Ethylene Glycol → 3-(3-phenylsulfanyl-1H-pyrrolo[2,3-b]pyridine-5-yl)-phenol

HRID 729834ノート

反応式

HRID 729834 の反応式
I[C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8]([C:11]3[CH:12]=[C:13]([O:17]S(C4C=CC(C)=CC=4)(=O)=O)[CH:14]=[CH:15][CH:16]=3)[CH:9]=2)[N:4](S(C2C=CC(C)=CC=2)(=O)=O)[CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[C:44]1([SH:50])[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1.C(O)CO.[OH-].[K+].Cl>[Cu]I.C(O)(C)C>[C:44]1([S:50][C:2]2[C:10]3[C:5](=[N:6][CH:7]=[C:8]([C:11]4[CH:12]=[C:13]([OH:17])[CH:14]=[CH:15][CH:16]=4)[CH:9]=3)[NH:4][CH:3]=2)[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1

参加物

9

反応物 6

HCID 174Ethylene GlycolHCID 313Hydrochloric AcidHCID 7969ThiophenolHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 59699703toluene-4-sulfonic acid 3-[3-iodo-1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine-5-yl]-phenyl ester

生成物 1

HCID 160391543-(3-phenylsulfanyl-1H-pyrrolo[2,3-b]pyridine-5-yl)-phenol収率 17.5%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 3776Isopropanol溶媒

反応条件

温度
80 °C

実験手順

To toluene-4-sulfonic acid 3-[3-iodo-1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine-5-yl]-phenyl ester (50 mg, 0.077 mmol), copper(I) iodide (1.5 mg, 0.004 mmol), and potassium carbonate (16 mg, 0.155 mmol) under nitrogen atmosphere was added isopropanol (0.2 mL), benzenethiol (8 μL, 0.077 mmol), and ethylene glycol (9 uL, 0.155 mmol). The reaction mixture was stirred at 80° C. for 24 h. A (1:1) mixture of 2 M aqueous KOH and MeOh (1 mL) was added, and the reaction mixture was further stirred at 50° C. for 3 h. The mixture was acidified to pH5 with 1N aqueous HCl and extracted with EtOAc twice. Extracts were combined and concentrated under vacuum. Purification by reverse phase chromatography using a gradient of H2O and acetonitrile (with 0.1% formic acid as a modifier) afforded 3-(3-phenylsulfanyl-1H-pyrrolo[2,3-b]pyridine-5-yl)-phenol as a white solid (4.3 mg, 17% yield). 1H NMR (500 MHz, DMSO-d6) δ 6.74 (dd, J=2.5, 9.0 Hz, 1H), 6.98 (t, J=2.0 Hz, 1H), 7.08 (m, 4H), 7.23 (m, 3H), 7.85 (d, J=2.5 Hz, 1H), 7.98 (s, 1H), 8.56 (d, J=2.0 Hz, 1H), 9.55 (broad s, 1H), 12.4 (broad s, 1H). MS: m/z 319 (M+H+).

後処理

  1. additionwas added
  2. stirringthe reaction mixture was further stirred at 50° C. for 3 h
  3. extractionextracted with EtOAc twice
  4. concentrationconcentrated under vacuum
  5. customPurification by reverse phase chromatography

出典と根拠

ORDレコード
ord-dd444d593a204408b97fa5057597697d
出典データセット
uspto-grants-2009_09
特許番号
US07582637B2

反応ノート

読み込み中…