bis{[3,5-bis(octyloxy)phenyl]methyl} 11''-(carboxymethoxy)-4'',15''-dioxo-3',3''-(methanoxymethano[1,3]benzenomethanoxymethano)-3'H,3''H-dicyclopropa[1,9:3,15][5,6]fullerene-C60-I_h-3',3''-dicarboxylate | 220791-20-8

• 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{[3,5-bis(octyloxy)phenyl]methyl} 11''-(carboxymethoxy)-4'',15''-dioxo-3',3''-(methanoxymethano[1,3]benzenomethanoxymethano)-3'H,3''H-dicyclopropa[1,9:3,15][5,6]fullerene-C60-I_h-3',3''-dicarboxylate
• 英文别名: 2-[[5,65-Bis[(3,5-dioctoxyphenyl)methoxycarbonyl]-4,66-dioxo-3,67-dioxapentatriacontacyclo[67.3.1.17,18.05,31.06,31.06,45.08,46.09,17.010,48.011,16.012,50.013,52.014,22.015,20.019,28.021,26.023,53.024,55.025,61.027,62.030,63.032,64.033,44.034,58.035,43.036,40.037,57.038,54.039,51.041,49.042,47.056,60.059,64.059,65.029,74]tetraheptaconta-1(73),7(74),8(46),9(17),10,12(50),13,15,18,20,22,24(55),25,27,29,32,34(58),35,37,39,41(49),42,44,47,51,53,56,60,62,69,71-hentriacontaen-71-yl]oxy]acetic acid；2-[[5,65-bis[(3,5-dioctoxyphenyl)methoxycarbonyl]-4,66-dioxo-3,67-dioxapentatriacontacyclo[67.3.1.17,18.05,31.06,31.06,45.08,46.09,17.010,48.011,16.012,50.013,52.014,22.015,20.019,28.021,26.023,53.024,55.025,61.027,62.030,63.032,64.033,44.034,58.035,43.036,40.037,57.038,54.039,51.041,49.042,47.056,60.059,64.059,65.029,74]tetraheptaconta-1(73),7(74),8(46),9(17),10,12(50),13,15,18,20,22,24(55),25,27,29,32,34(58),35,37,39,41(49),42,44,47,51,53,56,60,62,69,71-hentriacontaen-71-yl]oxy]acetic acid
• CAS: 220791-20-8
• 化学式: C₁₂₂H₈₈O₁₅
• 分子量: 1794.03
• InChiKey: AVQUUTYNRXPCNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  28.6
• 重原子数：
  137
• 可旋转键数：
  43
• 环数：
  38.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  189
• 氢给体数：
  1
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  (4-羟基甲基苄基)-氨基甲酸叔丁酯 、 bis{[3,5-bis(octyloxy)phenyl]methyl} 11''-(carboxymethoxy)-4'',15''-dioxo-3',3''-(methanoxymethano[1,3]benzenomethanoxymethano)-3'H,3''H-dicyclopropa[1,9:3,15][5,6]fullerene-C60-I_h-3',3''-dicarboxylate 在 4-二甲氨基吡啶 、 1-羟基苯并三唑 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以61%的产率得到
  参考文献：
  名称：

  异位低聚亚苯基亚乙烯基/冠醚主体对C60铵底物的协同识别。

  摘要：

  已经制备了具有铵亚基的新的富勒烯衍生物。通过电喷雾质谱，UV-可见光谱和发光光谱实验证明了其与带有一个或两个冠醚部分的低聚亚苯基亚乙烯基衍生物形成超分子配合物的能力。有趣的是，由于分子内富勒烯-富勒烯相互作用，C60-铵阳离子与带有两个冠醚部分的低聚亚苯基亚乙烯基衍生物的组装导致2：1配合物的协同形成。

  DOI：

  10.1002/chem.200500246
• 作为产物：
  描述：

  bis{[3,5-bis(octyloxy)phenyl]methyl} 11''-[2-(1,1-dimethylethoxy)-2-oxoethoxy]-4'',15''-dioxo-3',3''-(methanoxymethano[1,3]benzenomethanoxymethano)-3'H,3''H-dicyclopropa[1,9:3,15][5,6]fullerene-C60-I_h-3',3''-dicarboxylate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以98%的产率得到bis{[3,5-bis(octyloxy)phenyl]methyl} 11''-(carboxymethoxy)-4'',15''-dioxo-3',3''-(methanoxymethano[1,3]benzenomethanoxymethano)-3'H,3''H-dicyclopropa[1,9:3,15][5,6]fullerene-C60-I_h-3',3''-dicarboxylate
  参考文献：
  名称：

  两亲富勒烯衍生物的合成及其在朗缪尔和朗缪尔-布洛杰特薄膜中的结合

  摘要：

  通过用丙二酸单酯 5-7 酯化获得的丙二酸酯或双丙二酸酯衍生物对 [5,6] 富勒烯-C60-Ih (C60) 进行官能化制备各种两亲富勒烯衍生物。环丙富勒烯 10 是通过将 6 的羧酸官能团保护为叔丁酯，然后将 Bingel 添加到 C60 和脱保护步骤（方案 2）而获得的。还尝试在宾格尔条件下直接由丙二酸单酯 6 制备 10。令人惊讶的是，形成了相应的 3'-iodo-3'H-cyclopropa[1,9][5,6]fullerene-C60-Ih-3'-carboxylate 11 而不是 10（方案 3）。通过分别从丙二酸单酯 13 和 14 制备 15 和 16 证实了这种新反应的一般特征（方案 4）。所有其他两亲富勒烯衍生物都是利用 Diederich 及其同事开发的多功能区域选择性反应制备的，该反应通过在 C 球上与双丙二酸衍生物在双宾格尔中的环化反应生成 C60 的大环双加合物环丙烷化。分别由二醇

