Trimethyl orthoformate → 1-(2,6-Dichloro-4-trifluoromethylphenyl)-5-methoxymethylideneamino-3-(1,2,4-oxadiazol-3-yl)-4-trifluoromethylsulfonylpyrazole

HRID 429261Notes

Reaction equation

HRID 429261 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]2[N:23]=[CH:22][O:21][N:20]=2)[C:3]=1[S:24]([C:27]([F:30])([F:29])[F:28])(=[O:26])=[O:25].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH:43](OC)(OC)[O:44][CH3:45]>>[Cl:18][C:8]1[CH:9]=[C:10]([C:14]([F:17])([F:15])[F:16])[CH:11]=[C:12]([Cl:13])[C:7]=1[N:6]1[C:2]([N:1]=[CH:43][O:44][CH3:45])=[C:3]([S:24]([C:27]([F:30])([F:29])[F:28])(=[O:25])=[O:26])[C:4]([C:19]2[N:23]=[CH:22][O:21][N:20]=2)=[N:5]1

Participants

4

Reactant 3

HCID 9005Trimethyl orthoformateHCID 521998p-Toluenesulfonic acid monohydrateHCID 183547765-Amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1,2,4-oxadiazol-3-yl)-4-trifluoromethylsulfonylpyrazole

Product 1

HCID 734317151-(2,6-Dichloro-4-trifluoromethylphenyl)-5-methoxymethylideneamino-3-(1,2,4-oxadiazol-3-yl)-4-trifluoromethylsulfonylpyrazoleYield 23%

Procedure

To 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1,2,4-oxadiazol-3-yl)-4-trifluoromethylsulfonylpyrazole (1.00 g, 2.02 mmol) and 10 ml of trimethyl orthoformate was added p-toluenesulfonic acid monohydrate (0.05 g) with stirring at room temperature. The mixture was stirred with heating at reflux for 59 hours. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. The residue was dissolved in 50 ml of toluene and then concentrated under reduced pressure. After this procedure was repeated once again, the resulting concentrated residue was purified by subjecting to silica gel column chromatography [eluent: mixed solvent of ethyl acetate and chloroform (volume ratio=1:20)]. The resulting crystal was washed with hexane and filtered to obtain 124 mg (0.46 mmol) of the title compound as a colorless crystal. Yield 23.0%.

Workup

  1. stirringThe mixture was stirred
  2. temperaturewith heating
  3. temperatureat reflux for 59 hours
  4. temperatureThe reaction mixture was cooled to room temperature
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in 50 ml of toluene
  7. concentrationconcentrated under reduced pressure
  8. customthe resulting concentrated residue was purified
  9. additionby subjecting to silica gel column chromatography [eluent: mixed solvent of ethyl acetate and chloroform (volume ratio=1:20)]
  10. washThe resulting crystal was washed with hexane
  11. filtrationfiltered

Sources & evidence

ORD record
ord-8681cfd2b08f4bf6a789dfc1806a4f67
Source dataset
uspto-grants-2001_11
Patent number
US06316477B1

Reaction notes

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