m-Chloroperbenzoic acid → 3-Chloromethyl-4-trifluoromethylpyridine-N-oxide

HRID 1292046Notes

Reaction equation

HRID 1292046 reaction equation
Cl.[Cl:2][CH2:3][C:4]1[CH:5]=[N:6][CH:7]=[CH:8][C:9]=1[C:10]([F:13])([F:12])[F:11].C([O-])(O)=[O:15].[Na+].ClCC1C=NC=CC=1C(F)(F)F.C1C=C(Cl)C=C(C(OO)=O)C=1>C(Cl)(Cl)Cl>[Cl:2][CH2:3][C:4]1[CH:5]=[N+:6]([O-:15])[CH:7]=[CH:8][C:9]=1[C:10]([F:13])([F:11])[F:12]

Participants

6

Reactant 4

HCID 70297m-Chloroperbenzoic acid2×HCID 516892Sodium BicarbonateHCID 189140993-(Chloromethyl)-4-(trifluoromethyl)pyridineHCID 189141093-Chloromethyl-4-trifluoromethylpyridine hydrochloride

Product 1

HCID 189141073-Chloromethyl-4-trifluoromethylpyridine-N-oxide

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

3-Chloromethyl-4-trifluoromethylpyridine hydrochloride (204 mg, 0.88 mmol) from step 2 above was dissolved in CHCl3 (50 mL) and treated with saturated aqueous NaHCO3. The organic layer was removed, dried (Na2SO4), and concentrated to give the free pyridine. This 3-chloromethyl-4-(trifluoromethyl)pyridine was dissolved in CHCl3 (10 mL) and MCPBA was added (0.19 g of 80% MCPBA by weight; 0.88 mmol). After 29 h, the solution was extracted with saturated aqueous NaHCO3 (10 mL), dried (Na2SO4), filtered, and evaporated under reduced pressure. The residue was purified by pressurized silica gel column chromatography eluting with EtOAc. 3-Chloromethyl-4-trifluoromethylpyridine-N-oxide was obtained as a solid (TLC: Rf = 0.35 (EtOAc); FAB MS m/z 212 (M+ +H)).

Workup

  1. customThe organic layer was removed
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated
  4. customto give the free pyridine
  5. extractionthe solution was extracted with saturated aqueous NaHCO3 (10 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe residue was purified by pressurized silica gel column chromatography
  10. washeluting with EtOAc

Sources & evidence

ORD record
ord-2178c185ee0d46d1ad6992af6432361f
Source dataset
uspto-grants-1998_05
Patent number
US05756497

Reaction notes

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