<12-2H3>-isovelleral | 131434-68-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <12-2H3>-isovelleral
• CAS: 131434-68-9
• 化学式: C₁₅H₂₀O₂
• 分子量: 235.299
• InChiKey: PJAAESPGJOSQGZ-DFUKIKSTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  <12-2H3>-isovelleral 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  Marasmane倍半萜烯（+）-异戊二烯的热重排机理。通过分子内烯反应进行环丙烷闭环

  摘要：

  真菌倍半萜异戊二醛（2）到（1）的可逆热转化是通过双环烯醇（3）进行的独特的分子内烯反应，这通过动力学研究，氘掺入和（3）的俘获得以证明。

  DOI：

  10.1039/c39900001260
• 作为产物：
  描述：

  异-异绒白乳菇醛 在 重水 作用下， 以 氘代甲苯 、 甲苯 为溶剂， 反应 1.0h， 生成 <12-2H3>-isovelleral
  参考文献：
  名称：

  The thermal isomerization of the sesquiterpenes isovelleral and merulidial. A reversible ring opening of the cis-methylcyclopropanecarboxaldehyde group via an intramolecular ene reaction.

  摘要：

  Fungal sesquiterpene dialdehydes of marasmane and isolactarane types, such as isovelleral (1) and merulidial (7), undergo a reversible thermal rearrangement to products (e.g., 2 and 8) with inverted orientations of the cyclopropane rings. The process is shown to involve an intramolecular ene reaction with a bicyclic enol intermediate 13 which was trapped as an E-silyl ether 17. In the presence of D2O, deuterium is incorporated quantitatively into the C-12 methyl groups of 1 and 2. A high kinetic isotope effect is observed for the rearrangement of 1 and its deuterated analogue 24, and the reaction parameters are comparable to those reported for the thermal ring-opening reactions of cis-alkylvinylcyclopropanes and cis-alkyl cyclopropyl ketones. In the presence of weak acid or base, an equilibrium is established between 1, 2, and the hydroazulenic dialdehydes 14 and 15. Dialdehyde 7 reacts less cleanly and incorporates deuterium not only at C-13 but also at C-1 (26). The latter process presumably involves enolization via a [1,5] sigmatropic hydrogen shift.

  DOI：

  10.1021/jo00040a020