m-Chloroperbenzoic acid → 3-Chloro-4-cyano-5-(4-phenoxyphenyl)pyridine 1-oxide

HRID 81035Notes

Reaction equation

HRID 81035 reaction equation
[Cl:1][C:2]1[CH:9]=[N:8][CH:7]=[C:6]([C:10]2[CH:15]=[CH:14][C:13]([O:16][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[CH:12][CH:11]=2)[C:3]=1[C:4]#[N:5].ClC1C=CC=C(C(OO)=[O:31])C=1>ClCCl>[Cl:1][C:2]1[CH:9]=[N+:8]([O-:31])[CH:7]=[C:6]([C:10]2[CH:11]=[CH:12][C:13]([O:16][C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=3)=[CH:14][CH:15]=2)[C:3]=1[C:4]#[N:5]

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 669269133-Chloro-5-(4-phenoxyphenyl)isonicotinonitrile

Product 1

HCID 669269043-Chloro-4-cyano-5-(4-phenoxyphenyl)pyridine 1-oxideYield 63.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 3-chloro-5-(4-phenoxyphenyl)isonicotinonitrile (0.495 g, 1.614 mmol) and 77% 3-chloroperbenzoic acid (1.808 g, 8.07 mmol) in dichloromethane (20 mL) was stirred at room temperature. After 22 h at room temperature, the mixture was diluted with dichloromethane (100 mL), washed with 1 M sodium sulfite (25 mL), 1 N NaOH (2×25 mL), brined (25 mL), dried (MgSO4) and concentrated. Silica gel chromatography, loading with dichloromethane and eluting with 20-50% ethyl acetate in hexanes, gave 3-chloro-4-cyano-5-(4-phenoxyphenyl)pyridine 1-oxide as white solid (328.8 mg, 63% yield). 1H NMR (400 MHz, CDCl3) δ ppm 8.25 (1H, δ, J=1.51 Hz), 8.16 (1H, δ, J=1.51 Hz), 7.46-7.58 (2H, m), 7.36-7.45 (2H, m), 7.21 (1H, t, J=7.40 Hz), 7.03-7.16 (4H, m); MS (ES+) m/z: 323 (M+H); LC retention time: 3.863 min (analytical HPLC Method A).

Workup

  1. washwashed with 1 M sodium sulfite (25 mL), 1 N NaOH (2×25 mL)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated
  4. washeluting with 20-50% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-0f01cd78d9df4634a8b25a7b0fb51ddf
Source dataset
uspto-grants-2014_09
Patent number
US08846673B2

Reaction notes

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