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

HRID 84311

反応式

HRID 84311 の反応式
[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

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

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, 4 H) 1.73-1.82 (m, 1 H) 1.82-1.91 (m, 1 H) 2.51 (s, 3 H) 3.56-3.62 (m, 1 H) 3.89-3.96 (m, 1 H) 4.69 (d, J=12.88 Hz, 1 H) 4.76-4.79 (m, 1 H) 4.86 (d, J=12.88 Hz, 1 H) 6.51 (s, 1 H) 7.42-7.46 (m, 1 H) 7.48 (d, J=1.56 Hz, 1 H) 7.59 (d, J=8.20 Hz, 1 H).

後処理

  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%)

出典と根拠

ORDレコード
ord-2cb74bec6f0d4a15b08717c97ace5bdd
出典データセット
uspto-grants-2014_09
特許番号
US08846933B2

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