<3aS-(3aα,6β,8aα)>-1,2,3,3a,6,7,8,8a-octahydro-2,2-dimethyl-8-methylene-5,6-azulenedicarboxaldehyde | 131434-67-8

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: <3aS-(3aα,6β,8aα)>-1,2,3,3a,6,7,8,8a-octahydro-2,2-dimethyl-8-methylene-5,6-azulenedicarboxaldehyde
• 英文别名: (3aS,6S,8aS)-2,2-dimethyl-8-methylidene-1,3,3a,6,7,8a-hexahydroazulene-5,6-dicarbaldehyde
• CAS: 131434-67-8
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: QUTNYAFRZBJHLB-YRGRVCCFSA-N

物化性质

• 沸点：
  351.0±42.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  <3aS-(3aα,6β,8aα)>-1,2,3,3a,6,7,8,8a-octahydro-2,2-dimethyl-8-methylene-5,6-azulenedicarboxaldehyde 在 溶剂黄146 作用下， 以 甲苯 为溶剂， 生成 pyrovellerofuran
  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
• 作为产物：
  描述：

  (3aS,8aS)-6-[1-(tert-Butyl-dimethyl-silanyloxy)-meth-(E)-ylidene]-2,2-dimethyl-8-methylene-1,2,3,3a,6,7,8,8a-octahydro-azulene-5-carbaldehyde 在 四丁基氟化铵 作用下， 以 氯仿 、 水 为溶剂， 反应 1.0h， 以35%的产率得到<3aS-(3aα,6α,8aα)>-1,2,3,3a,6,7,8,8a-octahydro-2,2-dimethyl-8-methylene-5,6-azulenedicarboxaldehyde
  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

文献信息

• The thermal isomerization of the sesquiterpenes isovelleral and merulidial. A reversible ring opening of the cis-methylcyclopropanecarboxaldehyde group via an intramolecular ene reaction.
  作者：Thomas Hansson、Olov Sterner、Boerje Wickberg、Rolf Bergman

  DOI：10.1021/jo00040a020

  日期：1992.7

  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.