1,4-dihydro-1,4-methanotetracene | 85082-69-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1,4-dihydro-1,4-methanotetracene
• 英文别名: 2,3-Norbornadienoanthracene；Pentacyclo[14.2.1.02,15.04,13.06,11]nonadeca-2,4,6,8,10,12,14,17-octaene
• CAS: 85082-69-5
• 化学式: C₁₉H₁₄
• 分子量: 242.32
• InChiKey: MBLHQXVJPQXIOT-UHFFFAOYSA-N

物化性质

• 熔点：
  233.5-234.0 °C(Solv: ethanol (64-17-5))
• 沸点：
  432.4±25.0 °C(Predicted)
• 密度：
  1.232±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.16
• 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：

  1,4-dihydro-1,4-methanotetracene 在 palladium on activated charcoal 氢气 作用下， 生成 1,2,3,4-tetrahydro-1,4-methanotetracene
  参考文献：
  名称：

  Intramolecular Energy Transfer from Upper Triplet States in Rigidly-Linked Bichromophoric Molecules

  摘要：

  Intramolecular triplet energy transfer has been studied in bichromophoric molecules that incorporate an anthracene donor and ketone or alkene accepters connected by two rigid, bicyclic saturated hydrocarbon units. Two-laser excitation of the anthracene group results in production of the T-2 State which subsequently undergoes energy transfer to the accepters (k approximate to 10(10) s(-1)), as indicated by depletion of the T-T absorption. In 1, decay of the acceptor (ketone) triplet state involves a competition between ring opening and back energy transfer to the anthracene T-1 state. In 2-4, rotation of the alkene triplets to perpendicular geometries relieves ring strain in the bicyclic connecting units, thus providing a barrier to back energy transfer. A fraction of the twisted triplets relaxes to the ground state without irreversible chemistry.

  DOI：

  10.1021/ja00120a019
• 作为产物：
  描述：

  在 对甲苯磺酰氯 作用下， 以 吡啶 为溶剂， 反应 37.0h， 以68%的产率得到1,4-dihydro-1,4-methanotetracene
  参考文献：
  名称：

  An Improved Synthesis of 2,3-Norbornadienoanthracene and its Application to the Synthesis of Anthracene Annellated Norbornenylogs

  摘要：

  报道了一种改进的目标化合物1的合成方法，该方法涉及1,4-萘醌3与环戊二烯的热环加成反应，随后将所得加合物4用锂铝氢化物处理，并在吡啶中与对甲基苯磺酰氯反应。化合物1能够提供多种苊基取代的诺式化合物的合成示例，通过铑催化的热环加成反应将二甲基乙炔二羧酸酯与1反应，随后将四环烯加成至所得加合物8，合成了化合物9。

  DOI：

  10.1055/s-1986-31602

文献信息

• An Efficient Synthetic Strategy for Naphthalene Annellation of Norbornenylogous Systems
  作者：Michael N. Paddon-Row、Harish K. Patney

  DOI：10.1055/s-1986-31603

  日期：——

  Naphthalene annellation of norbornyl compounds can be readily achieved in good yields through in situ trapping of dibromonaphthoquinone (5), generated from 4 and sodium iodide, by the dienophilic norbornyl substrate. The dienophiles used include norbornadiene (which gave mono-adduct 8b or bis-adduct 3a depending on the conditions), norbornene, benzonorbornadiene (11), diene 9, and 13.

  由 4 和碘化钠生成的二溴萘醌（5）被亲二烯的降冰片基底物原位捕获，可以很容易地实现降冰片基化合物的萘环化，而且产量很高。 使用过的亲二烯烃包括降冰片二烯（根据不同的条件，可得到单加合物 8b 或双加合物 3a）、降冰片烯、苯并降冰片二烯 (11)、二烯 9 和 13。
• 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.
• HAYES, P. C.;PAQUETTE, L. A., J. ORG. CHEM., 1983, 48, N 8, 1257-1261
  作者：HAYES, P. C.、PAQUETTE, L. A.

  DOI：——

  日期：——
• PATNEY, HARISH, K.;PADDON-ROW, M. N., SYNTHESIS, BRD, 1986, N 4, 326-328
  作者：PATNEY, HARISH, K.、PADDON-ROW, M. N.

  DOI：——

  日期：——
• PADDON-ROW, M. N.;PATNEY, H. K., SYNTHESIS, BRD, 1986, N 4, 328-330
  作者：PADDON-ROW, M. N.、PATNEY, H. K.

  DOI：——

  日期：——