9-[bis(ethynyl)methylene]-9H-fluorene | 681164-25-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-[bis(ethynyl)methylene]-9H-fluorene
• 英文别名: Iewmsnfigtymne-uhfffaoysa-；9-penta-1,4-diyn-3-ylidenefluorene
• CAS: 681164-25-0
• 化学式: C₁₈H₁₀
• 分子量: 226.277
• InChiKey: IEWMSNFIGTYMNE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  9-[bis(ethynyl)methylene]-9H-fluorene 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Assembly of organosilver coordination frameworks with aromatic ligands bearing a terminal enediyne group

  摘要：

  In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H(2)L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H2L2), each resulting ethynide ligand is invariably inserted into a Ag-n (n = 3-4) basket, leading to the generation of coordination chains or multinuclear metallocycles, but the well shielded ethenyl group does not take part in silver-olefin binding. In (Ag(2)L1)center dot 9AgCF(3)CO(2)center dot 3H(2)O center dot 3CH(3)CN and (Ag(2)L1)(2)center dot 9AgCF(3)CO(2).11H(2)O, which can be crystallized in different polar protic solvent media, an infinite chain composed of metallocycles is favorably generated with the assistance of silver-aromatic interaction; such chains are further interconnected to form a two- or three-dimensional organosilver network. In (Ag2L2)center dot 5AgCF(3)CO(2)center dot 5DMSO, the fluorenyl group does not participate in silver-aromatic interaction; however, its planar skeleton directs the construction of a more closely packed metal-organic coordination chain. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.02.020
• 作为产物：
  描述：

  9-(dibromomethylene)-9H-fluorene 在 甲醇 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 18.0h， 生成 9-[bis(ethynyl)methylene]-9H-fluorene
  参考文献：
  名称：

  Assembly of organosilver coordination frameworks with aromatic ligands bearing a terminal enediyne group

  摘要：

  In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H(2)L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H2L2), each resulting ethynide ligand is invariably inserted into a Ag-n (n = 3-4) basket, leading to the generation of coordination chains or multinuclear metallocycles, but the well shielded ethenyl group does not take part in silver-olefin binding. In (Ag(2)L1)center dot 9AgCF(3)CO(2)center dot 3H(2)O center dot 3CH(3)CN and (Ag(2)L1)(2)center dot 9AgCF(3)CO(2).11H(2)O, which can be crystallized in different polar protic solvent media, an infinite chain composed of metallocycles is favorably generated with the assistance of silver-aromatic interaction; such chains are further interconnected to form a two- or three-dimensional organosilver network. In (Ag2L2)center dot 5AgCF(3)CO(2)center dot 5DMSO, the fluorenyl group does not participate in silver-aromatic interaction; however, its planar skeleton directs the construction of a more closely packed metal-organic coordination chain. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.02.020

文献信息

• Reductive Bergman-Type Cyclizations of Cross-Conjugated Enediynes to Fulvene and Fulvalene Anions:  The Role of the Substituent
  作者：Noach Treitel、Lior Eshdat、Tuvia Sheradsky、Patrick M. Donovan、Rik R. Tykwinski、Lawrence T. Scott、Henning Hopf、Mordecai Rabinovitz

  DOI：10.1021/ja0566477

  日期：2006.4.1

  Various cross-conjugated enediynes undergo "Bergman-type" cycloaromatizations upon reduction with potassium metal, generating anions of fulvenes and fulvalene derivatives. This new anionic cyclization is considerably more facile than the classic Bergman cyclization with linear enediynes, creating highly reactive diradicals at -78 degrees C. Not all cross-conjugated enediynes yield cyclized dianions

  各种交叉共轭的烯二炔在用金属钾还原后经历“伯格曼型”环芳构化，生成富烯和富瓦烯衍生物的阴离子。这种新的阴离子环化比使用线性烯二炔的经典 Bergman 环化容易得多，在 -78 摄氏度时产生高反应性双自由基。并非所有交叉共轭的烯二炔在还原时都会产生环化双阴离子。一些产生未环化的、Y 形的、交叉共轭的二价阴离子，而另一些显然产生二聚化或作为单体持续存在的自由基阴离子。一个系统产生环化和未环化的二价阴离子。因此，取代基被证明是决定还原结果的关键因素。环化发生在由取代基控制的特定“机会窗口”内。
• Elaboration of Diaryl Ketones into Naphthalenes Fused on Two or Four Sides:  A Naphthoannulation Procedure
  作者：Patrick M. Donovan、Lawrence T. Scott

  DOI：10.1021/ja038254i

  日期：2004.3.1

  Transition metal-catalyzed double ring closures of 1,1-diaryl-2,2-diethynylethylenes yield polycyclic aromatic hydrocarbons and heterocycles that contain a newly formed naphthalene ring system embedded in a larger polycyclic network. The diynes required for this procedure are readily synthesized from diaryl ketones by the Corey-Fuchs olefination and subsequent Sonogashira coupling with trimethylsilylacetylene

  1,1-二芳基-2,2-二乙炔基乙烯的过渡金属催化双环闭合产生多环芳烃和杂环，其中包含嵌入更大多环网络中的新形成的萘环系统。该过程所需的二炔很容易从二芳基酮通过 Corey-Fuchs 烯化和随后的 Sonogashira 与三甲基甲硅烷基乙炔偶联，然后脱甲硅烷基化合成。通过此程序，可以轻松获得新化合物，例如 3,11-二叔丁基 [4] 螺旋烯和 1,8,9- 环萘并噻吨。通过该程序对 9,10-蒽醌进行双环化，在一次操作中闭合四个新的苯环得到晕苯，尽管目前这种情况下的产率很低。
• Electrochromic Application of an Enediyne Scaffolding as a Redox-Active Chromophore− Synthesis and Redox Behavior of 9,10-Bis[3-(6-azulenyl)-1-(6-azulenylethynyl)-2-propynylidene]-9,10-dihydroanthracenes
  作者：Shunji Ito、Haruki Inabe、Noboru Morita、Akio Tajiri

  DOI：10.1002/ejoc.200300765

  日期：2004.4

  A bis(enediyne) system utilizing anthraquinodimethane as a platform for a redox-active substructure that bears azulenes as π-electron-accepting groups at the periphery has been prepared by a simple one-pot reaction involving repeated Pd-catalyzed alkynylation of 6-bromoazulenes with the bis(enediyne). The novel bis(enediyne)s exhibited two, one-step two-electron redox properties under electrochemical

  利用蒽醌二甲烷作为氧化还原活性亚结构平台的双（烯二炔）系统，通过简单的一锅反应制备了一个简单的一锅反应，涉及重复的 Pd 催化的 6-溴芘炔基化与双（烯二炔）。新型双（烯二炔）在电化学还原条件下表现出两种一步两电子氧化还原特性，同时由于两电子还原产生闭壳花青型亚结构而显着的颜色变化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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