Potassium Carbonate → 1-[4-chloro-2-fluoro-5-(5-hydroxypyridin-2-yloxy)-phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl,1,2,4-triazol-5(1H)-one

HRID 1090985Notes

Reaction equation

HRID 1090985 reaction equation
C(=O)([O-])[O-:2].[K+].[K+].F[B-](F)(F)F.[Cl:12][C:13]1[CH:27]=[C:26]([F:28])[C:25]([N:29]2[C:33](=[O:34])[N:32]([CH:35]([F:37])[F:36])[C:31]([CH3:38])=[N:30]2)=[CH:24][C:14]=1[O:15][C:16]1[CH:21]=[CH:20][C:19]([N+]#N)=[CH:18][N:17]=1>FC(F)(F)C(O)=O.O>[Cl:12][C:13]1[C:14]([O:15][C:16]2[CH:21]=[CH:20][C:19]([OH:2])=[CH:18][N:17]=2)=[CH:24][C:25]([N:29]2[C:33](=[O:34])[N:32]([CH:35]([F:36])[F:37])[C:31]([CH3:38])=[N:30]2)=[C:26]([F:28])[CH:27]=1

Participants

5

Reactant 2

HCID 11430Potassium CarbonateHCID 199122182-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridine-5-diazonium tetrafluoroborate

Product 1

HCID 199122291-[4-chloro-2-fluoro-5-(5-hydroxypyridin-2-yloxy)-phenyl]-4-difluoromethyl-4,5-dihydro-3-methyl,1,2,4-triazol-5(1H)-oneYield 177.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

To a stirred, cold (ice bath) solution of 0.67 g (0.0048 mole) of potassium carbonate in 20 mL of trifluoroacetic acid was added 4.7 g (0.097 mole) of 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro -3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]pyridine-5-diazonium tetrafluoroborate. The reaction mixture was allowed to warm to room temperature and was then heated at reflux for 5.5 hours. The mixture was cooled to room temperature, diluted with 50 mL of water, and the whole was extracted with four portions of methylene chloride. The extracts were combined, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure to give a red oil which was purified by column chromatography on silica gel. Elution with n-hexane:ethyl acetate (2:1) gave 3.3 g of 1-[4-chloro-2-fluoro-5-(5-hydroxypyridin-2-yloxy)-phenyl]-4-difluoromethyl-4,5-dihydro -3-methyl,1,2,4-triazol-5(1H)-one as a solid, m.p. 179°-181° C.

Workup

  1. temperaturewas then heated
  2. temperatureat reflux for 5.5 hours
  3. temperatureThe mixture was cooled to room temperature
  4. extractionthe whole was extracted with four portions of methylene chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customThe filtrate was evaporated under reduced pressure
  8. customto give a red oil which
  9. customwas purified by column chromatography on silica gel
  10. washElution with n-hexane:ethyl acetate (2:1)

Sources & evidence

ORD record
ord-2c5007295b1e417581b0f6b16953c6ce
Source dataset
uspto-grants-1992_01
Patent number
US05084085

Reaction notes

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