bis(ethoxycarbonyl)methanofullerene | 153218-90-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: bis(ethoxycarbonyl)methanofullerene
• 英文别名: Diethyl 1,2-methano-1,2-dihydro[60]fullerene-61,61-dicarboxylate；bis(ethoxycarbonyl)methano-1,2-dihydro[6]fullerene；Diethylcarboxylate methanofullerene；di(ethoxycarbonyl)methanofullerene；diethyl malonate fullerene；[60] fullerene cyclopropanedicarboxylic acid ethyl ester
• CAS: 153218-90-7
• 化学式: C₆₇H₁₀O₄
• 分子量: 878.814
• InChiKey: JBJAEUONJLPFFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.7
• 重原子数：
  71
• 可旋转键数：
  6
• 环数：
  33.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  bis(ethoxycarbonyl)methanofullerene 在 tert-butylammonium hexafluorophosphate(V) 作用下， 以 二氯甲烷 为溶剂， 以82%的产率得到足球烯
  参考文献：
  名称：

  Preparation of Enantiomerically Pure C76 with a General Electrochemical Method for the Removal of Di(alkoxycarbonyl)methano Bridges from Methanofullerenes: The Retro-Bingel Reaction

  摘要：

  DOI：

  10.1002/(sici)1521-3773(19980803)37:13/14<1919::aid-anie1919>3.0.co;2-x
• 作为产物：
  描述：

  溴代丙二酸二乙酯 、 足球烯 在 sodium acetate 作用下， 以59%的产率得到bis(ethoxycarbonyl)methanofullerene
  参考文献：
  名称：

  高速振动研磨条件下无机碱存在下富勒烯与溴丙二酸二乙酯的无溶剂反应

  摘要：

  摘要 在高速振动研磨 (HSVM) 条件下研究了 C60 和 C70 与溴丙二酸二乙酯在各种无机碱存在下的无溶剂反应，结果表明，基于消耗的富勒烯。发现几种弱无机碱在 HSVM 条件下对促进 C60 和 C70 的无溶剂机械化学宾格尔反应非常有效。在研究的碱中，乙酸钠的单加合物产量最高，而碳酸钾为 C60 和 C70 提供了大量的双加合物。#西南科技大学材料学院访问学者。

  DOI：

  10.1081/scc-120030320
• 作为试剂：
  描述：

  、 溴代丙二酸二乙酯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 bis(ethoxycarbonyl)methanofullerene 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 10.0h， 生成 (+/-)-tetraethyl 1,2:33,50-bis(methano)[60]fullerene-61,61,62,62-tetracarboxylate 、 、 Tetraethyl tritriacontacyclo[10.7.7.62,4.46,7.313,15.317,19.23,20.29,11.210,26.222,24.15,8.014,25.016,23.018,21.734,41.229,43.130,31.138,39.027,46.028,42.029,46.032,45.033,59.035,36.037,53.040,49.044,62.048,56.050,52.050,57.052,61.054,58.055,60]dohexaconta-1,3,5,7,9,11(39),12(26),13,15,17(35),18,20,22,24,27,30(62),31,33,36,38(61),40(49),41(48),42,44,53,55(60),56,58-octacosaene-47,47,51,51-tetracarboxylate
  参考文献：
  名称：

  凹凸 π-π 模板方法可合成 [10] 环对亚苯基-富勒烯 [2] 轮烷

  摘要：

  环对亚苯基 (CPP) 是一类紧张的大环化合物，直到 2008 年才被认为是有机合成无法实现的。凭借其十个对位取代亚苯基环的环状阵列，[10]CPP 具有凹 π 系统，该系统完美地预先组织为凸富勒烯（如 C60）的强超分子缔合。尽管已在气相中观察到机械互锁的 CPP 结构，但尚未实现批量的合理合成，这可能是由于常规模板策略不适用于缺乏杂原子的 CPP 环。在这里，我们报告了两种 [2] 轮烷的合成，其中 [10]CPP 环与中心富勒烯双加合物结合，并且由于存在两个庞大的富勒烯六加合物塞子而防止脱螺纹。轮烷合成的最后一步非常有效（产率高达约 40%）和区域选择性，因为富勒烯充当有效的凸模板，而 [10]CPP 充当超分子导向基团，控制中心富勒烯的反应专门针对两个反式区域异构体。综合物理化学研究证实了互锁结构，阐明了 CPP-富勒烯相互作用的动态性质，并揭示了机械键对电荷转移过程的有趣结果。鉴

