6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dicarbaldehde | 75616-63-6

• 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-dicarbaldehde
• 英文别名: 2,3-(4'-formylbenzo)-11,12-(5'-formylbenzo)-[18]-crown-6；4,4′-diformyldibenzo-18-crown-6；6,7,9,10,17,18,20,21-Octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecine-2,13-dicarbaldehyde；2,5,8,15,18,21-hexaoxatricyclo[20.4.0.09,14]hexacosa-1(22),9(14),10,12,23,25-hexaene-11,24-dicarbaldehyde
• CAS: 75616-63-6
• 化学式: C₂₂H₂₄O₈
• mdl: MFCD00196096
• 分子量: 416.428
• InChiKey: QYPDFOYBOVJVFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 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-2,13-dicarbaldehde 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 1,1'-bis{2-[2-(2-methoxyethoxy)ethoxy]ethyl} 3,3'-[(6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacylooctadecin-2,13-diyl)dimethylene] bis(malonate)
  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
• 作为产物：
  描述：

  4-[2-(2-chloroethoxy)ethoxy]-3-hydroxybenzaldehyde 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以31 %的产率得到6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dicarbaldehde
  参考文献：
  名称：

  用于离子对识别的富勒烯功能化卤素键异位主体

  摘要：

  尽管富勒烯的疏水表面具有局部π孔和刚性明确的结构，为预组织结合基序提供了支架，但富勒烯作为识别阴离子的潜在超分子宿主平台仍未被探索。在此，我们提出了新型富勒烯功能化卤素键合（XB）异二位离子对受体的合理设计、合成和独特识别特性的第一个例子，该受体含有由 C 60空间分隔的阳离子和阴离子结合域。 XB 供体和冠醚络合钾阳离子的富勒烯空间分离产生了一个罕见的人工受体实例，其中包含两个阴离子结合位点，对硬卤化物和软卤化物具有相反的偏好。重要的是，C 60基序并入异二位受体结构对卤化物结合选择性具有显着影响，并且在 K +阳离子结合时进一步放大。钾阳离子络合的富勒烯受体表现出对软极化碘离子的选择性增强，这得到了 C 60支架的帮助，预组织了有效的基于 XB 的结合域、阴离子-π 相互作用以及富勒烯部分的特殊极化性，如所证明的来自 DFT 计算。这些观察结果突出了富勒烯表面用于近端带电客体结合的独特

  DOI：

  10.1021/jacs.3c07774
• 作为试剂：
  描述：

  盐酸甲胺 、 4,4'-diformyldibenzo-18-crown-6 、 甲胺 在 6,7,9,10,17,18,20,21-octahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin-2,13-dicarbaldehde 作用下， 以 乙醇 为溶剂， 反应 60.0h， 以36%的产率得到3-[2-[2-[5-Formyl-2-(methylamino)phenoxy]ethoxy]ethoxy]-4-(methylamino)benzaldehyde
  参考文献：
  名称：

  Macrocycle opening in formyl derivatives of benzocrown ethers under the action of methylamine

  摘要：

  A new method for synthesizing nitrogen-containing podands by nucleophilic regioselective cleavage of the macrocycle in formyl derivatives of benzocrown ethers by heating with methylamine and methylammonium chloride has been developed. This reaction is the first example of crown ether opening by a nitrogen-containing nucleophile.

  DOI：

  10.1007/bf00696929

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。
• New Applications of Crown Ethers. II. Synthesis of 4′-Formylbenzocrown Ethers
  作者：Fumio Wada、Hiroshi Hirayama、Hiroshi Namiki、Kiyoshi Kikukawa、Tsutomu Matsuda

  DOI：10.1246/bcsj.53.1473

  日期：1980.5

  4′-Formylbenzo-15-crown-5, -18-crown-6, and bis(4′-formylbenzo)-18-crown-6 were conveniently synthesized in excellent yields by Smith modification of Duff reaction: formylation with hexamethylenetetramine and trifluoroacetic acid or methanesulfonic acid.

  4'-Formylbenzo-15-crown-5、-18-crown-6 和双 (4'-formylbenzo)-18-crown-6 通过 Duff 反应的 Smith 改进以优异的产率方便地合成：用六亚甲基四胺和三氟乙酸甲酰化酸或甲磺酸。
• 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.
• Molecular Assembly and Disassembly:  Novel Photolabile Molecular Hosts
  作者：Yongqin Wan、Oleg Mitkin、Loren Barnhurst、Alexei Kurchan、Andrei Kutateladze

  DOI：10.1021/ol006692d

  日期：2000.11.1

  [GRAPHICS]A new approach to the assembly and photochemical disassembly of molecular hosts is developed. It is based on photoinduced fragmentation in hydroxyalkyl dithianes and utilizes a novel spiro-bis-dithiane as a photolabile molecular tether to link two formylated macromolecular blocks, e.g., formyl calixarenes or formyl dibenzocrown ethers. A key feature of this molecular system is that after an assembly-disassembly cycle the starting macromolecular blocks are recovered intact and can be used again.