cis-5,8-dimethoxy-3a,4,9,9a-tetrahydronaphtho<2,3-c>furan-1,3-dione | 148493-92-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: cis-5,8-dimethoxy-3a,4,9,9a-tetrahydronaphtho<2,3-c>furan-1,3-dione
• 英文别名: cis-5,8-dimethoxy-1,2,3,4-tetrahydro-2,3-naphthalenedicarboxylic anhydride；cis-5,8-dimethoxy-1,2,3,4-tetrahydronaphthalene-2,3-dicarboxylic anhydride；cis-5,8-dimethoxy-3a,4,9,9a-tetrahydronaphtho[2,3-c]furan-1,3-dione；(3aR,9aS)-5,8-dimethoxy-3a,4,9,9a-tetrahydrobenzo[f][2]benzofuran-1,3-dione
• CAS: 148493-92-9
• 化学式: C₁₄H₁₄O₅
• 分子量: 262.262
• InChiKey: PIIHLLJTAIZAJL-AOOOYVTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.12
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  cis-5,8-dimethoxy-3a,4,9,9a-tetrahydronaphtho<2,3-c>furan-1,3-dione 在 lithium aluminium tetrahydride 、 硝酸异戊酯 、 potassium tert-butylate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 sodium iodide 、 三氯乙酸 作用下， 以 四氢呋喃 、 丁酮 为溶剂， 反应 58.0h， 生成 8-bromo-13,13-dichloro-5,6,11,12-tetrahydro-1,4-dimethoxy-5a,11a-methanonaphthacene
  参考文献：
  名称：

  Large Acceleration Effect of Photoinduced Electron Transfer in Porphyrin−Quinone Dyads with a Rigid Spacer Involving a Dihalosubstituted Three-Membered Ring

  摘要：

  To understand the contribution of spacer structure toward electron transfer (ET) and to regulate electronic coupling between a redox pair, porphyrin-spacer-benzoquinone molecules were prepared where spacers are trans-decalin and dihalosubstituted tricyclo[4.4.1.0]undecane including a three-membered ring. These compounds were designed to have almost the same separation distance between a redox pair, the same number of intervening bonds, and the nearly equal free energy change associated with the ET reaction. The ET rates for the charge separation process were evaluated on the basis of the fluorescence lifetimes. A quite large difference in the ET rates was observed among these compounds, and the ET rates for the compounds having the three-membered rings were ca. 50 to 60 times larger than that with trans-decalin spacer in THF. From the analysis of temperature dependence of the ET rates, it was shown that the observed rate acceleration is caused by both an increase of the electronic coupling and a decrease of the reorganization energy, Ab initio calculations of the electronic coupling elements and on molecular orbitals for the cyclopropanes predicted that the former may be due to the enhancement of the ET pathways arising from the bent geometry of the spacer or of the mixing pathway induced by a very low lying antibonding orbital in the dihalosubstituted cyclopropane.

  DOI：

  10.1021/ja9900454
• 作为产物：
  描述：

  1,4-二甲氧基-2,3-甲基苯 在 N-溴代丁二酰亚胺(NBS) 、 锌 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 N,N-二甲基甲酰胺 为溶剂， 生成 cis-5,8-dimethoxy-3a,4,9,9a-tetrahydronaphtho<2,3-c>furan-1,3-dione
  参考文献：
  名称：

  电有机反应。第54部分。喹喔啉甲烷化学。第2部分。邻喹啉甲烷的电产生和反应性

  摘要：

  描述了各种邻喹啉甲烷（o- QDMs）的电化学生成和表征，以及以它们为关键中间体的制备实验的结果。这醌二甲烷在DMF中，通过直接和氧化还原催化的1，2-双（卤甲基）芳烃的电还原可方便地形成芳烃。他们的主要反应是聚合反应到聚（邻二甲苯）（o -PX）聚合物。在存在亲双烯体的情况下，电生成的o- QDM可以进行有效的环加成反应，并且已经基于伏安法，制备和立体化学实验尝试了可能机制之间的区别。与相应甲酯的先例相反，马来酸二苯酯自由基-阴离子仅缓慢地异构化为富马酸酯自由基-阴离子，但会共电解2,3-双（溴甲基）-1,4-二甲氧基苯 和 马来酸二苯酯 或者 富马酸二苯酯仅给出相应的反式加合物。共电解马来酸二甲酯 与任一 1,2-双（溴甲基）苯 （更容易减少）或 2,3-双（溴甲基）-1,4-二甲氧基苯（不太容易还原的），得到仅Ô -PX聚合物。根据双亲核取代机制对结果进行了合理化，其中电子转移在亲二