  DOI：

  10.1021/jacs.8b08244

文献信息

• Facile Catch and Release of Fullerenes Using a Photoresponsive Molecular Tube
  作者：Norifumi Kishi、Munetaka Akita、Motoshi Kamiya、Shigehiko Hayashi、Hsiu-Fu Hsu、Michito Yoshizawa

  DOI：10.1021/ja406893y

  日期：2013.9.4

  A novel M2L2 molecular tube capable of binding fullerene C60 was synthesized from bispyridine ligands with embedded anthracene panels and Ag(I) hinges. Unlike previous molecular cages and capsules, this open-ended tubular host can accommodate a single molecule of various C60 derivatives with large substituents. The fullerene guest can then be released by using the ideal, noninvasive external stimulus

  一种能够结合富勒烯 C60 的新型 M2L2 分子管是由双吡啶配体合成的，具有嵌入的蒽板和 Ag(I) 铰链。与以前的分子笼和胶囊不同，这种开放式管状主体可以容纳具有大取代基的各种 C60 衍生物的单个分子。然后可以通过使用理想的非侵入性外部刺激光释放富勒烯客体。
• Bromination by means of sodium monobromoisocyanurate (SMBI)
  作者：Yukihiro Okada、Masanori Yokozawa、Miwa Akiba、Kazuhiko Oishi、Kyoji O-kawa、Tomohiro Akeboshi、Yasuo Kawamura、Seiichi Inokuma、Yosuke Nakamura、Jun Nishimura

  DOI：10.1039/b302738d

  日期：——

  monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that

  用一溴异氰尿酸钠（SMBI）1溴化具有激活和失活取代基的各种芳族化合物，将二乙醚，二乙醚-甲磺酸，三氟乙酸或硫酸用作溶剂。因此，硝基苯在硫酸中方便地被溴化，苯在乙醚-甲磺酸中很容易被单溴化，并且苯酚在回流条件下在温和条件下在邻位选择性溴化。对于容易质子化的取代基，在与1的反应中可以使用三氟乙酸作为溶剂，相反​​，NBS在三氟乙酸中无效。相对于NBS，这提供了一种更好的试剂。除芳族化合物外，烯烃，酮和酯也用1溴化。
• Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units
  作者：David Kreher、Michel Cariou、Sheng-Gao Liu、Eric Levillain、Jaume Veciana、Concepció Rovira、Alain Gorgues、Piétrick Hudhomme

  DOI：10.1039/b201695h

  日期：2002.6.21

  Our recent works on fused TTF–C60 dyads, (TTF)n–C60 polyads and C60–TTF–C60 dumbbell triads in which the acceptor C60 is doubly tethered to the donor tetrathiafulvalene through a rigidified cyclohexene ring are presented. This approach was developed in order to control the relative orientation as well as the distance between both donor and acceptor entities. Thereby, through-space interactions which are of great importance for photoinduced electron- and/or energy-transfer processes are expected to dominate because of the special topology of the molecules. The two linked C60 and TTF chromophores in such adducts are not only in close proximity but also have optimal orbital orientations, thus facilitating these through-space electronic interactions. These new C60-based assemblies were synthesized by [4 + 2] Diels–Alder cycloaddition reactions. The different methodologies considered for their synthesis are discussed, their analytical, spectroscopic characterizations and electrochemical properties are also described. The selective electro-oxidation or reduction afforded the corresponding radical cation and radical anion which were characterized by EPR. These C60-based assemblies were studied for their nonlinear optical and optical limiting applications. Moreover, intramolecular photoinduced charge-separation and charge-recombination processes in a fused C60–TTF–C60 dumbbell triad which was designed to be soluble in organic solvents were investigated by time-resolved absorption and fluorescence techniques. Appreciable interaction between the C60 moiety and TTF moiety in the ground state was suggested by steady-state absorption spectra and the fluorescence spectra showed considerable interaction in the singlet excited state. The nanosecond transient absorption spectra displayed the formation of the charge-separated radical pair C60–TTF˙+–C60˙−, characterized by a lifetime of ca. 20 ns in benzonitrile.

