Hydrogen Peroxide → HCID 86699904, compound

HRID 1428995Notes

Reaction equation

HRID 1428995 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:10]([S:11][C:12]([F:15])([F:14])[F:13])=[C:9]([CH3:16])[N:8]([C:17]2[C:22]([F:23])=[CH:21][C:20]([C:24]([F:27])([F:26])[F:25])=[CH:19][C:18]=2[Cl:28])[N:7]=1)=[O:5])[CH3:2].FC(F)(F)C(O)=[O:32].OO>ClCCl>[CH2:1]([O:3][C:4]([C:6]1[C:10]([S:11]([C:12]([F:15])([F:13])[F:14])=[O:32])=[C:9]([CH3:16])[N:8]([C:17]2[C:22]([F:23])=[CH:21][C:20]([C:24]([F:26])([F:27])[F:25])=[CH:19][C:18]=2[Cl:28])[N:7]=1)=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 86699905HCID 86699905, compound

Product 1

HCID 86699904HCID 86699904, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 1-(2-Chloro-6-fluoro-4-trifluoromethyl-phenyl)-5-methyl-4-trifluoromethylsulfanyl-1H-pyrazole-3-carboxylic acid ethyl ester (1.2 g, 2.7 mmol) in dichloromethane (6 mL) was added trifluoroacetic acid (2.4 mL) at 0° C. To the reaction mixture was added an aqueous solution of hydrogen peroxide (30 wt %, 0.9 g, 8.3 mmol) at 0° C. The reaction mixture was stirred at 0° C. for 6 h. The reaction was quenched by addition of a solution of sodium bisulfite (0.8 g) in water (12 mL). The resulting mixture was extracted with dichloromethane. The organic layer was dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by column chromatography, elution with heptanes/EtOAc, to give 1-(2-Chloro-6-fluoro-4-trifluoromethyl-phenyl)-5-methyl-4-trifluoromethanesulfinyl-1H-pyrazole-3-carboxylic acid ethyl ester as a white solid (1.2 g, 2.6 mmol, 99%). 1H NMR (400 MHz, CDCl3) δ ppm 1.42 (t, J=7.1 Hz, 3H), 2.51 (s, 3H), 4.36-4.55 (m, 2H), 7.54 (dd, J=8.3, 1.6 Hz, 1H), 7.72 (s, 1H). 19F NMR (376 MHz, CDCl3) δ ppm −113.2 (d, J=7.9 Hz, 0.5F), −112.8 (d, J=9.2 Hz, 0.5F), −74.0 (s, 1.5F), −73.8 (s, 1.5F), −63.8 (s, 3F).

Workup

  1. customThe reaction was quenched by addition of a solution of sodium bisulfite (0.8 g) in water (12 mL)
  2. extractionThe resulting mixture was extracted with dichloromethane
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by column chromatography, elution with heptanes/EtOAc

Sources & evidence

ORD record
ord-91920f617ec04bf5b63f621cc543bf28
Source dataset
uspto-grants-2015_01
Patent number
US08937185B2

Reaction notes

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