Hydrogen Peroxide → Pyridine, 4-[4-fluoro-3-(trifluoromethyl)phenyl]-, 1-oxide

HRID 1005801Notes

Reaction equation

HRID 1005801 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)=[CH:4][C:3]=1[C:14]([F:17])([F:16])[F:15].[OH:18]O>ClCCl.O.C[Re](=O)(=O)=O.[O-2].[Mn+4].[O-2]>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][N+:11]([O-:18])=[CH:12][CH:13]=2)=[CH:4][C:3]=1[C:14]([F:17])([F:15])[F:16]

Participants

7

Reactant 2

HCID 784Hydrogen PeroxideHCID 219067584-[4-Fluoro-3-(trifluoromethyl)phenyl]pyridine

Product 1

HCID 21906801Pyridine, 4-[4-fluoro-3-(trifluoromethyl)phenyl]-, 1-oxideYield 94%

Reagents, catalysts & solvents 4

HCID 178418406HCID 178418406, compoundCatalystHCID 178477782HCID 178477782, compoundCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Then, 4-(4-fluoro-3-trifluoromethyl-phenyl)-pyridine-1-oxide 74 was prepared as follows. To a solution of compound 73 (2.49 g, 10.3 mmol) in dichloromethane (10 mL) was added methyltrioxorhenium(VII) (0.128 g, 0.515 mmol), followed by hydrogen peroxide in water (30%, 5.15 mL). The reaction mixture was stirred at room temperature for 16 hours. Manganese (IV) oxide (0.050 g) was added. The mixture was stirred for another 30 minutes. The organic layer was separated. The aqueous layer was extracted with more dichloromethane (2×10 mL). The combined organic phase was washed with brine (3×30 mL), dried over MgSO4 and filtered. After evaporating the solvent, the crude material was loaded to a silica gel column, eluting with 10% methanol in ethyl acetate to give a white solid 74 (2.51 g, 94%). 1H-NMR (CDCl3, 400 MHz) δ 7.35 (t, J=9.3 Hz, 1H), 7.49 (d, J=7.2 Hz, 2H), 7.74-7.82 (m, 2H), 8.30 (d, J=7.1 Hz, 2H); MS (DCI) m/z 258, 259 (M+H)+.

Workup

  1. customThen, 4-(4-fluoro-3-trifluoromethyl-phenyl)-pyridine-1-oxide 74 was prepared
  2. stirringThe mixture was stirred for another 30 minutes
  3. customThe organic layer was separated
  4. extractionThe aqueous layer was extracted with more dichloromethane (2×10 mL)
  5. washThe combined organic phase was washed with brine (3×30 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customAfter evaporating the solvent
  9. washeluting with 10% methanol in ethyl acetate

Sources & evidence

ORD record
ord-6e91c7ac2193413ca715665301e30868
Source dataset
uspto-grants-2004_09
Patent number
US06787542B2

Reaction notes

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