  我们最近的研究工作集中在融合的TTF–C60二聚体、(TTF)n–C60多聚体和C60–TTF–C60哑铃三聚体，这些体系中受体C60通过刚性的环己烯环与供体四硫富瓦烯双重连接。此方法的开发旨在控制供体和受体之间的相对方向和距离。因此，由于分子的特殊拓扑结构，空间内的相互作用在光诱导电子及/或能量转移过程中预计将占主导地位。这种加合物中连接的C60和TTF色团不仅相互接近，而且具有最佳的轨道取向，从而促进这些跨空间的电子相互作用。这些新的基于C60的组装体是通过[4 + 2]迪尔斯－阿尔德环加成反应合成的。文中讨论了其合成过程中考虑的不同方法，并描述了它们的分析、光谱特性及电化学性质。选择性电氧化或还原生成了相应的自由基阳离子和自由基阴离子，这些都通过电子顺磁共振（EPR）进行了表征。这些基于C60的组装体也被研究用于其非线性光学和光限制应用。此外，设计为可溶于有机溶剂的融合C60–TTF–C60哑铃三聚体中的分子内光诱导电荷分离和电荷重组过程通过时间分辨吸收和荧光技术进行了研究。在基态中，稳态吸收光谱表明C60基团与TTF基团之间存在显著的相互作用，而荧光光谱则显示在单重激发态中也存在较强的相互作用。纳秒瞬态吸收光谱显示了电荷分离的自由基对C60–TTF˙+–C60˙–，其在苯腈中表征的寿命约为20纳秒。
• Effect of different substituents on the water-solubility and stability properties of 1 : 2 [60]fullerene derivative·gamma-cyclodextrin complexes
  作者：Atsushi Ikeda、Akiko Hirata、Michiko Ishikawa、Jun-ichi Kikuchi、Shunsuke Mieda、Wataru Shinoda

  DOI：10.1039/c3ob41513a

  日期：——

  We have demonstrated that C60 derivatives bearing a pyrrolidine moiety as well as a variety of other substituents can form 1 : 2 complexes with γ-cyclodextrin (γ-CDx) using a mechanochemical high-speed vibration milling apparatus. When the influence of the steric hindrance of the substituents on the formation of the complexes was negligible, the water-solubilities of the complexes were shown experimentally to be completely dependent on the hydrophobic properties of the substituent. Furthermore, the stabilities of the γ-CDx-complexes of several different C60 derivatives were found to be similar to or slightly higher than that of the C60·γ-CDx complex, with the solubilities of the complexes showing no correlation to the stabilities. Based on the results of a series of theoretical investigations, we have shown that the stabilities of the γ-CDx-complexes can be affected not only by steric effects but also by the polarities of the substituent groups, which exist in the vicinity of the upper rim of γ-CDx, because the water bound to the polar group can assist in the stabilisation of the complexes.

  我们利用机械化学高速振动研磨装置证明，含有吡咯烷分子以及其他多种取代基的 C60 衍生物可以与δ³-环糊精（δ³-CDx）形成 1:◎2 复合物。当取代基的立体阻碍对络合物形成的影响可以忽略不计时，实验证明络合物的水溶性完全取决于取代基的疏水性。此外，研究还发现几种不同 C60 衍生物的 δ³-CDx 复合物的稳定性与 C60Â-δ³-CDx 复合物的稳定性相似或略高于后者，而复合物的溶解度与稳定性没有相关性。根据一系列理论研究的结果，我们发现 δ³-CDx 复合物的稳定性不仅会受到立体效应的影响，还会受到存在于 δ³-CDx 上缘附近的取代基团极性的影响，因为与极性基团结合的水可以帮助稳定复合物。
• Sequential Fullerenylation of Bis-malonates - Efficient Access to Oligoclusters with Different Fullerene Building Blocks
  作者：Lennard K. Wasserthal、Andreas Kratzer、Andreas Hirsch

  DOI：10.1002/ejoc.201300122

  日期：2013.4

  A method for the sequential fullerenylation of bis-malonates with parent C60 and C2v-symmetric pentakis-adducts is reported. This approach relies on the finding that (a) chloromalonates can be used for the nucleophilic cyclopropanation of [6,6] double bonds of C60, and (b) chloromalonates, in contrast to bromomalonates, do not undergo base-catalyzed halogen exchange reactions. For the proof of concept

  报告了双丙二酸酯与母体 C60 和 C2v 对称五角加合物的连续富勒烯化的方法。这种方法依赖于以下发现：(a) 氯丙二酸酯可用于 C60 的 [6,6] 双键的亲核环丙烷化，并且 (b) 氯丙二酸酯与溴丙二酸酯相比，不进行碱催化的卤素交换反应。为了证明概念，我们使用基于富勒烯六加合物的发散方法合成了七富勒烯，在八面体位置具有六个双丙二酸加合物，每个加合物都适用于富勒烯结构单元的额外环丙烷化。