6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dimethanol | 214076-93-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dimethanol
• 英文别名: 2,3-(4'-hydroxymethylbenzo)-11,12-(5'-hydroxymethylbenzo)-[18]-crown-6；6,7,9,10,17,18,20,21-Octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecine-2,13-diyldimethanol；[24-(hydroxymethyl)-2,5,8,15,18,21-hexaoxatricyclo[20.4.0.09,14]hexacosa-1(22),9(14),10,12,23,25-hexaen-11-yl]methanol
• CAS: 214076-93-4
• 化学式: C₂₂H₂₈O₈
• 分子量: 420.46
• InChiKey: YIUPQOFDHUJGKK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  95.8
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  氯甲酰乙酸乙酯 、 6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dimethanol 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以70%的产率得到1,1'-diethyl 3,3'-[(6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-diyl)dimethylene] bis(malonate)
  参考文献：
  名称：

  冠醚系链指导的反式-1富勒烯双加合物的区域选择性合成：碱金属阳离子调节的富勒烯冠醚共轭物的氧化还原特性。

  摘要：

  用含有新型二苯并[18]冠-6系链的双丙二酸酯对C 60进行区域选择性Bingel宏环化，可广泛地利用反式1富勒烯双加合物，例如（±）-1。钾离子与（±）-1的络合对碳球的氧化还原特性有显着影响，这是由于富勒烯表面与冠醚键合阳离子紧密接近的结果，这是通过双桥作用实现的。

  DOI：

  10.1002/(sici)1521-3773(19980817)37:15<2118::aid-anie2118>3.0.co;2-9
• 作为产物：
  描述：

  二苯并-18-冠醚-6 在 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 甲醇 为溶剂， 反应 25.0h， 生成 6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dimethanol
  参考文献：
  名称：

  冠醚系链指导的反式-1富勒烯双加合物的区域选择性合成：碱金属阳离子调节的富勒烯冠醚共轭物的氧化还原特性。

  摘要：

  用含有新型二苯并[18]冠-6系链的双丙二酸酯对C 60进行区域选择性Bingel宏环化，可广泛地利用反式1富勒烯双加合物，例如（±）-1。钾离子与（±）-1的络合对碳球的氧化还原特性有显着影响，这是由于富勒烯表面与冠醚键合阳离子紧密接近的结果，这是通过双桥作用实现的。

  DOI：

  10.1002/(sici)1521-3773(19980817)37:15<2118::aid-anie2118>3.0.co;2-9

文献信息

• Intramolecular Triplet Energy Transfer in Donor–Acceptor Molecules Linked by a Crown Ether Bridge
  作者：Xiao-He Xu、Xiao-Gang Fu、Li-Zhu Wu、Bin Chen、Li-Ping Zhang、Chen-Ho Tung、Hai-Feng Ji、Kirk S. Schanze、Rui-Qin Zhang

  DOI：10.1002/chem.200501151

  日期：2006.7.5

  group (NBD) as the acceptor, respectively. Their intramolecular triplet energy transfer was examined. The bridges linking the donor and acceptors in these molecules involve a crown ether moiety complexing a sodium ion. Phosphorescence quenching, flash photolysis and photosensitized isomerization experiments indicate that intramolecular triplet energy transfer occurs with rate constants of about 3.3 x 10(5)

  以二苯甲酮发色团（BP）为供体，2-萘基（NP）和降冰片二烯基团（NBD）为受体，合成了双发色化合物BP-C-NP和BP-C-NBD。他们的分子内三重态能量转移进行了检查。在这些分子中连接供体和受体的桥包括与钠离子络合的冠醚部分。磷光猝灭，快速光解和光敏异构化实验表明，分子内三重态能量转移发生的速率常数约为3.3 x 10（5）和4.8 x 10（5）s（-1），BP-的效率约为33％和42％ C-NP和BP-C-NBD。理论计算表明，这些分子在室温以下采用构象，这使得它们的两端发色团有助于空间能量传递。
• Hexakis-Adducts of [60]Fullerene with Different Addition Patterns: Templated Synthesis, Physical Properties, and Chemical Reactivity
  作者：Jean-Pascal Bourgeois、Craig R. Woods、Francesca Cardullo、Tilo Habicher、Jean-François Nierengarten、Regula Gehrig、François Diederich

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

  日期：2001.5.16

  of C60 were prepared by templated synthesis strategies. Compound 8 with a dipyridylmethano addend in a pseudo-octahedral addition pattern was obtained by DMA-templated addition (DMA=9,10-dimethylanthracene; Scheme 1) and served as the starting material for the first supramolecular fullerene dimer 2. Hexakis-adduct 12 also possesses a pseudo-octahedral addition pattern and was obtained by a sequence of

  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
• Regioselective Synthesis oftrans-1 Fullerene Bis-Adducts Directed by a Crown Ether Tether: Alkali Metal Cation Modulated Redox Properties of Fullerene-Crown Ether Conjugates
  作者：Jean-Pascal Bourgeois、Luis Echegoyen、Monia Fibbioli、Ernö Pretsch、François Diederich

  DOI：10.1002/(sici)1521-3773(19980817)37:15<2118::aid-anie2118>3.0.co;2-9

  日期：1998.8.17

  Regioselective Bingel macrocyclization of C60 with a bis-malonate containing a novel dibenzo[18] crown-6 tether provides a versatile access to trans-1 fullerene bis-adducts such as (±)-1. Complexation of a potassium ion by (±)-1 has a pronounced effect on the redox properties of the carbon sphere as a result of the close proximity of the fullerene surface to the crown ether bound cation, which is enforced by the

  用含有新型二苯并[18]冠-6系链的双丙二酸酯对C 60进行区域选择性Bingel宏环化，可广泛地利用反式1富勒烯双加合物，例如（±）-1。钾离子与（±）-1的络合对碳球的氧化还原特性有显着影响，这是由于富勒烯表面与冠醚键合阳离子紧密接近的结果，这是通过双桥作用实现的。
• 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
  作者：Jean-Pascal Bourgeois、Paul Seiler、Monia Fibbioli、Ernö Pretsch、François Diederich、Luis Echegoyen

  DOI：10.1002/(sici)1522-2675(19991006)82:10<1572::aid-hlca1572>3.0.co;2-b

  日期：1999.10.6

  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.