  DOI：

  10.1039/b007476o

文献信息

• The anodic oxidation of cis-1,2,3,4-tetrahydronaphthalene-2,3-dicarboxylic acid and its derivatives: competition between oxidative bisdecarboxylation and dilactone formation
  作者：Abid Hussain、Majid Motevalli、James H. P. Utley、Peter B. Wyatt、Yaping Gao

  DOI：10.1021/jo00065a023

  日期：1993.6
• Electro-organic reactions. Part 54. Quinodimethane chemistry. Part 2. Electrogeneration and reactivity of o-quinodimethanes
  作者：James H. P. Utley、Shalini Ramesh、Xavier Salvatella、Sabine Szunerits、Majid Motevalli、Merete F. Nielsen

  DOI：10.1039/b007476o

  日期：——

  electrochemical generation and characterisation of a variety of o-quinodimethanes (o-QDMs) are described together with the outcome of preparative experiments in which they are key intermediates. The quinodimethanes are conveniently formed, in DMF, by both direct and redox-catalysed electroreduction of 1,2-bis(halomethyl)arenes. Their predominant reaction is polymerisation to poly(o-xylylene) (o-PX) polymers

  描述了各种邻喹啉甲烷（o- QDMs）的电化学生成和表征，以及以它们为关键中间体的制备实验的结果。这醌二甲烷在DMF中，通过直接和氧化还原催化的1，2-双（卤甲基）芳烃的电还原可方便地形成芳烃。他们的主要反应是聚合反应到聚（邻二甲苯）（o -PX）聚合物。在存在亲双烯体的情况下，电生成的o- QDM可以进行有效的环加成反应，并且已经基于伏安法，制备和立体化学实验尝试了可能机制之间的区别。与相应甲酯的先例相反，马来酸二苯酯自由基-阴离子仅缓慢地异构化为富马酸酯自由基-阴离子，但会共电解2,3-双（溴甲基）-1,4-二甲氧基苯 和 马来酸二苯酯 或者 富马酸二苯酯仅给出相应的反式加合物。共电解马来酸二甲酯 与任一 1,2-双（溴甲基）苯 （更容易减少）或 2,3-双（溴甲基）-1,4-二甲氧基苯（不太容易还原的），得到仅Ô -PX聚合物。根据双亲核取代机制对结果进行了合理化，其中电子转移在亲二
• Large Acceleration Effect of Photoinduced Electron Transfer in Porphyrin−Quinone Dyads with a Rigid Spacer Involving a Dihalosubstituted Three-Membered Ring
  作者：Hirohito Tsue、Hiroshi Imahori、Takahiro Kaneda、Yoshinori Tanaka、Tadashi Okada、Koichi Tamaki、Yoshiteru Sakata

  DOI：10.1021/ja9900454

  日期：2000.3.1

  To understand the contribution of spacer structure toward electron transfer (ET) and to regulate electronic coupling between a redox pair, porphyrin-spacer-benzoquinone molecules were prepared where spacers are trans-decalin and dihalosubstituted tricyclo[4.4.1.0]undecane including a three-membered ring. These compounds were designed to have almost the same separation distance between a redox pair, the same number of intervening bonds, and the nearly equal free energy change associated with the ET reaction. The ET rates for the charge separation process were evaluated on the basis of the fluorescence lifetimes. A quite large difference in the ET rates was observed among these compounds, and the ET rates for the compounds having the three-membered rings were ca. 50 to 60 times larger than that with trans-decalin spacer in THF. From the analysis of temperature dependence of the ET rates, it was shown that the observed rate acceleration is caused by both an increase of the electronic coupling and a decrease of the reorganization energy, Ab initio calculations of the electronic coupling elements and on molecular orbitals for the cyclopropanes predicted that the former may be due to the enhancement of the ET pathways arising from the bent geometry of the spacer or of the mixing pathway induced by a very low lying antibonding orbital in the dihalosubstituted cyclopropane.