Water → 3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)aniline

HRID 1183909Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1183909
[Br:1]N1C(=O)CCC1=O.[CH3:9][N:10]1[C:14]([C:15]2[CH:16]=[C:17]([NH:29]C(=O)C)[CH:18]=[CH:19][C:20]=2[O:21][CH2:22][C:23]([CH3:28])([N+:25]([O-:27])=[O:26])[CH3:24])=[CH:13][CH:12]=[N:11]1.[OH-].[Na+].O>CO>[Br:1][C:13]1[CH:12]=[N:11][N:10]([CH3:9])[C:14]=1[C:15]1[CH:16]=[C:17]([CH:18]=[CH:19][C:20]=1[O:21][CH2:22][C:23]([CH3:28])([N+:25]([O-:27])=[O:26])[CH3:24])[NH2:29]

Komponenten

6

Edukt 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 67265394N-(3-(2-methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)phenyl)acetamide

Produkt 1

HCID 672655183-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)anilineAusbeute 61 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

N-Bromosuccinimide (0.931 g, 5.23 mmol) was added to a suspension of N-(3-(2-Methyl-2H-pyrazol-3-yl)-4-(2-methyl-2-nitropropoxy)phenyl)acetamide (1.58 g, 4.75 mmol) in 10 mL of methanol, and the mixture was stirred at room temperature. A clear solution was obtained within minutes. After 20 min, a solution of sodium hydroxide (1.14 g, 28.5 mmol) in water (1.00 mL, 55.5 mmol) was added, and the solution was heated to 160° C. for 0.5 hr under microwave irradiation in a heavy walled sealed tube. The solvent was evaporated under reduced pressure, and the residue was taken up in saturated sodium bicarbonate and extracted twice with dichloromethane. The extracts were combined, dried with sodium sulfate, filtered, and evaporated to dryness. The crude product was purified by flash chromatography (ethyl acetate-hexanes 1:2, then 1:1) to afford the title compound as an off-white solid (1.07 g, 61%). LCMS m/z (%)=371.0 (M+H 81Br 36%), 369.1 (M+H 79Br 30%). 1H NMR (400 MHz, CDCl3) δ ppm 1.44 (s, 3 H), 1.50 (s, 3 H), 3.63 (s, 3 H), 3.81 (d, J=9.85 Hz, 1 H), 4.34 (d, J=9.85 Hz, 1 H), 6.72 (d, J=1.52 Hz, 1 H), 6.87-6.93 (m, 2 H), 7.51 (s, 1 H).

Aufarbeitung

  1. customA clear solution was obtained within minutes
  2. temperaturethe solution was heated to 160° C. for 0.5 hr under microwave irradiation in a heavy walled sealed tube
  3. customThe solvent was evaporated under reduced pressure
  4. extractionextracted twice with dichloromethane
  5. dry with materialdried with sodium sulfate
  6. filtrationfiltered
  7. customevaporated to dryness
  8. customThe crude product was purified by flash chromatography (ethyl acetate-hexanes 1:2

Quellen und Nachweise

ORD-Eintrag
ord-9516714f8a3a42588c88e87d53558792
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08664258B2

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