Phosphorus oxychloride → Triethyl 6-chloro-2,3,5-pyridinetricarboxylate

HRID 864301

反応式

HRID 864301 の反応式
O=[C:2]1[NH:7][C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:5]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:4]=[C:3]1[C:18]([O:20][CH2:21][CH3:22])=[O:19].P(Cl)(Cl)([Cl:25])=O>CN(C)C=O>[Cl:25][C:2]1[N:7]=[C:6]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:5]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:4][C:3]=1[C:18]([O:20][CH2:21][CH3:22])=[O:19]

参加物

4

反応物 2

HCID 24813Phosphorus oxychlorideHCID 19958207Triethyl 1,6-dihydro-6-oxo-2,3,5-pyridinetricarboxylate

生成物 1

HCID 19958209Triethyl 6-chloro-2,3,5-pyridinetricarboxylate収率 47%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A solution of triethyl 1,6-dihydro-6-oxo-2,3,5- pyridine-tricarboxylate (39.7 g) in 300 mL of phosphorous oxychloride and 0.5 mL dimethylformamide is stirred at 100° C. for four hours and 15 minutes. After cooling, the excess phosphorous oxychloride is removed under vacuum. The residue is taken up in 200 mL methylene chloride and the solution poured into 500 mL of ice water and the layers are separated. The aqueous layer, made basic with concentrated ammonium hydroxide and ice, is extracted with 150 mL methylene chloride. The combined methylene chloride extracts are dried over magnesium sulfate, filtered and concentrated under vacuum, and the resulting crude product is chromatographed on silica using 5:1 hexanes:ethyl acetate and then 4:1 hexanes:ethyl acetate as eluants affording 26.5 g (47%) of the title product as an oil.

後処理

  1. temperatureAfter cooling
  2. customthe excess phosphorous oxychloride is removed under vacuum
  3. additionthe solution poured into 500 mL of ice water
  4. customthe layers are separated
  5. extractionis extracted with 150 mL methylene chloride
  6. dry with materialThe combined methylene chloride extracts are dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customthe resulting crude product is chromatographed on silica using 5:1 hexanes

出典と根拠

ORDレコード
ord-ed46ad29850d4a3c8ed099f5ee3b0c11
出典データセット
uspto-grants-1996_10
特許番号
US05563113

関連ノート

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