4-(bicyclo[4.1.0]hept-7'-ylidene)pentacyclo[6.3.0^2,6.0^3,10.0^5,9]undecane

• 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: 4-(bicyclo[4.1.0]hept-7'-ylidene)pentacyclo[6.3.0^2,6.0^3,10.0^5,9]undecane
• 英文别名: 4-[(1S,6R)-7-bicyclo[4.1.0]heptanylidene]pentacyclo[6.3.0.02,6.03,10.05,9]undecane
• 化学式: C₁₈H₂₂
• 分子量: 238.373
• InChiKey: WWVWGIXYWAFDDQ-UWAXNYLUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  氯仿 、 4-(bicyclo[4.1.0]hept-7'-ylidene)pentacyclo[6.3.0^2,6.0^3,10.0^5,9]undecane 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 反应 24.0h， 以75%的产率得到
  参考文献：
  名称：

  Study of a Vinylidenecarbene−Cycloalkyne Equilibrium in the D₃-Trishomocubyl Ring System

  摘要：

  The same cage-annulated vinylidenecarbene, 7a, could be generated and subsequently trapped in situ by cyclohexene via either of the following methods: (i) low-temperature reaction of 4-(dibromomethylene)pentacyclo[6.3.0.0(2,6).0(3,10).0(5,9)]undecane (6) with n-BuLi-THF and (ii) low-temperature reaction of 5-bromopentacyclo[7.3.0.0(2,6).0(3,10).0(5,9)]dodec-4-ene (12) with LDA-THF. These results, together with the corresponding results of site-specific C-13-labeling experiments performed on 6-(C) over bar(4)=(CBr2)-C-13 and 12-C-13(5), provide evidence for the thermodynamic stability of 7a vis-h-vis 7b. In addition, the results of semiempirical and ab initio MO calculations demonstrate the relative kinetic as well as thermodynamic preference for 7a vis-a-vis 7b.

  DOI：

  10.1021/ja974313e
• 作为产物：
  描述：

  4-promppentacyclo[7.3.0.0^2,7.0^3,11.0^6,10]dodec-11ene 、 环己烯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 6.0h， 以36%的产率得到4-(bicyclo[4.1.0]hept-7'-ylidene)pentacyclo[6.3.0^2,6.0^3,10.0^5,9]undecane
  参考文献：
  名称：

  Study of a Vinylidenecarbene−Cycloalkyne Equilibrium in the D₃-Trishomocubyl Ring System

  摘要：

  The same cage-annulated vinylidenecarbene, 7a, could be generated and subsequently trapped in situ by cyclohexene via either of the following methods: (i) low-temperature reaction of 4-(dibromomethylene)pentacyclo[6.3.0.0(2,6).0(3,10).0(5,9)]undecane (6) with n-BuLi-THF and (ii) low-temperature reaction of 5-bromopentacyclo[7.3.0.0(2,6).0(3,10).0(5,9)]dodec-4-ene (12) with LDA-THF. These results, together with the corresponding results of site-specific C-13-labeling experiments performed on 6-(C) over bar(4)=(CBr2)-C-13 and 12-C-13(5), provide evidence for the thermodynamic stability of 7a vis-h-vis 7b. In addition, the results of semiempirical and ab initio MO calculations demonstrate the relative kinetic as well as thermodynamic preference for 7a vis-a-vis 7b.

  DOI：

  10.1021/ja974313e

文献信息

• Study of a Vinylidenecarbene−Cycloalkyne Equilibrium in the <i>D</i>₃-Trishomocubyl Ring System
  作者：Alan P. Marchand、I. N. N. Namboothiri、Bishwajit Ganguly、Simon G. Bott

  DOI：10.1021/ja974313e

  日期：1998.7.1

  The same cage-annulated vinylidenecarbene, 7a, could be generated and subsequently trapped in situ by cyclohexene via either of the following methods: (i) low-temperature reaction of 4-(dibromomethylene)pentacyclo[6.3.0.0(2,6).0(3,10).0(5,9)]undecane (6) with n-BuLi-THF and (ii) low-temperature reaction of 5-bromopentacyclo[7.3.0.0(2,6).0(3,10).0(5,9)]dodec-4-ene (12) with LDA-THF. These results, together with the corresponding results of site-specific C-13-labeling experiments performed on 6-(C) over bar(4)=(CBr2)-C-13 and 12-C-13(5), provide evidence for the thermodynamic stability of 7a vis-h-vis 7b. In addition, the results of semiempirical and ab initio MO calculations demonstrate the relative kinetic as well as thermodynamic preference for 7a vis-a-vis 7b.