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Phosphorus oxychloride → 2,5-Dichloropyridine-4-carbonitrile

HRID 963306
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Reaction equation

HRID 963306 reaction equation
[Cl:1][C:2]1[CH:3]=[N+:4]([O-])[CH:5]=[CH:6][C:7]=1[C:8]#[N:9].C(=O)([O-])O.[Na+].P(Cl)(Cl)([Cl:18])=O>>[C:8]([C:7]1[C:2]([Cl:1])=[CH:3][N:4]=[C:5]([Cl:18])[CH:6]=1)#[N:9].[C:8]([C:7]1[CH:6]=[CH:5][N:4]=[C:3]([Cl:18])[C:2]=1[Cl:1])#[N:9]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 152699483-chloro-4-cyanopyridine N-oxide

Product 2

HCID 135602102,5-Dichloropyridine-4-carbonitrileHCID 190820712,3-Dichloroisonicotinonitrile

Procedure

9.6 g of 3-chloro-4-cyanopyridine was dissolved in 70 ml of dichloromethane. Then, 23.2 g of a 31% hydrogen peroxide aqueous solution and 16.0 g of trifluoroacetic acid were added thereto, and the mixture was stirred overnight at room temperature. After completion of the reaction, the reaction solution was extracted with dichloromethane. The organic layer was washed sequentially with an aqueous sodium hydrogen carbonate solution and an aqueous sodium hydrogen sulfite solution and the dried over anhydrous magnesium sulfate. Then, dichloromethane was distilled off under reduced pressure. The obtained residue was washed with isopropyl ether to obtain 7.2 g of 3-chloro-4-cyanopyridine N-oxide as a white powder (melting point: 172° to 174° C.). Then, 20 ml of phosphorus oxychloride was added to this 3-chloro-4-cyanopyridine N-oxide, and the mixture was refluxed under heating for 5 hours. After cooling, the reaction solution was gradually poured into an aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Then, ethyl acetate was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate) to obtain 3.2 g of 4-cyano-2,5-dichloropyridine (melting point: 55° to 58° C.) and 2.5 g of 4-cyano-2,3-dichloropyridine (melting point: 65° to 69° C.).

Workup

  1. temperaturethe mixture was refluxed
  2. temperatureunder heating for 5 hours
  3. temperatureAfter cooling
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed with water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. distillationThen, ethyl acetate was distilled off under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate)

Sources & evidence

ORD record
ord-7d738ef5d994459ebdd427e485aaadef
Source dataset
uspto-grants-1998_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05763463

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes