m-Chloroperbenzoic acid → 3-Bromo-2-chloropyridine 1-oxide

HRID 2178677Notes

Reaction equation

HRID 2178677 reaction equation
[Br:1][C:2]1[C:3]([Cl:8])=[N:4][CH:5]=[CH:6][CH:7]=1.ClC1C=C(C=CC=1)C(OO)=[O:14]>ClCCCl>[Br:1][C:2]1[C:3]([Cl:8])=[N+:4]([O-:14])[CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 6933243-Bromo-2-chloropyridine

Product 1

HCID 866717273-Bromo-2-chloropyridine 1-oxide

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A solution of 3-bromo-2-chloropyridine (50 g, 0.26 mol) and 3-chloroperoxybenzoic acid (70-75% wet with water; 67.3 g, 0.39 mol) in 1,2-dichloroethane (600 mL) was heated under reflux for 7 hours. The reaction was then concentrated under reduced pressure to an approximate volume of 200 mL and purified by chromatography on silica gel (Gradient: 80% to 100% ethyl acetate in heptane, followed by 5% to 10% methanol in ethyl acetate) to yield the title compound as a brown solid. Yield: 32.9 g, 0.158 mol, 61%. LCMS m/z 210.0 (M+1). 1H NMR (400 MHz, CDCl3) δ 7.09 (dd, J=7.8, 6.9 Hz, 1H), 7.52 (d, J=8.2 Hz, 1H), 8.33 (d, J=6.4 Hz, 1H).

Workup

  1. temperatureunder reflux for 7 hours
  2. concentrationThe reaction was then concentrated under reduced pressure to an approximate volume of 200 mL
  3. custompurified by chromatography on silica gel (Gradient: 80% to 100% ethyl acetate in heptane, followed by 5% to 10% methanol in ethyl acetate)

Sources & evidence

ORD record
ord-23445e5eff1f4c5a82efdb77c7d14b06
Source dataset
uspto-grants-2015_06
Patent number
US09067934B2

Reaction notes

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