(1α,4α,4aβ,4bα,4cβ,5α,9aβ,10α,10aα,10bα,10cα)-1,2,3,4,4a,4b,4c,5,5a,9a,10,10a,10b,10c-tetradecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2-b]naphthalene | 180396-74-1

• 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,9aβ,10α,10aα,10bα,10cα)-1,2,3,4,4a,4b,4c,5,5a,9a,10,10a,10b,10c-tetradecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2-b]naphthalene
• 英文别名: (1R,2R,3S,4S,5R,8S,9R,10R,11S,12S,13R,18S)-3,10-dimethylheptacyclo[10.6.1.15,8.02,11.03,10.04,9.013,18]icosa-14,16-diene
• CAS: 180396-74-1
• 化学式: C₂₂H₂₈
• 分子量: 292.464
• InChiKey: GVUMCZLLFMHRNT-BZYQYCEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.82
• 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,9aβ,10α,10aα,10bα,10cα)-1,2,3,4,4a,4b,4c,5,5a,9a,10,10a,10b,10c-tetradecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2-b]naphthalene 在 palladium on activated charcoal lithium aluminium tetrahydride 、 potassium tert-butylate 、 氢气 作用下， 以 四氢呋喃 、 吡啶 、 二甲基亚砜 、 乙酸乙酯 、 苯 为溶剂， -5.0~25.0 ℃ 、101.33 kPa 条件下， 反应 90.0h， 生成 (1α,4α,4aβ,4bα,4cβ,5α,5aβ,6α,9α,9aβ,10α,10aα,10bα,10cα)-1,2,3,4,4a,4b,4c,5,5a,6,9,9a,10,10a,10b,10c-hexadecahydro-6,9-ethano-1,4:5,8-dimethano-4b,8b-dimethyl-7,8-bis(methylene)benzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2-b]naphthalene
  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：

  (1R,2R,3S,4S,5R,8S,9R,10R,11S,12S,13R,14R,17S,18S)-3,10-dimethyloctacyclo[10.6.1.15,8.114,17.02,11.03,10.04,9.013,18]henicos-15-en-20-one 以 甲苯 为溶剂， 反应 1.0h， 以85%的产率得到(1α,4α,4aβ,4bα,4cβ,5α,9aβ,10α,10aα,10bα,10cα)-1,2,3,4,4a,4b,4c,5,5a,9a,10,10a,10b,10c-tetradecahydro-1,4:5,8-dimethano-4b,8b-dimethylbenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2-b]naphthalene
  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 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.