Hydrogen Peroxide → HCID 22618410, compound

HRID 1078460Notes

Reaction equation

HRID 1078460 reaction equation
FC(F)(F)C(OC(=O)C(F)(F)F)=[O:4].OO.[NH2:16][C:17]1[C:21]([C:22]#[N:23])=[CH:20][N:19]([C:24]2[C:29]([Cl:30])=[CH:28][C:27]([C:31]([F:34])([F:33])[F:32])=[CH:26][C:25]=2[Cl:35])[N:18]=1.[OH2:36]>ClCCl>[Cl:30][C:29]1[CH:28]=[C:27]([C:31]([F:34])([F:32])[F:33])[CH:26]=[C:25]([Cl:35])[C:24]=1[N:19]1[CH:20]=[C:21]([C:22]#[N:23])[C:17]([N+:16]([O-:4])=[O:36])=[N:18]1

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 962WaterHCID 9845Trifluoroacetic anhydrideHCID 163845M&B 39279

Product 1

HCID 22618410HCID 22618410, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

Trifluoroacetic anhydride (3.5 ml) was added dropwise to a stiffed mixture of 85% w/v hydrogen peroxide solution (0.56 ml) in dichloromethane (15 ml) maintaining at 0°-10° C. After warming to 20° C. during 5 minutes, a solution of 3-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-cyanopyrazole (1.0 g; hereinafter described in Reference Example 33) in dichloromethane (10 ml) was added dropwise over 5 minutes. A temperature rise of 10° C. was observed during the addition, and the mixture heated under reflux for 1.5 hours. After cooling, the solution was poured onto excess water, and the organic solution washed in turn with solutions of sodium bicarbonate and sodium bisulphite. Drying over anhydrous magnesium sulphate, followed by evaporation in vacuo gave a buff solid, which was purified by chromatography on silica (Merck, 40-230 mesh, 0.7 kg cm-2) eluting with dichloromethane. The resultant white solid was recrystallized from a mixture of dichloromethane and hexane to give 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-cyano-3-nitropyrazole as white crystals (0.7 g), m.p. 163°-165° C.

Workup

  1. temperaturemaintaining at 0°-10° C
  2. additionwas added dropwise over 5 minutes
  3. additionA temperature rise of 10° C. was observed during the addition
  4. temperaturethe mixture heated
  5. temperatureunder reflux for 1.5 hours
  6. temperatureAfter cooling
  7. washthe organic solution washed in turn with solutions of sodium bicarbonate and sodium bisulphite
  8. dry with materialDrying over anhydrous magnesium sulphate
  9. customfollowed by evaporation in vacuo
  10. customgave a buff solid, which
  11. customwas purified by chromatography on silica (Merck, 40-230 mesh, 0.7 kg cm-2)
  12. washeluting with dichloromethane
  13. customThe resultant white solid was recrystallized from a mixture of dichloromethane and hexane

Sources & evidence

ORD record
ord-fe2289bbe981460d94e94108a18d3dd5
Source dataset
uspto-grants-1996_08
Patent number
US05547974

Reaction notes

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