6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,14-dimethanol | 214076-94-5

• 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-2,14-dimethanol
• 英文别名: 6,7,9,10,17,18,20,21-Octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecine-2,14-diyldimethanol；[25-(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: 214076-94-5
• 化学式: C₂₂H₂₈O₈
• 分子量: 420.46
• InChiKey: RAUGDYKZBGXCDC-UHFFFAOYSA-N

物化性质

• 沸点：
  626.3±55.0 °C(Predicted)
• 密度：
  1.191±0.06 g/cm3(Predicted)

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：

  6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,14-dimethanol 在 劳森试剂 、 lithium aluminium tetrahydride 作用下， 以 甲苯 、 四氢呋喃 为溶剂， 以37%的产率得到(6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecine-2,14-diyl)dimethanethiol
  参考文献：
  名称：

  通过超分子识别在离子感测中利用选择性和敏感性：3D混合金纳米颗粒网络化学分析仪

  摘要：

  唾液，血液，尿液或汗液中K +的监测代表了未来预防各种疾病的强大替代诊断工具。但是，一些K + 传感器无法满足即时医疗（POC）传感器的开发要求。为了应对这一巨大挑战，本文报道了基于由纳米级K +的特异超分子受体共价桥接的Au纳米粒子的3D网络（即二硫代亚甲基二苯并18-18冠-6醚）制造化学电阻器（CR）的方法。多种技术特性可优化用于制造高性能CR的新协议，以实时监控K +在复杂的水性环境中。传感器显示出优异的品质因数：i）在10 –3至10 –6 m浓度范围内的线性灵敏度；ii）在存在干扰阳离子（Na +，Ca 2+和Mg 2+）的情况下对K +的选择性高；iii）较高的货架期稳定性（> 45天）；iv）K +结合和释放的可逆性；v）成功将设备集成到微流体系统中以进行实时监控；vi）快速响应和恢复时间（< 18 s），和v）K +人工唾液中检测。所有这些特性使超分子CR成为POC设备未

  DOI：

  10.1002/adfm.202008554
• 作为产物：
  描述：

  4,4'-diformyldibenzo-18-crown-6 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 1.33h， 以98%的产率得到6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,14-dimethanol
  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

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。
• 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.