Iodine → 5-chloro-3-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde

HRID 1627135ノート

反応式

HRID 1627135 の反応式
[Cl:1][C:2]1[CH:7]=[N:6][C:5]2[NH:8][CH:9]=[CH:10][C:4]=2[C:3]=1[CH:11]=[O:12].[I:13]I.[I-].[Na+].[OH-].[Na+].[H-].[Na+].[S:21](Cl)([C:24]1[CH:30]=[CH:29][C:27]([CH3:28])=[CH:26][CH:25]=1)(=[O:23])=[O:22]>CCO.O.CCOC(C)=O>[Cl:1][C:2]1[CH:7]=[N:6][C:5]2[N:8]([S:21]([C:24]3[CH:30]=[CH:29][C:27]([CH3:28])=[CH:26][CH:25]=3)(=[O:23])=[O:22])[CH:9]=[C:10]([I:13])[C:4]=2[C:3]=1[CH:11]=[O:12]

参加物

10

反応物 6

HCID 807IodineHCID 5238Sodium IodideHCID 73974-Toluenesulfonyl chlorideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 242292805-Chloro-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde

生成物 1

HCID 582934415-chloro-3-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde収率 70.2%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of 5-chloro-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde (5.0 g, 27.7 mmol) in EtOH (100 mL) was added iodine (8.43 g, 33.2 mmol), sodium iodide (4.98 g, 33.2 mmol), and aqueous NaOH (1N, 35 mL, 35 mmol). After stirring for 4 h at room temperature, the reaction mixture was diluted with water (200 mL). An orange precipitate was collected by filtration and dried under vacuum. The solid was dissolved in DMF (60 mL) and sodium hydride (60%, 1.33 g, 33.2 mmol) was slowly added. The deep red solution was stirred for 30 min at room temperature. Tosyl chloride (5.81 g, 30.5 mmol) was added and the mixture was stirred at room temperature for 2 h. The mixture was diluted with EtOAc and the reaction was quenched with water. The organics were separated, washed with aqueous NaHSO3 (0.1 N) and brine, dried over MgSO4, and concentrated. Purification by silica gel chromatography (3:1:1 hexane/DCM/EtOAc) gave the title compound as a yellow solid (8.96 g, 70%). 1H NMR (500 MHz, DMSO-d6) δ 3.15 (s, 3 H), 8.24 (d, J=8.5 Hz, 2 H), 8.81 (d, J=8.5 Hz, 2 H), 9.17 (s, 1 H), 9.38 (s, 1 H), 11.81 (s, 1 H). [M+H] calc'd for C15H10ClIN2O3S, 461, 463; found, 461, 463.

後処理

  1. filtrationAn orange precipitate was collected by filtration
  2. customdried under vacuum
  3. dissolutionThe solid was dissolved in DMF (60 mL)
  4. stirringThe deep red solution was stirred for 30 min at room temperature
  5. stirringthe mixture was stirred at room temperature for 2 h
  6. customthe reaction was quenched with water
  7. customThe organics were separated
  8. washwashed with aqueous NaHSO3 (0.1 N) and brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated
  11. customPurification by silica gel chromatography (3:1:1 hexane/DCM/EtOAc)

出典と根拠

ORDレコード
ord-13106fd1255f4c208b5b7acaeb2a15da
出典データセット
uspto-grants-2014_07
特許番号
US08785429B2

反応ノート

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