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

HRID 603057Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 603057
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.[K].C(=O)([O-])[O-].[C:43]1([SH:49])[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1.C(O)CO.[OH-].[K+].Cl>[Cu]I.C(O)(C)C>[C:43]1([S:49][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:48]=[CH:47][CH:46]=[CH:45][CH:44]=1

Komponenten

10

Edukt 7

HCID 174Ethylene GlycolHCID 313Hydrochloric AcidHCID 7969ThiophenolHCID 14797Potassium HydroxideHCID 19660Carbonate IonHCID 5462222PotassiumHCID 59699703toluene-4-sulfonic acid 3-[3-iodo-1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine-5-yl]-phenyl ester

Produkt 1

HCID 160391543-(3-phenylsulfanyl-1H-pyrrolo[2,3-b]pyridine-5-yl)-phenolAusbeute 17,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 3776IsopropanolLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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+).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-ee8ce95094d8440daf8152f5eaa671c2
Quelldatensatz
uspto-grants-2011_03
Patentnummer
US07906648B2

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