Phosphorus oxychloride → 2-chloro-5-phenylnicotinonitrile

HRID 1078248ノート

反応式

HRID 1078248 の反応式
P(Cl)(Cl)(Cl)=O.[C:6]([C:8]1[C:9](=O)[NH:10][CH:11]=[C:12]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:13]=1)#[N:7].P(Cl)(Cl)(Cl)(Cl)[Cl:22]>>[Cl:22][C:9]1[C:8]([C:6]#[N:7])=[CH:13][C:12]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:11][N:10]=1

参加物

4

反応物 3

HCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachlorideHCID 2970612-oxo-5-phenyl-1H-pyridine-3-carbonitrile

生成物 1

HCID 27640432-chloro-5-phenylnicotinonitrile収率 91.6%

反応条件

温度
140 °C

実験手順

Under a nitrogen atmosphere, 68.4 grams (0.45 mole) of phosphorus oxychloride is warmed to a gentle reflux, and 38.9 grams (0.18 mole) of 3-cyano-5-phenylpyridin-2-one is added. Upon completion of addition, 93.6 grams (0.45 mole) of phosphorous pentachloride is added in small portions to maintain the gentle reflux. Upon completion of addition, the reaction mixture is then warmed slowly to about 140° C. where it is stirred for one hour. The reaction mixture is cooled, and excess phosphorus oxychloride is removed under reduced pressure. The concentrate is then poured into 400 grams of ice, where it is stirred until the ice melts. The mixture is then extracted with three 200 mL portions of methylene chloride and 100 mL of diethyl ether. The combined extracts are washed with 150 mL of water and 150 mL of an aqueous solution saturated with sodium chloride. The organic layer is dried with sodium sulfate and filtered. The filtrate is concentrated under reduced pressure at 30° C. to a residue. The residue is distilled under vacuum, yielding 35.4 grams of 2-chloro-3-cyano-5-phenylpyridine, bp 175°-179° C./4 mm Hg., as a crystalline material. The crystalline 2-chloro-3-cyano-5-phenylpyridine is recrystallized from hexane/methylene chloride, mp 149°-150° C.

後処理

  1. additionis added
  2. additionis added in small portions
  3. temperatureto maintain the gentle reflux
  4. additionUpon completion of addition
  5. temperatureThe reaction mixture is cooled
  6. customexcess phosphorus oxychloride is removed under reduced pressure
  7. additionThe concentrate is then poured into 400 grams of ice, where it
  8. stirringis stirred until the ice
  9. extractionThe mixture is then extracted with three 200 mL portions of methylene chloride and 100 mL of diethyl ether
  10. washThe combined extracts are washed with 150 mL of water and 150 mL of an aqueous solution saturated with sodium chloride
  11. dry with materialThe organic layer is dried with sodium sulfate
  12. filtrationfiltered
  13. concentrationThe filtrate is concentrated under reduced pressure at 30° C. to a residue
  14. distillationThe residue is distilled under vacuum

出典と根拠

ORDレコード
ord-64e415468a874cf2bedaba7fce3e5376
出典データセット
uspto-grants-1996_08
特許番号
US05547954

反応ノート

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