Chlorotrifluoroethylene → (RS)-3-carboethoxy-4-(2-chloro-1,1,2-trifluoroethoxy)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

HRID 345117Notes

Reaction equation

HRID 345117 reaction equation
[C:1]([C:6]1[C:10]([OH:11])=[CH:9][N:8]([C:12]2[C:17]([Cl:18])=[CH:16][C:15]([C:19]([F:22])([F:21])[F:20])=[CH:14][C:13]=2[Cl:23])[N:7]=1)([O:3][CH2:4][CH3:5])=[O:2].[H-].[Na+].[Cl:26][C:27]([F:31])=[C:28]([F:30])[F:29]>O1CCOCC1>[C:1]([C:6]1[C:10]([O:11][C:28]([F:30])([F:29])[CH:27]([Cl:26])[F:31])=[CH:9][N:8]([C:12]2[C:17]([Cl:18])=[CH:16][C:15]([C:19]([F:20])([F:22])[F:21])=[CH:14][C:13]=2[Cl:23])[N:7]=1)([O:3][CH2:4][CH3:5])=[O:2]

Participants

5

Reactant 3

HCID 6594ChlorotrifluoroethyleneHCID 24758Sodium hydrideHCID 19993700HCID 19993700, compound

Product 1

HCID 19993695(RS)-3-carboethoxy-4-(2-chloro-1,1,2-trifluoroethoxy)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

3-Carboethoxy-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxypyrazole (2.0 g) was added to a stirred suspension of sodium hydride (80% dispersion in oil; 0.2 g) in dry dioxan (20 ml). When the resultant effervescence had subsided, the solution was heated to 80°-900 °C. and stirred while 2-chloro-1,1,2-trifluoroethylene was passed through. After 6 hours, the reaction was complete and the solvent was evaporated to dryness. The residue was dissolved in dilute hydrochloric acid (2M; 10 ml) and dichloromethane (20 ml) and the layers were separated. The aqueous layer was extracted with dichloromethane (30 ml) and the combined organic layers were washed with water (20 ml), dried over magnesium sulfate, filtered and evaporated. The residue was purified by dry-column chromatography (eluant ether:hexane 1:3) to give (RS)-3-carboethoxy-4-(2-chloro-1,1,2-trifluoroethoxy)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (1.0 g). This was recrystallised from hexane to yield colorless needles, m.p. 105°-106.5° C.

Workup

  1. temperaturethe solution was heated to 80°-900 °C.
  2. customthe solvent was evaporated to dryness
  3. dissolutionThe residue was dissolved in dilute hydrochloric acid (2M; 10 ml)
  4. customdichloromethane (20 ml) and the layers were separated
  5. extractionThe aqueous layer was extracted with dichloromethane (30 ml)
  6. washthe combined organic layers were washed with water (20 ml)
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by dry-column chromatography (eluant ether:hexane 1:3)

Sources & evidence

ORD record
ord-6f85515d64b74f9f950b076b22e47e68
Source dataset
uspto-grants-1991_10
Patent number
US05055482

Reaction notes

Loading…