<1aR-(1aβ,3aβ,6aβ,6bβ)>-3a,4,5,6,6a,6b-hexahydro-2-(hydroxymethyl)-5,5,6b-trimethylcyclopropindene-1a(1H)-carboxaldehyde | 141315-80-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <1aR-(1aβ,3aβ,6aβ,6bβ)>-3a,4,5,6,6a,6b-hexahydro-2-(hydroxymethyl)-5,5,6b-trimethylcyclopropindene-1a(1H)-carboxaldehyde
• CAS: 141315-80-2
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: MRWQPWOAWYZTBU-WCUVEOEZSA-N

物化性质

• 沸点：
  330.0±25.0 °C(Predicted)
• 密度：
  1.149±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  isovellerol 以 甲苯 为溶剂， 反应 3.0h， 以29%的产率得到<1aR-(1aβ,3aβ,6aβ,6bβ)>-3a,4,5,6,6a,6b-hexahydro-2-(hydroxymethyl)-5,5,6b-trimethylcyclopropindene-1a(1H)-carboxaldehyde
  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