(1R,4S,4aS,5R,8S,8aS,9aR,10aR)-1,4,5,8-Tetrachloro-11,11,12,12-tetramethoxy-octahydro-1,4;5,8-dimethano-anthracene-2,3,6,7-tetraone | 308820-28-2

• 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: (1R,4S,4aS,5R,8S,8aS,9aR,10aR)-1,4,5,8-Tetrachloro-11,11,12,12-tetramethoxy-octahydro-1,4;5,8-dimethano-anthracene-2,3,6,7-tetraone
• 英文别名: (1R,2R,4S,5S,8R,9R,11S,12S)-1,5,8,12-tetrachloro-15,15,16,16-tetramethoxypentacyclo[10.2.1.15,8.02,11.04,9]hexadecane-6,7,13,14-tetrone
• CAS: 308820-28-2
• 化学式: C₂₀H₂₀Cl₄O₈
• 分子量: 530.186
• InChiKey: KUVHOAJERYOATI-HDPOSUPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1R,4S,4aS,5R,8S,8aS,9aR,10aR)-1,4,5,8-Tetrachloro-11,11,12,12-tetramethoxy-octahydro-1,4;5,8-dimethano-anthracene-2,3,6,7-tetraone 在 zinc diacetate 作用下， 以 氯苯 为溶剂， 反应 67.0h， 生成 (1S,2S,4R,5R,16S,17S,19R,20R)-1,5,16,20-tetrachloro-35,35,36,36-tetramethoxy-10,11-dinitro-7,14,22,33-tetrazadecacyclo[18.14.1.15,16.02,19.04,17.06,15.08,13.021,34.023,32.025,30]hexatriaconta-6,8,10,12,14,21,23,25,27,29,31,33-dodecaene
  参考文献：
  名称：

  Synthesis and Luminescence Properties of U-Shaped Polycyclic Molecules Containing Syn-Facial Functionalized Quinoxaline Rings

  摘要：

  [GRAPHICS]Rigid U-shaped molecules containing syn-facially situated quinoxaline rings have been synthesized in three steps, by a combination of the Diels-Alder reaction, the ruthenium-catalyzed oxidation, and the Zn(OAc)(2)-catalyzed condensation of the resulting bis-alpha-diketones with benzene-1,2-diamines. The unsymmetric bis-quinoxalines, with electronically different substituents, and the quinoxaline ring-attached alpha-diketones were also prepared. Their luminescence properties were examined and described.

  DOI：

  10.1021/ol051707z
• 作为产物：
  描述：

  5,5-二甲氧基-1,2,3,4-四氯环戊二烯 在 sodium periodate 、 ruthenium(III) chloride trihydrate 作用下， 以 氯仿 、 对二甲苯 、 乙腈 为溶剂， 反应 69.5h， 生成 (1R,4S,4aS,5R,8S,8aS,9aR,10aR)-1,4,5,8-Tetrachloro-11,11,12,12-tetramethoxy-octahydro-1,4;5,8-dimethano-anthracene-2,3,6,7-tetraone
  参考文献：
  名称：

  含表面噻吩取代的喹喔啉环的C形非对映异构体：合成，光物理性质和X射线晶体学

  摘要：

  描述和合成两个非对映体的C形分子，它们含有表面噻吩取代的喹喔啉环。在乙酸锌的存在下，将先前已知的双-α-二酮与过量的4-溴-1,2-二氨基苯缩合，得到两个C形非对映异构体的混合物，所述C形非对映异构体具有被溴表面取代的喹喔啉环。色谱分离后，通过微波辅助的Suzuki偶联反应安装噻吩环，从而产生高发射率的非对映异构化合物，并通过UV-vis，荧光和NMR光谱以及X射线晶体学对其进行了研究。每个非对映异构体的独特对称性均通过NMR光谱证实。NMR数据表明，顺式异构体绕着连接噻吩和喹喔啉环的键的旋转受到限制，这也是在固态下观察到的。将C形非对映异构体的光谱性质与仅包含一个噻吩取代的喹喔啉环的模型化合物进行了比较。核磁共振和紫外可见光谱检测溶液中基态分子内π-π相互作用。观察到红移的发射带，谱带展宽和较大的斯托克斯频移，这共同表明激发态π-π相互作用产生准分子样的发射，以及显着的正发射溶剂变色，表明激发态下的电荷转移特性。

  DOI：

  10.1021/jo500053m

文献信息

• A Ruthenium-Catalyzed, Novel and Facile Procedure for the Conversion of Vicinal Dihaloalkenes to α-Diketones
  作者：Faiz Ahmed Khan、B. Prabhudas、Jyotirmayee Dash、Nilam Sahu

  DOI：10.1021/ja001956c

  日期：2000.10.1

  transition metal chemistry, used in the preparation of variety of heterocycles and natural products. α-Diketones also function as the key elements in the Weiss reaction and in the construction of rigid molecular assemblies (molecular wires, rods, etc.) based on ‘block’ chemistry. Some of the common methods to obtain α-diketones are: (i) oxidation of αhydroxyketones, (ii) oxidation of alkynes, and (iii)

