(1α,4α,4aβ,4bα,4cβ,5α,8α,8aα,8bβ,8cα)-1,4,4a,4b,4c,5,6,7,8,8a,8b,8c-dodecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2]benzene | 180396-63-8

• 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: (1α,4α,4aβ,4bα,4cβ,5α,8α,8aα,8bβ,8cα)-1,4,4a,4b,4c,5,6,7,8,8a,8b,8c-dodecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2]benzene
• 英文别名: (1R,2S,3S,4R,5R,8S,9S,10R,11R,12S)-3,10-dimethylhexacyclo[10.2.1.15,8.02,11.03,10.04,9]hexadec-6-ene
• CAS: 180396-63-8
• 化学式: C₁₈H₂₄
• 分子量: 240.389
• InChiKey: NNRQDKYVHSOPOT-YYGMFGEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  6.0
• 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：

  (1α,4α,4aβ,4bα,4cβ,5α,8α,8aα,8bβ,8cα)-1,4,4a,4b,4c,5,6,7,8,8a,8b,8c-dodecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2]benzene 在 sodium 作用下， 以 四氢呋喃 、 异丙醇 、 甲苯 为溶剂， 反应 35.0h， 生成 (1R,2R,3S,4S,5R,8S,9R,10R,11S,12S,13R,14R,17S,18S)-20,20-dimethoxy-3,10-dimethyloctacyclo[10.6.1.15,8.114,17.02,11.03,10.04,9.013,18]henicos-15-ene
  参考文献：
  名称：

  Synthesis of a Variety of Bichromophoric “Ball-and-Chain” Systems Based on Buckminsterfullerene (C₆₀) for the Study of Intramolecular Electron and Energy Transfer Processes

  摘要：

  Diels-Alder reaction of C-60 with the 1,3-dienes 7e-h, 8a, 8b, and 8d-h affords the ''ball-and-chain'' systems 2e-h, 3a, 3b, and 3d-h bearing two chromophores linked via a rigid, hybrid saturated polynorbornane-bicyclo[2.2.0]hexane (''norbornylogous'') hydrocarbon bridge. Analogous reaction with the bis(diene) 9 affords the soluble dumbbell system 4 bearing two C-60, chromophores. The norbornylogous bridge is a strong mediator of electron and energy transfer via a through-bond coupling mechanism. The norbornylogous donor-bridge-diene units 7d-h, 8a, 8b, and 8d-h were prepared in a straightforward manner from bicyclo[2.2.2]octane precursors by extending the bridges with linearly fused norbornane-bicyclo[2.2.0]hexane moieties through execution of the tandem Mitsudo-Smith series of reactions. The X-ray structure of the dimethoxybenzene-bridge-C-60 system 3a reveals favorable self-complementarity manifested by the unusual packing structure of 3a in the crystal. Molecular mechanics, semiempirical, and ab initio conformational analyses of compounds 2e, 3a, 3b, 3e, 3f, 3h, 68, and 70 (MM2, Sybyl, CVFF, AM1, HF/3-21G) were performed to quantify their ability to adopt two nondegenerate boat conformations, i.e,, extended and folded conformers, as well as their kinetic barrier of interconversion. A similar treatment of the C-60-bridge-C-60 system 4 revealed unusual preference for the folded-folded conformer (18.9 kcal/mol at CVFF level), which was not reproduced by the AM1 method (0.11 kcal/mol). The reduction potentials of the systems 2e, 3a, and 3e were about 0.1-0.5 V more negative than C-60, and the third reduction potential (E(3)) Of the 6-bond system 2e was 0.14 V more negative than the corresponding wave for the 10-bond system 3e. This shift was attributed to the closer proximity of the dimethylaniline donor group to the C-60 surface for 2e vs 3e.

  DOI：

  10.1021/jo960512p
• 作为产物：
  描述：

  C₂₀H₂₈O₆S₂ 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以91%的产率得到(1α,4α,4aβ,4bα,4cβ,5α,8α,8aα,8bβ,8cα)-1,4,4a,4b,4c,5,6,7,8,8a,8b,8c-dodecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2]benzene
  参考文献：
  名称：

  Synthesis of a Variety of Bichromophoric “Ball-and-Chain” Systems Based on Buckminsterfullerene (C₆₀) for the Study of Intramolecular Electron and Energy Transfer Processes

