Hydrochloric Acid → HCID 58382001、化合物

HRID 1627993ノート

反応式

HRID 1627993 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:13]([CH:20]([CH3:22])[CH3:21])([CH:17]([CH3:19])[CH3:18])[CH:14]([CH3:16])[CH3:15])[CH:9]=[C:10]([CH2:11][CH3:12])[C:3]=12.[Li]C(CC)C.CN([CH:31]=[O:32])C.Cl.C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O>[Cl:1][C:2]1[C:7]([CH:31]=[O:32])=[CH:6][N:5]=[C:4]2[N:8]([Si:13]([CH:14]([CH3:15])[CH3:16])([CH:20]([CH3:21])[CH3:22])[CH:17]([CH3:19])[CH3:18])[CH:9]=[C:10]([CH2:11][CH3:12])[C:3]=12

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 516892Sodium BicarbonateHCID 58382052HCID 58382052、化合物HCID 178418400CID 53628100

生成物 1

HCID 58382001HCID 58382001、化合物収率 91.1%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-70 °C

実験手順

4-Chloro-3-ethyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (1.5 g, 4.45 mmol) in THF (25 mL) was cooled to about −70° C. then the sec-BuLi (1.4 M in cyclohexane, 6.36 mL, 8.90 mmol) was added over about 10 min. The mixture was stirred for about 1.25 h at about −70° C. then DMF (1.00 mL, 13.4 mmol) was added over about 5 min. The mixture was stirred for about 30 min then HCl (4.0 M in 1,4-dioxane, 1.11 mL, 4.45 mmol) was added. The mixture was allowed to warm to rt then saturated aqueous NaHCO3 (50 mL) and EtOAc (50 mL) were added. The layers were separated then the aqueous layer was extracted with EtOAc (25 mL) then the combined organics were extracted with saturated aqueous NaCl (25 mL), dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. The material was purified on a 80 g silica gel column with 9:1 heptane/EtOAc as an eluent to give 4-chloro-3-ethyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde (1.48 g, 91%): LC/MS (Table 2, Method g) Rt=2.44 min; MS m/z 365 (M+H)+.

後処理

  1. stirringThe mixture was stirred for about 30 min
  2. temperatureto warm to rt
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with EtOAc (25 mL)
  5. extractionthe combined organics were extracted with saturated aqueous NaCl (25 mL)
  6. dry with materialdried over anhydrous MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe material was purified on a 80 g silica gel column with 9:1 heptane/EtOAc as an eluent

出典と根拠

ORDレコード
ord-247498361eec4ab68ab7541c9d9ddcef
出典データセット
uspto-grants-2014_07
特許番号
US08785639B2

反応ノート

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