(1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-5b,11b-dimethyl-7,10,15,15-tetramethoxy-1,4:5,12:6,11-trimethanonaphtho<2'',3'':3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>... | 180396-67-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-5b,11b-dimethyl-7,10,15,15-tetramethoxy-1,4:5,12:6,11-trimethanonaphtho<2'',3'':3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>...
• 英文别名: (1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-5b,11b-dimethyl-7,10,15,15-tetramethoxy-1,4:5,12:6,11-trimethanonaphtho<2",3":3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>...；(1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-1,4:5,12:6,11-trimethano-7,10,15,15-tetramethoxy-5b,11b-dimethylnaphtho<2'',3'':3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>..；(1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-5b,11b-dimethyl-7,10,15,15-tetramethoxy-1,4:5,12:6,11-trimethanonaphtho[2",3":3',4']cyclobuta[1',2':3,4]cyclobuta[1,2-b]...
• CAS: 180396-67-2
• 化学式: C₃₁H₃₈O₄
• 分子量: 474.64
• InChiKey: IVYAWFGZLWXBLW-NHMQFAOLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.48
• 重原子数：
  35.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-5b,11b-dimethyl-7,10,15,15-tetramethoxy-1,4:5,12:6,11-trimethanonaphtho<2'',3'':3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>... 在 甲酸 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以91%的产率得到
  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：

  (1α,4α,4aβ,4bα,4cβ,5α,10α,10aβ,10bα,10cβ)-1,4,4a,4b,4c,5,10,10a,10b,10c-decahydro-1,4:5,10-dimethano-6,9-dimethoxy-4b,10b-dimethylbenzo<3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>naphthalene 在 sodium 作用下， 以 四氢呋喃 、 异丙醇 、 xylene 为溶剂， 反应 35.0h， 生成 (1α,4α,4aα,5β,5aα,5bβ,5cα,6β,11β,11aα,11bβ,11cα,12β,12aα)-1,4,4a,,5,5a,5b,5c,6,11,11a,11b,11c,12,12a-tetradecahydro-5b,11b-dimethyl-7,10,15,15-tetramethoxy-1,4:5,12:6,11-trimethanonaphtho<2'',3'':3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2-b>...
  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 and structural characterization of a novel pair of rigid diastereomeric triads
  作者：James M. Lawson、Donald C. Craig、Anna M. Oliver、Michael N. Paddon-Row

  DOI：10.1016/0040-4020(95)00107-j

  日期：1995.3

  A method is described for constructing totally rigid triad (nichromophoric) systems, D2-B1-D1-B2-A, in which the chromophores D2 (= dimethylaniline), D1 (= 1,4-dimethoxynaphthalene), and A (= dicyanovinyl) are fused to rigid hydrocarbon bridges, B1 and B2, comprising linearly fused norbornane and bicyclo[2.2.0]hexane units.

  描述了一种用于构建完全刚性的三联体（发色团）系统D 2 -B 1 -D 1 -B 2 -A的方法，其中发色团D 2（=二甲基苯胺），D 1（= 1,4-二甲氧基萘），和A（＝二氰基ovyl）稠合到刚性烃桥B 1和B 2，其包括线性稠合的降冰片烷和双环[2.2.0]己烷单元。