(+/-)-tetraethyl 1,2:67,68-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate | 170503-86-3

• 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: (+/-)-tetraethyl 1,2:67,68-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate
• 英文别名: Tetraethyl 1,2:67,68-bis(methano)[70]fullerene-71,71,72,72-tetracarboxylate
• CAS: 170503-86-3
• 化学式: C₈₄H₂₀O₈
• 分子量: 1157.08
• InChiKey: PWVZTURTZPUJDR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.07
• 重原子数：
  92.0
• 可旋转键数：
  8.0
• 环数：
  39.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  105.2
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  (+/-)-tetraethyl 1,2:67,68-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate 、 丙二酸二乙酯 在 碘 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二甲基亚砜 、 甲苯 、 乙腈 为溶剂， 以75%的产率得到(+/-)-octaethyl 1,2:31,32:39,40:69,70-tetramethano[70]fullerene-71,71,72,72,73,73,74,74-octacarboxylate
  参考文献：
  名称：

  超分子富勒烯化学：C70 的环烷型单冠醚和双冠醚共轭物的综合研究

  摘要：

  C70 的共价模板化双功能化，使用由抗二取代二苯并 [18]crown-6 (DB18C6) 醚连接的双丙二酸 5，以完全区域特异性进行并提供两个非对映异构体对的对映体 C70 冠醚缀合物，（± )-7a 和 (±)-7b，具有在顺序变换中不受欢迎的五点钟双加法模式（方案 1）。通过 X 射线晶体结构分析揭示了 (±)-7a 的身份（图 6）。使用含有顺二取代 DB18C6 系链的双丙二酸酯 6，通过双宾格尔环丙烷化的大环化反应的区域选择性完全改变，在大约 1:1 的比例分别具有十二 (16) 和两点 ((±)-15) 加法模式（方案 3）。十二点钟双加合物 16 的 X 射线晶体结构分析表明，在冠醚腔中包含一个 H2O 分子（图 7 和图 8）。两个连续的 Bingel 大环化，首先是抗 DB18C6-tethered (5)，然后是 syn-DB18C6-tethered (6) 双丙

  DOI：

  10.1002/1522-2675(200207)85:7<2009::aid-hlca2009>3.0.co;2-g
• 作为产物：
  描述：

  tetrakis<(ethoxycarbonyl)methyl> 1,2:67:68-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate 在 potassium carbonate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 2.0h， 以72%的产率得到(+/-)-tetraethyl 1,2:67,68-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate
  参考文献：
  名称：

  Achiral and Chiral Higher Adducts of C70 byBingel Cyclopropanation

  摘要：

  Five optically active isomeric C-70 bis-adducts with (R)-configured chiral malonate addends were prepared by Bingel cyclopropanation (Scheme 1) and their circular dichroism (CD) spectra investigated in comparison to those of the corresponding five bis-adducts with (S)-configured addends (Fig. 2). Pairs of diastereoisomers, in which the inherently chiral addition patterns on the fullerene surface have an enantiomeric relationship, display mirror-image shaped CD spectra that are nearly identical to those of the corresponding pairs of enantiomers (Fig. 3, b and c). This result demonstrates that the Cotton effects arising from the chiral malonate addends are negligible as compared to the chiroptical contribution of the chirally functionalized fullerene chromophore. A series of four stereoisomeric tetrakis-adducts (Fig. 4) was prepared by Bingel cyclopropanation starting from four stereoisomeric bis-adducts. A comparison of the CD spectra of both series of compounds showed that the magnitude of the Cotton effects does not decrease with increasing degree of functionalization (Fig. 5). Bingel cyclopropanations of C-70 in Me2SO are dramatically faster than in apolar solvents such as CCl4, and the reaction of bis-adducts (+/-)-13 and 15 with large excesses of diethyl 2-bromomalonate and DBU generate 1, via the intermediacy of defined tetrakis-adducts (+/-)-16 and 17, respectively, a series of higher adducts including hexakis-, heptakis-, and octakis-adducts (Table 1). A high regioselectivity was observed up to the stage of the hexakis-adducts, whereas this selectivity became much reduced at higher stages of addition. The regioselectivity of the nucleophilic cyclopropanations of C-70 correlates with the coefficients of the LUMO (lowest unoccupied molecular orbital) and LUMO + 1 at the positions of preferential attack calculated by restricted Hartree-Fock self-consistent field (RHF-SCF) methods (Figs. 9-11). Based on predictions from molecular-orbital calculations (Fig. II) and the analysis of experimental C-13-NMR data (Fig. 7,a), the structure of a unique hexakis-adduct ((+/-)-22, Fig. 12),prepared from (+/-)-13, was assigned. The C-2-symmetrical compound contains four 6-6-closed methanofullerene sub-structures in its polar regions (at the bonds C(1)-C(2), C(31)-C(32), C(54)-C(55),and C(59)-C(60)), and two 6-5-open methanofullerene sub-structures parallel to the equator (at C(22)- C(23) and C(26)- C(27)). The 6-5-open sub-structures are formed by malonate additions to near-equatorial 6-5 bonds with enhanced LUMO coefficients: followed by valence isomerization (Fig. 12).

