Phenyl isocyanate → 5-(4-bromo-2-methylphenyl)-3-[(tetrahydro-2H-pyran-2-yloxy)methyl]isoxazole

HRID 709293

Reaktionsgleichung

Reaktionsgleichung von HRID 709293
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]#[CH:9])=[C:4]([CH3:10])[CH:3]=1.[N+:11]([CH2:14][CH2:15][O:16][CH:17]1[CH2:22][CH2:21][CH2:20][CH2:19][O:18]1)([O-])=[O:12].C1(N=C=O)C=CC=CC=1.C(N(CC)CC)C>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[O:12][N:11]=[C:14]([CH2:15][O:16][CH:17]3[CH2:22][CH2:21][CH2:20][CH2:19][O:18]3)[CH:9]=2)=[C:4]([CH3:10])[CH:3]=1

Komponenten

6

Edukt 4

HCID 7672Phenyl isocyanateHCID 8471TriethylamineHCID 37486562-(2-Nitroethoxy)tetrahydropyranHCID 866719694-Bromo-1-ethynyl-2-methylbenzene

Produkt 1

HCID 672484415-(4-bromo-2-methylphenyl)-3-[(tetrahydro-2H-pyran-2-yloxy)methyl]isoxazole

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a flask containing a solution of 4-bromo-1-ethynyl-2-methylbenzene (875 mg, 4.49 mmol) (may be prepared according to the procedures in Journal of Chemical Research (2007), 12 728-732) in toluene (20 mL), was added 2-(2-nitroethoxy)tetrahydro-2H-pyran (1.34 g, 7.63 mmol), phenyl isocyanate (1.82 g, 15.3 mmol), and triethylamine (1.50 mL, 10.8 mmol). The reaction was heated at 100° C. and stirred under nitrogen overnight. The reaction was cooled, quenched with methanol and filtered. The filtrate was evaporated in vacuo onto silica gel. Chromatography on silica gel with a heptane-ethyl acetate gradient (0-35% ethyl acetate) eluted 5-(4-bromo-2-methylphenyl)-3-[(tetrahydro-2H-pyran-2-yloxy)methyl]isoxazole as an orange oil (581 mg, 36.8%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.57-1.71 (m, 4H) 1.73-1.82 (m, 1H) 1.82-1.91 (m, 1H) 2.51 (s, 3H) 3.56-3.62 (m, 1H) 3.89-3.96 (m, 1H) 4.69 (d, J=12.88 Hz, 1H) 4.76-4.79 (m, 1H) 4.86 (d, J=12.88 Hz, 1H) 6.51 (s, 1H) 7.42-7.46 (m, 1H) 7.48 (d, J=1.56 Hz, 1H) 7.59 (d, J=8.20 Hz, 1H).

Aufarbeitung

  1. custommay be prepared
  2. temperatureThe reaction was cooled
  3. customquenched with methanol
  4. filtrationfiltered
  5. customThe filtrate was evaporated in vacuo onto silica gel
  6. washChromatography on silica gel with a heptane-ethyl acetate gradient (0-35% ethyl acetate) eluted 5-(4-bromo-2-methylphenyl)-3-[(tetrahydro-2H-pyran-2-yloxy)methyl]isoxazole as an orange oil (581 mg, 36.8%)

Quellen und Nachweise

ORD-Eintrag
ord-e586cc54656e4e17b662017111b343e5
Quelldatensatz
uspto-grants-2015_11
Patentnummer
US09180123B2

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