Phosphorus oxychloride → 3-Chloropyridine-4-carbonitrile

HRID 1736588

反応式

HRID 1736588 の反応式
[C:1]([C:3]1[CH:8]=[CH:7][N+:6]([O-])=[CH:5][CH:4]=1)#[N:2].P(Cl)(Cl)([Cl:12])=O.P(Cl)(Cl)(Cl)(Cl)[Cl:16]>>[Cl:12][C:7]1[CH:8]=[C:3]([C:1]#[N:2])[CH:4]=[CH:5][N:6]=1.[Cl:16][C:4]1[CH:5]=[N:6][CH:7]=[CH:8][C:3]=1[C:1]#[N:2]

参加物

5

反応物 3

HCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachlorideHCID 846844-Pyridinecarbonitrile, 1-oxide

生成物 2

HCID 5686382-Chloro-4-cyanopyridine収率 24%HCID 106783063-Chloropyridine-4-carbonitrile収率 30%

実験手順

A mixture of 4-cyanopyridine N-oxide (30 g, 0.25 mol), phosphorous oxychloride (96 ml, 0.35 mol) and phosphorous pentachloride (72 g, 0.38 mol) was refluxed at 120°-130° C. for 6 hours and then stirred at room temperature for 12 hours. The reaction mixture was slowly poured into a mixture of ice/Na2CO3 /K2CO3 and was extracted with chloroform (4×250 ml). The solvent was removed in vacuo and the residue was purified by column chromatography on silica eluting with 50% ether/hexanes to afford 8.4 g (24%) of 2-chloro-4-cyanopyridine, m.p. 69.5°-70.5° C. and 10.5 g (30%) of 3-chloro-4-cyanopyridine, m.p. 71.5°-72° C.

後処理

  1. temperaturewas refluxed at 120°-130° C. for 6 hours
  2. extractionwas extracted with chloroform (4×250 ml)
  3. customThe solvent was removed in vacuo
  4. customthe residue was purified by column chromatography on silica eluting with 50% ether/hexanes

出典と根拠

ORDレコード
ord-a76b0051cb7a4357aedaa7d94e168dfa
出典データセット
uspto-grants-1996_07
特許番号
US05541187

関連ノート

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