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

HRID 1449465

反応式

HRID 1449465 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-967ab7a52e7b4c28a33be5afc0552ffa
出典データセット
uspto-grants-1997_02
特許番号
US05599772

関連ノート

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