  DOI：

  10.1002/(sici)1522-2675(19990210)82:2<261::aid-hlca261>3.0.co;2-x

文献信息

• Selective Electrolytic Removal of Bis(alkoxycarbonyl)methano Addends from C60 Bis-adducts and Electrochemical Stability of C70 Derivatives
  作者：Roland Kessinger、Nicolette S. Fender、Lourdes E. Echegoyen、Carlo Thilgen、Luis Echegoyen、François Diederich

  DOI：10.1002/1521-3765(20000616)6:12<2184::aid-chem2184>3.0.co;2-6

  日期：2000.6.16

  group in the construction of multiple adducts of C60 with unusual addition patterns. The Bingel-type mono-adduct of C70 10 and the constitutionally isomeric bis-adducts 11, (+/-)-12, and (+/-)-13 were also included in this investigation. A large difference in the electrochemical behavior between C70 bis-adducts and the corresponding C60 derivatives was observed. Thus, the intramolecular "walk-on-the-sphere"

  C60（+/-）-4-（+/-）-8和9的新型混合双加合物，带有双（乙氧基羰基）甲醇加成物（Bingel加成物）和第二个加成物（[1,2] benzeno ，但分两步反应合成了碳球的6,6-闭合键的[2] eno，甲基苯胺基甲基或二芳基甲基）桥连。每个二加合物在第二个富勒烯中心还原步骤的电位下进行彻底电解，从而选择性除去Bingel加成物（复古宾格尔反应），生成相应的单加合物，将其分离后收率超过60 ％。这些结果开辟了将Bingel加成物用作具有不同加成模式的C60的多个加合物的构建中的临时保护和指导基团的可能性。C70 10的Bingel型单加合物和组成异构的双加合物11（+/-）-12，和（+/-）-13也包括在这项调查中。观察到C70双加合物与相应的C60衍生物之间的电化学行为存在很大差异。因此，在两电子控制电位电解（CPE）的条件下，C60的Bingel型双加合物容易发生的分子内“
• Solvent‐Free Reactions of Fullerenes with Diethyl Bromomalonate in the Presence of Inorganic Bases Under High‐Speed Vibration Milling Conditions
  作者：Ru‐Fang Peng、Guan‐Wu Wang、Ye‐Bing Shen、Yu‐Jin Li、Ting‐Hu Zhang、You‐Cheng Liu、Yasujiro Murata、Koichi Komatsu

  DOI：10.1081/scc-120030320

  日期：2004.12.31

  Abstract Solvent‐free reactions of C60 and C70 with diethyl bromomalonate in the presence of various inorganic bases were investigated under the high‐speed vibration milling (HSVM) conditions, and are shown to give methanofullerenes 1 and 2 in good to excellent yields based on consumed fullerenes. Several weak inorganic bases were found to be quite effective in promoting the solvent‐free mechanochemical

  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。
• First tether-directed regioselective bis-functionalisation of C70: effects of cation complexation on the redox properties of diastereoisomeric fullerene crown ether conjugates
  作者：Maurice J. van Eis、Paul Seiler、François Diederich、Robert J. Alvarado、Luis Echegoyen

  DOI：10.1039/b006066f

  日期：——

  The covalently templated bis-functionalisation of C70, employing a dibenzo-18-crown-6 tether, proceeds with complete regiospecificity and provides a bis-addition pattern which is disfavoured in sequential transformations.

  C70 的共价模板化双功能化，使用 dibenzo-18-crown-6 系链，以完全区域特异性进行，并提供在连续转化中不受欢迎的双加成模式。
• Bingel, Carsten; Schiffer, Heinz, Liebigs Annalen, 1995, # 8, p. 1551 - 1554
  作者：Bingel, Carsten、Schiffer, Heinz

  DOI：——

  日期：——