  DOI：

  10.1002/1522-2675(200201)85:1<288::aid-hlca288>3.0.co;2-i

文献信息

• Fullerodendrimers with a tris-isothiocyanate core allowing their anchoring onto gold electrodes
  作者：Jose Antonio Camerano、Miguel Angel Casado、Uwe Hahn、Jean-François Nierengarten、Emmanuel Maisonhaute、Christian Amatore

  DOI：10.1039/b706319a

  日期：——

  Dendrimers with peripheral fullerene subunits and a tris-isothiocyanate core have been prepared and self-assembled onto a gold surface; detailed electrochemical studies revealed that electron transfer from the electrode to the fullerene subunits occurs through space at a short distance from the electrode.

  我们制备了具有外围富勒烯亚基和三异硫氰酸酯核心的树枝状聚合物，并将其自组装到金表面；详细的电化学研究表明，电子从电极转移到富勒烯亚基是通过距离电极很近的空间进行的。
• Fullerohelicates: a new class of fullerene-containing supermoleculesElectronic supplementary information (ESI) available: 1H-NMR spectra of 1 and Cu2(1)2. See http://www.rsc.org/suppdata/cc/b4/b404742g/
  作者：Fran�ois Cardinali、Hind Mamlouk、Yannick Rio、Nicola Armaroli、Jean-Fran�ois Nierengarten

  DOI：10.1039/b404742g

  日期：——

  A multicomponent array made of a bis-copper(I) helicate core and two peripheral fullerene subunits has been prepared and electron transfer from the photoexcited Cu(I)-complexed unit to C60 occurs.

  我们制备了一个由双铜（I）合核和两个外围富勒烯亚基组成的多组分阵列，并实现了从光激发的铜（I）络合单元到 C60 的电子转移。
• Phenanthroline ligands substituted with fullerene-functionalized dendritic wedges and their copper(I) complexes
  作者：Jean-François Nierengarten、Delphine Felder、Jean-François Nicoud

  DOI：10.1016/s0040-4039(98)02379-x

  日期：1999.1

  Fullerene-functionalized dentritic wedges with a car☐ylic acid function have been attached to a phenanthroline diol derivative. Assembling of the resulting phenanthroline ligands around a copper(I) center gives the corresponding dendritic complexes with 4, 8 or 16 peripherical C60 groups.

  具有邻氨基苯甲酸功能的富勒烯官能化的树枝状楔形物已连接到菲咯啉二醇衍生物上。围绕铜（I）中心组装得到的菲咯啉配体得到相应的具有4、8或16个外围C 60基团的树状络合物。
• Preparation of dendrons with peripheral fullerene units
  作者：Jean-François Nierengarten、Delphine Felder、Jean-François Nicoud

  DOI：10.1016/s0040-4039(98)02378-8

  日期：1999.1

  Highly soluble dendritic branches with fullerene subunits at the periphery and a carboxylic acid function at the focal point have been prepared by a convergent approach, using successive DCC-mediated esterifications followed by cleavage of a t-butyl ester moiety under acidic conditions. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.
• Synthesis of fullerohelicates and fine tuning of the photoinduced processes by changing the number of addends on the fullerene subunits
  作者：Michel Holler、François Cardinali、Hind Mamlouk、Jean-François Nierengarten、Jean-Paul Gisselbrecht、Maurice Gross、Yannick Rio、Francesco Barigelletti、Nicola Armaroli

  DOI：10.1016/j.tet.2005.07.126

  日期：2006.2

  Two fullerene-substituted m-phenylene-bis-phenanthroline ligands have been prepared. The synthesis of the first derivative (L1) is based on an esterification reaction between a C-s symmetrical cis-2 fullerene bis-adduct bearing a carboxylic acid function and a bisphenanthroline alcohol (5). The second ligand (L2) has been obtained by reaction of a bis-phenanthroline malonate (9) and C-60 under Bingel conditions. The copper(I) complexes of L1 and L2 have been prepared by treatment with a slight excess of Cu(CH3CN)(4)BF4. NMR spectroscopy and mass spectrometry analysis have unambiguously shown that these complexes are bis-copper(l) helicates substituted with two fullerene moieties. The photophysical properties of the copper(I) complexes Cu-2(L1)(2) and Cu-2(L2)(2) have been investigated. In both systems photoinduced electron transfer from the central metal-complexed unit to the external fullerenes may occur, in principle, by excitation of both moieties. However, this is found to be the case only for the methanofullerene system Cu-2(L2)(2). Unexpectedly, for Cu-2(L1)(2), photoexcitation of the peripheral carbon spheres is followed by regular internal deactivation. Possible reasons for this behavior are examined in light of current theories for photoinduced energy and electron transfer. (c) 2006 Elsevier Ltd. All rights reserved.