2-Chloro-3-methyl-5-nitropyridine → 2-Fluoro-3-methyl-5-nitropyridine

HRID 2185734Notes

Reaction equation

HRID 2185734 reaction equation
Cl[C:2]1[C:7]([CH3:8])=[CH:6][C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1.[F-:12].[K+]>[Br-].C1([P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(#N)C.CCOCC>[F:12][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1

Participants

6

Reactant 2

HCID 896482-Chloro-3-methyl-5-nitropyridineHCID 522689Potassium Fluoride

Product 1

HCID 124081842-Fluoro-3-methyl-5-nitropyridineYield 61.9%

Reagents, catalysts & solvents 3

HCID 2724163Tetraphenylphosphonium BromideCatalystHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

2-Chloro-3-methyl-5-nitropyridine (15.0 g, 86.9 mmol; from Maybridge Chemical Co.), KF (12 g, 258 mmol), and tetraphenylphosphonium bromide (20 g, 47.7 mmol) were combined in 200 mL of acetonitrile and heated at reflux for 4 days. The mixture was diluted with Et2O (500 mL), filtered, and the solution was concentrated. The residue was triturated with hot hexane, then the combined hexane solutions were concentrated to give 8.4 g (60%) of the title compound: 1H NMR (DMSO-d6, 300 MHz) δ8.95 (dd, J=1.6 Hz, 1H), 8.43 (m, 1H), 2.42 (s, 1H); MS (CI/NH3) m/z: 157 (M+H)+.

Workup

  1. temperatureheated
  2. temperatureat reflux for 4 days
  3. filtrationfiltered
  4. concentrationthe solution was concentrated
  5. customThe residue was triturated with hot hexane
  6. concentrationthe combined hexane solutions were concentrated

Sources & evidence

ORD record
ord-7b42fde34f0c4ce285e3f12477424135
Source dataset
uspto-grants-2002_06
Patent number
US06403575B1

Reaction notes

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