Ethyl chloroformate → HCID 58382073、化合物

HRID 1628017ノート

反応式

HRID 1628017 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[CH:9]=[CH:10][C:3]=12.[Li]C(CC)C.Cl[C:27]([O:29][CH2:30][CH3:31])=[O:28]>C1COCC1>[Cl:1][C:2]1[C:7]([C:27]([O:29][CH2:30][CH3:31])=[O:28])=[CH:6][N:5]=[C:4]2[N:8]([Si:11]([CH:15]([CH3:17])[CH3:16])([CH:18]([CH3:20])[CH3:19])[CH:12]([CH3:13])[CH3:14])[CH:9]=[CH:10][C:3]=12

参加物

5

反応物 3

HCID 10928Ethyl chloroformateHCID 114382724-Chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridineHCID 178418400CID 53628100

生成物 1

HCID 58382073HCID 58382073、化合物収率 97%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To a solution of 4-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (0.856 g, 2.77 mmol, Preparation #1, Step A) in THF (20 mL) at about −78° C. was added sec-BuLi (4.35 mL1, 6.10 mmol) dropwise. The reaction was stirred at −78° C. for about 80 min. To the mixture was added ethyl chloroformate (0.665 mL, 6.93 mmol. The flask was removed from the cooling bath and stirred for about 70 min at rt. The mixture was quenched by the addition of a saturated aqueous NH4Cl (5 mL). EtOAc (20 mL) and water (20 mL) were added and the layers were separated. The aqueous layer was extracted with EtOAc (2×15 mL), and the combined organic layers were washed with brine (20 mL). The organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The material was purified by flash chromatography (40 g Redi-Sep™ silica column) eluting with 0-10% EtOAc in heptane to give ethyl 4-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-5-carboxylate (1.02 g, 97%): 1H NMR (400 MHz, DMSO) δ 8.69 (s, 1H), 7.69 (d, J=3.6, 1H), 6.72 (dd, J=68.4, 3.5, 1H), 4.34 (q, J=7.0, 2H), 1.86 (dt, J=15.0, 7.5, 3H), 1.34 (t, J=7.1, 3H), 1.05 (d, J=7.5, 18H).

後処理

  1. customThe flask was removed from the cooling bath
  2. stirringstirred for about 70 min at rt
  3. customThe mixture was quenched by the addition of a saturated aqueous NH4Cl (5 mL)
  4. additionEtOAc (20 mL) and water (20 mL) were added
  5. customthe layers were separated
  6. extractionThe aqueous layer was extracted with EtOAc (2×15 mL)
  7. washthe combined organic layers were washed with brine (20 mL)
  8. dry with materialThe organic layer was dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe material was purified by flash chromatography (40 g Redi-Sep™ silica column)
  12. washeluting with 0-10% EtOAc in heptane

出典と根拠

ORDレコード
ord-411de61ea2024292aa9dd8996eda2926
出典データセット
uspto-grants-2014_07
特許番号
US08785639B2

反応ノート

読み込み中…