11-(carbethoxymethylene)-anti-8-(methoxymethoxy)pentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecane | 137894-48-5

• 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: 11-(carbethoxymethylene)-anti-8-(methoxymethoxy)pentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecane
• CAS: 137894-48-5
• 化学式: C₁₇H₂₂O₄
• 分子量: 290.359
• InChiKey: OTJCNTBERXKNFR-UHFFFAOYSA-N

物化性质

• 沸点：
  378.4±32.0 °C(predicted)
• 密度：
  1.26±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.85
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  11-(carbethoxymethylene)-anti-8-(methoxymethoxy)pentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecane 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 8.0h， 以96%的产率得到syn/anti-8-(methoxymethoxy)-syn-11-pentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecaneacetic acid ethyl ester
  参考文献：
  名称：

  Further studies in pentacycloundecan-8-one photochemistry

  摘要：

  Three new syn-11-substituted pentacycloundecan-8-ones 1a-c (X = CN, CO2CH3, C6H5) have been synthesized and evaluated for photochemical reactivity in the context of the development of a force field methodology for evaluation of Norrish Type II reactions. None of these compounds underwent significant intramolecular hydrogen abstraction reactions or showed evidence for interactions between the excited alkanone and the proximate methylene hydrogens. The absence of isotope effect in the fluorescence of the deuteriated analogue of 1a provides strong evidence that there are no radiationless processes involving the proximate hydrogens that deactivate the singlet state of this ketone. A novel photostimulated interaction between alkanone singlet states and a ''remote'' cyano group was observed and rationalized in terms of dynamic processes during the excited state lifetime. Evidence is presented for competing long-range and contact interactions between singlet aryl rings and ground-state carbonyl groups. syn-11-tert-Butylpentacycloundecanone (2) was prepared and found to be photochemically unreactive as a consequence of a large increase in steric energy associated with formation of the transition structure.

  DOI：

  10.1021/jo00028a050
• 作为产物：
  描述：

  anti-11-hydroxypentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecane-8-one 在 sodium hydride 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 68.25h， 生成 11-(carbethoxymethylene)-anti-8-(methoxymethoxy)pentacyclo<5.4.0.0^2,6.0^3,10.0^5,9>undecane
  参考文献：
  名称：

  Further studies in pentacycloundecan-8-one photochemistry

  摘要：

  Three new syn-11-substituted pentacycloundecan-8-ones 1a-c (X = CN, CO2CH3, C6H5) have been synthesized and evaluated for photochemical reactivity in the context of the development of a force field methodology for evaluation of Norrish Type II reactions. None of these compounds underwent significant intramolecular hydrogen abstraction reactions or showed evidence for interactions between the excited alkanone and the proximate methylene hydrogens. The absence of isotope effect in the fluorescence of the deuteriated analogue of 1a provides strong evidence that there are no radiationless processes involving the proximate hydrogens that deactivate the singlet state of this ketone. A novel photostimulated interaction between alkanone singlet states and a ''remote'' cyano group was observed and rationalized in terms of dynamic processes during the excited state lifetime. Evidence is presented for competing long-range and contact interactions between singlet aryl rings and ground-state carbonyl groups. syn-11-tert-Butylpentacycloundecanone (2) was prepared and found to be photochemically unreactive as a consequence of a large increase in steric energy associated with formation of the transition structure.

  DOI：

  10.1021/jo00028a050