Sodium Acetate → 1h-Indazole,6-bromo-3-ethyl-1-(4-methoxyphenyl)-

HRID 849317Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 849317
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:13](=O)[CH2:14][CH3:15])=[C:6](OS(C)(=O)=O)[CH:7]=1.Cl.[CH3:18][O:19][C:20]1[CH:25]=[CH:24][C:23]([NH:26][NH2:27])=[CH:22][CH:21]=1.C([O-])(=O)C.[Na+]>ClCCl>[Br:1][C:2]1[CH:7]=[C:6]2[C:5]([C:13]([CH2:14][CH3:15])=[N:27][N:26]2[C:23]2[CH:24]=[CH:25][C:20]([O:19][CH3:18])=[CH:21][CH:22]=2)=[CH:4][CH:3]=1

Komponenten

5

Edukt 3

HCID 517045Sodium AcetateHCID 27239044-Methoxyphenylhydrazine hydrochlorideHCID 109248095-Bromo-2-propionylphenyl methanesulfonate

Produkt 1

HCID 110349101h-Indazole,6-bromo-3-ethyl-1-(4-methoxyphenyl)-Ausbeute 40 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
135 °C

Versuchsvorschrift

Methanesulfonic acid 5-bromo-2-propionyl-phenyl ester (5.00 g, 16.3 mmol) was combined with 4-methoxyphenylhydrazine hydrochloride (4.00 g, 22.9 mmol) and sodium acetate (4.01 g, 48.9 mmol) in xylenes (30 mL). The reaction mixture was heated to 135° C. for 36 hours using a Dean Stark apparatus. The reaction was cooled to room temperature, diluted with dichloromethane (50 mL), and washed with water (50 mL) and 1N aqueous hydrochloric acid (50 mL). The organic extract were dried over magnesium sulfate and concentrated. The crude product was purified by chromatography on silica gel eluting with 4:1 hexanes/ethyl acetate to yield 2.14 g of 6-bromo-3-ethyl-1-(4-methoxy-phenyl)-1H-indazole (40% yield). 1H NMR (400 MHz, CDCl3) δ 1.43 (t, 3, J=7.7), 3.00 (q, 2, J=7.7), 3.86 (s, 3), 7.03 (d, 2, J=8.9), 7.25 (dd, 1, J=8.5, 1.5), 7.53 (d, 2, J=9.1), 7.58 (d, 1, J=8.5), 7.73 (d, 1, J=1.5). 13C NMR (100 MHz, CDCl3) δ 13.53, 20.34, 55.61, 113.02, 114.70, 121.33, 121.70, 122.45, 123.93, 124.50, 132.90, 140.67, 148.83, 158.42. IR 2970, 2934, 1604, 1519, 1461, 1442, 1300, 1250, 1050, 1035, 945, 832 cm-1. Analysis calculated for C16H15BrN2O: C, 58.02; H, 4.56; N, 8.46. Found: C, 58.39; H, 4.69; N, 8.13.

Aufarbeitung

  1. temperatureThe reaction was cooled to room temperature
  2. washwashed with water (50 mL) and 1N aqueous hydrochloric acid (50 mL)
  3. extractionThe organic extract
  4. dry with materialwere dried over magnesium sulfate
  5. concentrationconcentrated
  6. customThe crude product was purified by chromatography on silica gel eluting with 4:1 hexanes/ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-19dbd272e77a48b382c7cef0d015af51
Quelldatensatz
uspto-grants-2000_01
Patentnummer
US06011159

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