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.
• Supramolecular Fullerene Chemistry: A Comprehensive Study of Cyclophane-Type Mono- and Bis-Crown Ether Conjugates of C70
  作者：Maurice J. van Eis、Paul Seiler、Liya A. Muslinkina、Martin Badertscher、Ernö Pretsch、François Diederich、Robert J. Alvarado、Luis Echegoyen、Ignacio Pérez Núñez

  DOI：10.1002/1522-2675(200207)85:7<2009::aid-hlca2009>3.0.co;2-g

  日期：2002.7

  tetrakis-adducts of C70, featuring two covalently attached crown ethers, form stable 1 : 1 and 1 : 2 host-guest complexes (Table 2). Comparative studies showed that the conformation of the DB18C6 ionophore imposed by the macrocyclic bridging to the fullerene is not particularly favorable for strong association. Reference compound (±)-22 (Scheme 4), in which the DB18C6 moiety is attached to the C70 sphere by

  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
• Harnessing Selectivity and Sensitivity in Ion Sensing via Supramolecular Recognition: A 3D Hybrid Gold Nanoparticle Network Chemiresistor
  作者：Verónica Montes‐García、Rafael Furlan Oliveira、Ye Wang、Andrey Berezin、Pablo Fanjul‐Bolado、María Begoña González García、Thomas M. Hermans、Davide Bonifazi、Stefano Casalini、Paolo Samorì

  DOI：10.1002/adfm.202008554

  日期：2021.3

  K+ sensors are unable to meet the requirements for the development of point‐of‐care (POC) sensors. To tackle this grand‐challenge, the fabrication of chemiresistors (CRs) based on 3D networks of Au nanoparticles covalently bridged by ad‐hoc supramolecular receptors for K+, namely dithiomethylene dibenzo‐18‐crown‐6 ether is reported here. A multi‐technique characterization allows optimizing a new protocol

  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