tetrakis<(ethoxycarbonyl)methyl> 1,2:56,57-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate | 173202-47-6

• 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: tetrakis<(ethoxycarbonyl)methyl> 1,2:56,57-bis(methano)<70>fullerene-71,71,72,72-tetracarboxylate
• CAS: 173202-47-6
• 化学式: C₉₂H₂₈O₁₆
• 分子量: 1389.22
• InChiKey: AFIQZULWCQPNJY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.24
• 重原子数：
  108.0
• 可旋转键数：
  16.0
• 环数：
  39.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  210.4
• 氢给体数：
  0.0
• 氢受体数：
  16.0

反应信息

• 作为反应物：
  描述：

  tetrakis<(ethoxycarbonyl)methyl> 1,2:56,57-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91%的产率得到(+/-)-tetraethyl 1,2:56,57-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
• 作为产物：
  描述：

  富勒烯 、 2-Bromo-malonic acid diethoxycarbonylmethyl ester 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以47%的产率得到bis[(ethoxycarbonyl)methyl] 1,2-methanol[70]fullerene-71,71-dicarboxylate
  参考文献：
  名称：

  C 70的多次环丙烷化。双-，三-和四-加合物的合成和表征以及具有手性加成的双-加合物的手性，包括关于具有手性加成形式的富勒烯衍生物的构型描述的建议

  摘要：

  在系统研究中，研究了在以1,8-二氮杂双环[5.4.0] undec-7-ene（DBU）为碱的情况下，C 70与2-溴丙二酸酯的多个环丙烷化的区域选择性（Bingel反应）。在富勒烯的两个相反的极点上，由最金字塔形的sp 2 -C原子形成的66个键优先发生双加合物的形成，并且在与非手性双[（乙氧基羰基）甲基] 2-溴丙二酸酯（13a）的反应中产生三个组成上异构的双（甲基）富勒烯（方案2）。其中两个C 2-对称（±）-1和（±）-2，是手性的；以前的调查中未曾考虑过的事实。首次观察到第三C 2 v对称异构体3的形成。提出了富勒烯衍生物的构型描述，所述富勒烯衍生物由于特定的官能化模式而具有手性发色团。C 70与旋光性双[（S）-1-苯基丁基] 2-溴丙二酸双（（S）-1-苯基丁基）（13b）的环丙烷化反应生成五个旋光性C 2对称双加合物7-11，可以通过制备型HPLC分离并进行充分表征（方案

  DOI：

  10.1002/hlca.19950780705