  丰富的官能团以及在各种键形成反应中创建、相互转化和利用它们的大量方法是设计任何目标分子化学合成的重要资产。α-二酮是两个相邻羰基的强大组合，由于其广泛的应用而备受关注。α-二酮表现出有趣的光化学，用作调味剂，用作过渡金属化学中配体的前体，用于制备各种杂环和天然产物。α-二酮也是 Weiss 反应和基于“嵌段”化学的刚性分子组件（分子线、棒等）的构建中的关键元素。获得 α-二酮的一些常用方法是： (i) α-羟基酮的氧化，(ii) 炔烃的氧化，和 (iii) α-亚甲基酮的氧化。尽管烯烃的受控氧化很困难，但据报道，KMnO4/Ac2O 会产生低到中等产率的 α-二酮和副产物。但是，该方法不适用于小环（环辛烯以下）和双环系统。我们发现，邻位二卤代烯烃可以作为掩蔽的 α-二酮（方案 1）。我们特别选择了
• Intramolecular strong electronic coupling in a discretely H-aggregated phthalocyanine dimer connected with a rigid linker
  作者：Yasuyuki Yamada、Katsuhiko Nawate、Tomoaki Maeno、Kentaro Tanaka

  DOI：10.1039/c8cc04335c

  日期：——

  accurate assembly of phthalocyanines is rather difficult because of the high aggregation property of phthalocyanines. In this study, a novel discrete phthalocyanine dimer was prepared in which the relative configuration of each component was tightly and accurately fixed in an H-aggregate form by a rigid U-shaped linker. Electrochemical measurements showed that there were strong intramolecular electronic interactions

  由于酞菁的高聚集性质，制备精确组装的酞菁是相当困难的。在这项研究中，制备了一种新颖的离散的酞菁二聚体，其中每个组分的相对构型通过刚性U形接头牢固而精确地固定为H聚集体形式。电化学测量表明，两种酞菁之间存在强烈的分子内电子相互作用。
• Concise Synthesis of Novel Oxa-Bridged Compounds
  作者：Faiz Ahmed Khan、Jyotirmayee Dash、Ch. Sudheer、Nilam Sahu、Karuppasamy Parasuraman

  DOI：10.1021/jo0507385

  日期：2005.9.1

  The two oxa bridges are syn to each other, separated by central cyclohexane and cycloheptane rings in 10 and 27, while they are anti to each other and are separated by central cyclopentane and furan rings in 28 and 29. In the case of the highly symmetric bis-oxa-bridged derivative 10 the two syn oxa bridges constrain the central cyclohexane ring into the boat form. The endo,anti,endo 2:1 bis adducts of

  设计了一种立体选择性策略，用于用氧桥取代四卤代降冰片基衍生物的1，2-二卤代烯烃桥，所述氧桥涉及逐步控制的氧化，如此形成的二酮的裂解以及两个桥头卤素的分子内S N 2的迭代式置换。四个高度应变五环双氧杂桥接衍生物的合成10，27，28，和29与有趣的结构变化被呈现。这两个氧杂桥彼此同构，在10和27中被中央环己烷和环庚烷环隔开，而在它们之间彼此相反并被中央环戊烷和呋喃环隔开。28和29。在高度对称的双-氧杂桥联衍生物10的情况下，两个顺式氧杂桥将中央环己烷环约束为船形。首次制备了1,2,3,4-四卤代5,5-二甲氧基环戊-1,3-二烯与环戊二烯的内，反，内2：1双加合物，而先前未开发的双加合物的反应活性揭示了呋喃和环庚三烯的衍生物。
• Preparation, structures and preliminary host–guest studies of fluorinated <i>syn</i>-bis-quinoxaline molecular tweezers
  作者：Markus Etzkorn、Jacob C Timmerman、Matthew D Brooker、Xin Yu、Michael Gerken

  DOI：10.3762/bjoc.6.39

  日期：——

  potential molecular tweezers for electron-rich guest compounds. Our synthetic route to the cyclooctadiene-derived scaffolds 16a-d takes advantage of the facile isolation of a novel spirocyclic precursor 9b with the crucial syn-orientation of its two alkene moieties. The crystal structure of 16c displays two features typical of a molecular tweezer: inclusion of a solvent molecule in the molecular cleft and

  已经制备了一系列具有氟化同面喹喔啉侧壁的多环骨架作为富电子客体化合物的潜在分子镊子。我们的环辛二烯衍生支架 16a-d 的合成路线利用了新型螺环前体 9b 的简便分离及其两个烯烃部分的关键顺向取向。16c 的晶体结构显示出分子镊子的两个典型特征：在分子裂缝中包含溶剂分子和自互补支架的自缔合。此外，溶液中化合物 16c 的主客​​体 NMR 研究表明，未结合和结合的富电子客体 N,N,N',N'-四甲基-对苯二胺之间存在化学交换。
• Synthesis of a Novel, Highly Symmetric Bis-Oxa-Bridged Compound
  作者：Faiz Ahmed Khan、Jyotirmayee Dash

  DOI：10.1021/ja017371f

  日期：2002.3.1

  A highly oxygenated, novel pentacyclic bis-oxa-bridged compound 8 was synthesized with remarkable efficiency starting from readily available tetrachloro-5,5-dimethoxyclopentadiene and 1,4-cyclohexadiene in three steps. The ruthenium-catalyzed oxidation of 2:1 bis-adduct 1 followed by a one-pot transformation of the resulting bis-alpha-diketone 3 furnished (after esterification) the title compound in an overall yield of 29.1%. The versatility of this simple method was further demonstrated with other norbornyl alpha-diketones to obtain the corresponding strained oxa-bridged derivatives.