3-Methyl-tricyclo[4.2.0.02,5]octa-3,7-diene | 135191-80-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 3-Methyl-tricyclo[4.2.0.02,5]octa-3,7-diene
• CAS: 135191-80-9
• 化学式: C₉H₁₀
• 分子量: 118.178
• InChiKey: QFAWYHQFOQJJSU-UYXSQOIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.99
• 重原子数：
  9.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  N-hydroxy-2-pyridinethione ester of cubylacetic acid 在 苯硒酚 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 7-Methylene-tricyclo[4.2.0.02,5]oct-3-ene 、 3-Methyl-tricyclo[4.2.0.02,5]octa-3,7-diene
  参考文献：
  名称：

  The preparation and fate of cubylcarbinyl radicals

  摘要：

  The cubylcarbinyl radical has been generated from cubylcarbinyl bromide and from the N-hydroxy-2-pyridinethione ester of cubylacetic acid under various conditions favoring hydrogen-atom transfer to the radical. Only when selenophenol in high concentration is used as the hydrogen donor is any methylcubane formed. Otherwise the cubylcarbinyl radical rearranges. There is no evidence of a 1,2-shift into the homocubyl system. Instead, one, two, or three bonds of the cubane nucleus cleave, leading to a variety of olefinic products. For the most part, these have been characterized. A mechanistic scheme accounting for their formation is presented; sequential sigma-bond breaking occurs regioselectively, favoring processes in which there is good overlap between the radical orbital and that of the breaking bond. The distribution of products is shown to depend qualitatively on the time the radical intermediates are let live, that is, on the concentration and effectiveness of the hydrogen atom transfer agent. From product distributions, the rate constant for ring cleavage of cubylcarbinyl radical is calculated to be at least 2 X 10(10) s-1, substantially greater than that of any radical derived to date from a saturated hydrocarbon system. Methodology is given for the synthesis of cubylcarbinol, cubylacetic acid, 1,4-bis(hydroxymethyl)cubane, methylcubane, and a variety of other new cubane compounds.

  DOI：

  10.1021/ja00020a035