oil.

Workup

  1. customthe solvent was then removed under reduced pressure
  2. dissolutionThe residue was dissolved in 25 ml of abs
  3. customdid not exceed 30° C
  4. waitAfter 30 minutes at room temperature
  5. extractionthe reaction mixture was extracted repeatedly with ethyl acetate
  6. washThe combined organic phases were washed with water
  7. dry with materialdried over sodium sulfate
  8. customThe solvent was subsequently removed under reduced pressure
  9. customThe resulting residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-a6e7bdf57a9546ff9be37b47fa5eb1cf
Source dataset
uspto-grants-2002_03
Patent number
US06362192B1

Reaction notes

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