4a,5,6,7,8,8a-Hexahydro-8a-hydroxy-3-(trifluoromethyl)-4H-1,2-benzoxazine | 137496-28-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 4a,5,6,7,8,8a-Hexahydro-8a-hydroxy-3-(trifluoromethyl)-4H-1,2-benzoxazine
• 英文别名: 3-(trifluoromethyl)-4,4a,5,6,7,8-hexahydro-1,2-benzoxazin-8a-ol
• CAS: 137496-28-7
• 化学式: C₉H₁₂F₃NO₂
• 分子量: 223.195
• InChiKey: SZTJADXSMNPQFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  41.8
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4a,5,6,7,8,8a-Hexahydro-3-(trifluoromethyl)-8a-(trimethylsiloxy)-4H-1,2-benzoxazine 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以96%的产率得到4a,5,6,7,8,8a-Hexahydro-8a-hydroxy-3-(trifluoromethyl)-4H-1,2-benzoxazine
  参考文献：
  名称：

  Efficient synthesis of trifluoromethyl-substituted 5,6-dihydro-4H-1,2-oxazines by the hetero-Diels-Alder reaction of 1,1,1-trifluoro-2-nitroso-2-propene and electron-rich olefins

  摘要：

  1,1,1-Trifluoro-2-nitroso-2-propene (1) was generated in situ by treatment of the alpha-bromo oxime 5 with base. Moderate to excellent yields of the 3-trifluoromethyl-substituted 1,2-oxazines 17-27 were obtained from the reaction of 1 and the silyl enol ethers 6-16, respectively. Other dienophiles, i.e., allyltrimethylsilane, cyclopentadiene, furan, and dihydropyran, upon reaction with 1 provided the cycloadducts 31-34, respectively, in good yield. The results demonstrated that 1 is probably the most reactive heterodiene that has so far been employed in this type of Diels-Alder reaction (i.e., Diels-Alder reaction with inverse electron demand). The mechanism of the reaction and diastereoselectivity of the cycloadditions are discussed. The reaction of 1 with indole and acetyl acetone afforded the oxime 38 and a mixture of the isomers 40-42, respectively. Also, ring openings and other transformations of the trifluoromethyl-substituted 1,2-oxazines were effected. Acid-induced desilylation of the silylated 1,2-oxazines provided oximes like 46 and 48 or 6-hydroxy-1,2-oxazines like 47. Treatment of the 1,2-oxazines with Mo(CO)6 in the presence of trifluoroacetic acid produced 2-trifluoromethyl-substituted pyrroles (e.g., 18 --> 50). The reduction of the 1,2-oxazines afforded either gamma-hydroxy oximes (e.g., 19 --> 51) or amino alcohols (e.g., 32 --> 52, 31 --> 55). The reduction of the indole derivative 38 by LiAlH4 provided the trifluoromethyl-substituted tryptamine 56. The results of these explorative studies demonstrated that readily available trifluoromethyl-substituted 1,2-oxazines could be efficiently converted into other compounds that bear a trifluoromethyl group.

  DOI：

  10.1021/jo00027a058