Allyl chloroformate → 5-(N-[prop-1-en-3-yloxycarbonyl]amino)-3-(1-tert-butoxycarbonylpiperidin-4-yl)pyrrolo[3,2-b]pyridine

HRID 398983ノート

反応式

HRID 398983 の反応式
[NH2:1][C:2]1[N:7]=[C:6]2[C:8]([CH:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]3)=[CH:9][NH:10][C:5]2=[CH:4][CH:3]=1.Cl[C:25]([O:27][CH2:28][CH:29]=[CH2:30])=[O:26]>N1C=CC=CC=1>[CH2:30]=[CH:29][CH2:28][O:27][C:25]([NH:1][C:2]1[N:7]=[C:6]2[C:8]([CH:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]3)=[CH:9][NH:10][C:5]2=[CH:4][CH:3]=1)=[O:26]

参加物

4

反応物 2

HCID 18052Allyl chloroformate2 回HCID 117268345-Amino-3-(1-tert-butoxycarbonylpiperidin-4-yl)pyrrolo[3,2-b]pyridine

生成物 1

HCID 196015485-(N-[prop-1-en-3-yloxycarbonyl]amino)-3-(1-tert-butoxycarbonylpiperidin-4-yl)pyrrolo[3,2-b]pyridine収率 60%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒

反応条件

温度
50 °C

実験手順

A mixture of 4.0 gm (12.6 mMol) 5-amino-3-(1-tert-butoxycarbonylpiperidin-4-yl)pyrrolo[3,2-b]pyridine and 2.7 mL (25.2 mMol) allyl chloroformate in 200 mL pyridine was heated at 50° C. for 5 hours. At this point an additional 2 mL of allyl chloroformate were added and heating was continued for another 1.5 hours. The reaction mixture was concentrated under reduced pressure and the resulting residue partitioned between 1N sodium hydroxide and chloroform. The phases were separated and the aqueous phase was extracted well with chloroform. The organic phases were combined, washed with saturated aqueous sodium chloride, dried over sodium sulfate and concentrated under reduced pressure. This residue was dissolved in 2M ammonia in methanol for two hours. The reaction mixture was concentrated under reduced pressure and the residue subjected to flash silica gel chromatography, eluting with dichloromethane containing from 2-5% methanol and 1% ammonium hydroxide. Fractions containing product were combined and concentrated under reduced pressure. The residue was crystallized from aqueous ethanol to provide 2.9 gm (60%) 5-(N-[prop-1-en-3-yloxycarbonyl]amino)-3-(1-tert-butoxycarbonylpiperidin-4-yl)pyrrolo[3,2-b]pyridine.

後処理

  1. temperatureheating
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. customthe resulting residue partitioned between 1N sodium hydroxide and chloroform
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted well with chloroform
  6. washwashed with saturated aqueous sodium chloride
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThis residue was dissolved in 2M ammonia in methanol for two hours
  10. concentrationThe reaction mixture was concentrated under reduced pressure
  11. washeluting with dichloromethane containing from 2-5% methanol and 1% ammonium hydroxide
  12. additionFractions containing product
  13. concentrationconcentrated under reduced pressure
  14. customThe residue was crystallized from aqueous ethanol

出典と根拠

ORDレコード
ord-8af0be4458f54d83a8dff315f5939ec0
出典データセット
uspto-grants-1998_10
特許番号
US05817671

反応ノート

読み込み中…