| 321402-53-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• CAS: 321402-53-3
• 化学式: C₆₆Cl₄O₄
• 分子量: 998.536
• InChiKey: CCVHDHWYMVOOBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.92
• 重原子数：
  74.0
• 可旋转键数：
  4.0
• 环数：
  34.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  68.28
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  、 正己醇 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以45%的产率得到tetrahexyl 1,2:55,60-bismethano[60]fullerene-61,61,62,62-tetracarboxylate
  参考文献：
  名称：

  Cyclophane-Type Fullerene-dibenzo[18]crown-6 Conjugates withtrans-1,trans-2, andtrans-3 Addition Patterns: Regioselective Templated Synthesis, X-Ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior

  摘要：

  The fullerene-crown ether conjugates (+/-)-1 to (+/-)-3 with trans-1 ((+/-)-1), trans-2 ((+/-)-2),and trans-3 ((+/-)-3) addition patterns on the C-sphere were prepared by Bingel macrocyclization. The trans-1 derivative (+/-)-1 was obtained in 30% yield, together with a small amount of (+/-)-2 by cyclization of the dibenzo[18]crown-6(DB18C6)-tethered bis-malonate 4 with C-60 (Scheme 1). When the crown-ether tether was further rigidified by K+-ion complexation, the yield and selectivity were greatly enhanced, and (+/-)-1 was obtained as the only regioisomer in 50% yield. The macrocyclization, starting from a mixture of tethered bis-malonates with anti (4) and syn (10) bisfunctionalized DB18C6 moieties, afforded the trans-1 ((+/-)-1, 15%), trans-2 ((+/-)-2, 1.5%), and trans-3 ((+/-)-3, 20%) isomers (Scheme 2). Variable-temperature H-1-NMR (VT-NMR) studies showed that the DB18C6 moiety in C-2-symmetrical (+/-)-1 cannot rotate around the two arms fixing it to the C-sphere, even at 393 K. The planar chirality of (+/-)-1 was confirmed in H-1-NMR experiments using the potassium salts of (S)-1,1'-binaphthalene-2,2'-diyl phosphate ((+/-)-(S)-19) or (+)-(1S)-camphor-10-sulfonic acid ((+)-20) as chiral shift reagents (Fig. 1). The DB18C6 tether in (+/-)-1 is a true covalent template: it is readily removed by hydrolysis or transesterification, which opens up new perspectives for molecular scaffolding using trans-1 fullerene derivatives. Characterization of the products 11 (Scheme 3) and 18 (Scheme 4) obtained by tether removal unambiguously confirmed the trans-1 addition pattern and the out-out geometry of (+/-)-1. VT-NMR Studies established that (+/-)-2 is a C-2-symmetrical out-out trans-2 and (+/-)-3 a C-1-symmetrical in-out trans-3 isomer. Upon changing from (+/-)-1 to (+/-)-3, the distance between the DB18C6 moiety and the fullerene surface increases and. correspondingly, rotation of the ionophore becomes increasingly facile. The ionophoric properties of (+/-)-1 were investigated with an ion-selective electrode membrane (Fig. 2 and Table 2), and K+ was found to form the most stable complex among the alkali-metal ions. The complex between (+/-)-1 and KPF6 was characterized by X-ray crystal-structure analysis (Figs. 3 and 4), which confirmed the close tangential orientation of the ionophore atop the fullerene surface. Addition of KPF6 to a solution of (+/-)-1 resulted in a lar-ge anodic shift (90 mV) of the first fullerene-centered reduction process, which is attributed to the electrostatic effect of the K+ ion bound in close proximity to the C-sphere (Fig. 5). Smaller anodic shifts were measured for the KPF6 complexes of (+/-)-2 (50 mV) and (+/-)-3 (40 mV), in which the distance between ionophore and fullerene surface is increased (Table 3). The effects of different alkali- and alkaline-earth-metal ion salts on the redox properties of (+/-)-1 were investigated (Table 4). These are the first-ever observed effects of cation complexation on the redox properties of the C-sphere in fullerene-crown ether conjugates.

  DOI：

  10.1002/(sici)1522-2675(19991006)82:10<1572::aid-hlca1572>3.0.co;2-b
• 作为产物：
  描述：

  在 草酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  具有不同加成模式的 [60] 富勒烯的 Hexakis-加合物：模板合成、物理性质和化学反应性

  摘要：

  通过模板化合成策略制备了两类 C60 六角形加合物的代表。通过 DMA 模板加成 (DMA=9,10-二甲基蒽; 方案 1) 获得具有假八面体加成模式的二吡啶基甲烷加成物的化合物 8，并用作第一个超分子富勒烯二聚体 2 的起始材料。Hexakis-加合物 12还具有伪八面体添加模式，是通过一系列系链定向远程功能化、系链去除和区域选择性双功能化获得的（方案 2）。它的两个二乙炔基甲烷加合物位于 trans-1 位置，它是令人着迷的新低聚物和聚合物的前体，这些低聚物和聚合物具有 C60 部分作为聚合物骨架的一部分（图 1）。随着剩余的富勒烯π电子发色团还原为“立方环烷” -型子结构（图4），并且由于空间原因，8和12不再显示出亲电反应性。作为第二类六角形加合物的代表，(±)-1 具有沿赤道带呈不同螺旋阵列的六个加合物，其制备路线涉及两个连续的系链定向远程功能化步骤（方案 3和 5）。在化合物 (±)-1

  DOI：

  10.1002/1522-2675(20010516)84:5<1207::aid-hlca1207>3.0.co;2-b

文献信息

• Higher Adducts of C60 by Tether-Directed Remote Functionalization: X-Ray Crystal Structure and Reactivity of a Chiral Hexakis-Cyclopropanated Fullerene with all Addends Located along an Equatorial Belt
  作者：Craig R. Woods、Jean-Pascal Bourgeois、Paul Seiler、François Diederich

  DOI：10.1002/1521-3773(20001103)39:21<3813::aid-anie3813>3.0.co;2-5

  日期：2000.11.3