dimethyl (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-dimethanobenzo<3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2>benzene-4b,8b-dicarboxylate | 176387-24-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: dimethyl (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-dimethanobenzo<3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2>benzene-4b,8b-dicarboxylate
• 英文别名: dimethyl (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-dimethanobenzo[3',4']cyclobuta[1',2':3,4]cyclobuta[1,2]benzene-4b,8b-dicarboxylate；dimethyl (1S,2R,3S,4S,5S,8R,9R,10R,11S,12R)-hexacyclo[10.2.1.15,8.02,11.03,10.04,9]hexadec-6-ene-3,10-dicarboxylate
• CAS: 176387-24-9
• 化学式: C₂₀H₂₄O₄
• 分子量: 328.408
• InChiKey: SIVIRVZRVAQVNN-HRPYVWAMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl (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-dimethanobenzo<3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2>benzene-4b,8b-dicarboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 138.0h， 生成 (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
• 作为产物：
  描述：

  Dimethyl-tricyclo[4.2.1.0^2,5]nona-3-ene-3,4-dicarboxylate 、 四环庚烷 反应 18.0h， 以86.6%的产率得到dimethyl (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-dimethanobenzo<3',4'>cyclobuta<1',2':3,4>cyclobuta<1,2>benzene-4b,8b-dicarboxylate
  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

• The preparation of rigidly-linked 4,5-diazafluorenes: New molrac bidentate ligand systems
  作者：Ronald N. Warrener、Aurélio B.B. Ferreira、Edward R.T. Tiekink

  DOI：10.1016/0040-4039(96)00223-7

  日期：1996.3

  New rigid molracs have been prepared in which terminal positions are occupied by spiro-fused 4,5-diazafluorene ligand. This is achieved via a thermally-induced (or high pressure) 1,3-dipolar cycloaddition of 9-diazo-4,5-diazafluorene onto the π-bond of the molrac followed by thermal (or photochemical) ejection of dinitrogen from the intermediate pyrazoline; norbornadiene alone gives a rearranged product

  已经制备了新的刚性分子，其中末端位置被螺旋稠合的4，5-二氮杂芴配体占据。这是通过将9-重氮-4,5-二氮杂芴通过热诱导（或高压）的1,3-偶极环加成到软体动物的π键上，然后从中间体热（或光化学）喷出二氮来实现的吡唑啉 单独降冰片二烯在脱氮叠氮时产生重排产物22。
• 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.