10,14-Dimethylenehexacyclo<6.6.0.0^2,6.0^3,13.0^4,11.0^5,9>tetradecane | 123105-16-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 10,14-Dimethylenehexacyclo<6.6.0.0^2,6.0^3,13.0^4,11.0^5,9>tetradecane
• 英文别名: 10,14-Dimethylenehexacyclo[6.6.0.0^2,6.0^3,13.0^4,11.0^5,9]tetradecane；10,14-Dimethylidenehexacyclo[6.6.0.02,6.03,13.04,11.05,9]tetradecane；10,14-dimethylidenehexacyclo[6.6.0.02,6.03,13.04,11.05,9]tetradecane
• CAS: 123105-16-8
• 化学式: C₁₆H₁₈
• 分子量: 210.319
• InChiKey: VNPBLLWKZWNBKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  10,14-Dimethylenehexacyclo<6.6.0.0^2,6.0^3,13.0^4,11.0^5,9>tetradecane 在 氧气 、 rose bengal 作用下， 以 正己烷 为溶剂， 反应 18.0h， 以45%的产率得到16-oxaoctacyclo[9.6.0.01,14.02,6.03,10.04,8.07,14.09,13]heptadecan-15-one
  参考文献：
  名称：

  Transannular Interactions in Polycyclic Hydrocarbons. The System of Cage-Shaped Hexacyclo[6.6.0.02,6.03,13.04,11.05,9]tetradecane Derivatives

  摘要：

  The gas phase He(I alpha) photoelectron spectra (PES) of several ketone and olefinic derivatives of the titled compound are measured. The high energy pi-orbitals (HOMO and SHOMO) of 1e show an unusually large energy splitting of 0.90 eV, while the corresponding n-orbitals of 1d appear to be nearly degenerate (<0.1 eV). The difference between these observations is analyzed with the aid of theoretical models. It is concluded in this work that the pi-pi energy splitting of 1e is derived mainly from an orbital interaction transmitted through-space (TS) across the ring. Since such a nonbonded interaction is sensitive to distance, a conformational analysis of the cycloctane ring moiety of 1e is also performed. As compared to the result of PES, it seems that the ab initio (STO-3G) method is more reliable than AM1, in which the TS interaction is somewhat underestimated.

  DOI：

  10.1021/jo00122a055
• 作为产物：
  描述：

  hexacyclo[6.6.0.0^2,6.0^3,13.0^4,11.0^5,9]tetradecane-10,14-dione 、 二溴甲烷 在 四氯化钛 、 锌 作用下， 以 四氢呋喃 为溶剂， 生成 10,14-Dimethylenehexacyclo<6.6.0.0^2,6.0^3,13.0^4,11.0^5,9>tetradecane
  参考文献：
  名称：

  碳13 nmr位移用于测量笼形聚喹烷衍生物中的跨环相互作用

  摘要：

  通过测量碳13化学位移的变化，可以检测到两个刚性聚奎宁衍生物的环空中相互作用。

  DOI：

  10.1039/c39890000490

文献信息

• Carbon-13 n.m.r. shifts for measuring transannular interaction in cage-shaped polyquinane derivatives
  作者：Tahsin J. Chow、Tung-Kung Wu、Huey-Jen Shih

  DOI：10.1039/c39890000490

  日期：——

  Transannular interactions in two systems of rigid polyquinane derivatives are detected by measuring the changes of carbon-13 chemical shifts.

  通过测量碳13化学位移的变化，可以检测到两个刚性聚奎宁衍生物的环空中相互作用。
• Transannular Interactions in Polycyclic Hydrocarbons. The System of Cage-Shaped Hexacyclo[6.6.0.02,6.03,13.04,11.05,9]tetradecane Derivatives
  作者：Tahsin J. Chow、Chin-Chuan Wei、Tung-Kung Wu、Hans-Dieter Martin、Bernhard Mayer

  DOI：10.1021/jo00122a055

  日期：1995.9

  The gas phase He(I alpha) photoelectron spectra (PES) of several ketone and olefinic derivatives of the titled compound are measured. The high energy pi-orbitals (HOMO and SHOMO) of 1e show an unusually large energy splitting of 0.90 eV, while the corresponding n-orbitals of 1d appear to be nearly degenerate (<0.1 eV). The difference between these observations is analyzed with the aid of theoretical models. It is concluded in this work that the pi-pi energy splitting of 1e is derived mainly from an orbital interaction transmitted through-space (TS) across the ring. Since such a nonbonded interaction is sensitive to distance, a conformational analysis of the cycloctane ring moiety of 1e is also performed. As compared to the result of PES, it seems that the ab initio (STO-3G) method is more reliable than AM1, in which the TS interaction is somewhat underestimated.