  摘要：

  Diels-Alder reaction of C-60 with the 1,3-dienes 7e-h, 8a, 8b, and 8d-h affords the ''ball-and-chain'' systems 2e-h, 3a, 3b, and 3d-h bearing two chromophores linked via a rigid, hybrid saturated polynorbornane-bicyclo[2.2.0]hexane (''norbornylogous'') hydrocarbon bridge. Analogous reaction with the bis(diene) 9 affords the soluble dumbbell system 4 bearing two C-60, chromophores. The norbornylogous bridge is a strong mediator of electron and energy transfer via a through-bond coupling mechanism. The norbornylogous donor-bridge-diene units 7d-h, 8a, 8b, and 8d-h were prepared in a straightforward manner from bicyclo[2.2.2]octane precursors by extending the bridges with linearly fused norbornane-bicyclo[2.2.0]hexane moieties through execution of the tandem Mitsudo-Smith series of reactions. The X-ray structure of the dimethoxybenzene-bridge-C-60 system 3a reveals favorable self-complementarity manifested by the unusual packing structure of 3a in the crystal. Molecular mechanics, semiempirical, and ab initio conformational analyses of compounds 2e, 3a, 3b, 3e, 3f, 3h, 68, and 70 (MM2, Sybyl, CVFF, AM1, HF/3-21G) were performed to quantify their ability to adopt two nondegenerate boat conformations, i.e,, extended and folded conformers, as well as their kinetic barrier of interconversion. A similar treatment of the C-60-bridge-C-60 system 4 revealed unusual preference for the folded-folded conformer (18.9 kcal/mol at CVFF level), which was not reproduced by the AM1 method (0.11 kcal/mol). The reduction potentials of the systems 2e, 3a, and 3e were about 0.1-0.5 V more negative than C-60, and the third reduction potential (E(3)) Of the 6-bond system 2e was 0.14 V more negative than the corresponding wave for the 10-bond system 3e. This shift was attributed to the closer proximity of the dimethylaniline donor group to the C-60 surface for 2e vs 3e.

  DOI：

  10.1021/jo960512p

文献信息

• Synthesis, Structure, and Photophysical Studies of a Pair of Novel Rigid Bichromophoric Systems Bearing a Methyl Viologen Acceptor Unit
  作者：Donald C. Craig、Kenneth P. Ghiggino、Katrina A. Jolliffe、Steven J. Langford、Michael N. Paddon-Row

  DOI：10.1021/jo9620371

  日期：1997.4.1

  The rigid bichromophoric systems7a.2BF(4) and7b.2BF(4), comprising either a dimethoxybenzene (a) or dimethoxynaphthalene (b) unit, each covalently linked through a six-bond norbornylogous bridge to a methyl viologen unit, were synthesized with a view to studying long-range intramolecular energy (EnT) and/or electron (ET) transfer. X-ray crystallography has been used to illustrate that 7b.2BF(4) has

  刚性双发色体系7a.2BF（4）和7b.2BF（4）包含二甲氧基苯（a）或二甲氧基萘（b）单元，每个单元通过六键降冰片异源桥共价连接至甲基紫精单元，并与研究远距离分子内能量（EnT）和/或电子（ET）转移。X射线晶体学已用于说明7b.2BF（4）具有在结晶时经历自组织以在晶格内形成扩展的线性阵列的能力。对7b.2BF（4）的初步光物理研究表明，与模型二甲氧基萘单元相比，双发色团中存在一个额外的快速非辐射过程（速率常数> 2.5 x 10（10）s（-）（1））。介绍了此过程。
• Synthesis of a Variety of Bichromophoric “Ball-and-Chain” Systems Based on Buckminsterfullerene (C₆₀) for the Study of Intramolecular Electron and Energy Transfer Processes
  作者：James M. Lawson、Anna M. Oliver、Daniel F. Rothenfluh、Yi-Zhong An、George A. Ellis、Millagahamada G. Ranasinghe、Saeed I. Khan、Andreas G. Franz、Padma S. Ganapathi、Michael J. Shephard、Michael N. Paddon-Row、Yves Rubin

  DOI：10.1021/jo960512p

  日期：1996.1.1

  Diels-Alder reaction of C-60 with the 1,3-dienes 7e-h, 8a, 8b, and 8d-h affords the ''ball-and-chain'' systems 2e-h, 3a, 3b, and 3d-h bearing two chromophores linked via a rigid, hybrid saturated polynorbornane-bicyclo[2.2.0]hexane (''norbornylogous'') hydrocarbon bridge. Analogous reaction with the bis(diene) 9 affords the soluble dumbbell system 4 bearing two C-60, chromophores. The norbornylogous bridge is a strong mediator of electron and energy transfer via a through-bond coupling mechanism. The norbornylogous donor-bridge-diene units 7d-h, 8a, 8b, and 8d-h were prepared in a straightforward manner from bicyclo[2.2.2]octane precursors by extending the bridges with linearly fused norbornane-bicyclo[2.2.0]hexane moieties through execution of the tandem Mitsudo-Smith series of reactions. The X-ray structure of the dimethoxybenzene-bridge-C-60 system 3a reveals favorable self-complementarity manifested by the unusual packing structure of 3a in the crystal. Molecular mechanics, semiempirical, and ab initio conformational analyses of compounds 2e, 3a, 3b, 3e, 3f, 3h, 68, and 70 (MM2, Sybyl, CVFF, AM1, HF/3-21G) were performed to quantify their ability to adopt two nondegenerate boat conformations, i.e,, extended and folded conformers, as well as their kinetic barrier of interconversion. A similar treatment of the C-60-bridge-C-60 system 4 revealed unusual preference for the folded-folded conformer (18.9 kcal/mol at CVFF level), which was not reproduced by the AM1 method (0.11 kcal/mol). The reduction potentials of the systems 2e, 3a, and 3e were about 0.1-0.5 V more negative than C-60, and the third reduction potential (E(3)) Of the 6-bond system 2e was 0.14 V more negative than the corresponding wave for the 10-bond system 3e. This shift was attributed to the closer proximity of the dimethylaniline donor group to the C-60 surface for 2e vs 3e.