1,5-bis<2-<2-<2-(o-formylphenoxy)ethoxy>ethoxy>ethoxy>naphthalene bis(4-methylbenzenesulfonate) | 157720-62-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,5-bis<2-<2-<2-(o-formylphenoxy)ethoxy>ethoxy>ethoxy>naphthalene bis(4-methylbenzenesulfonate)
• 英文别名: 1,5-bis[2-(2-(2-((2-formylphenoxy)ethoxy)ethoxy)ethoxy)]naphthalene；1,5-bis[2-{2-[2-(o-formylphenoxy)ethoxy]ethoxy}ethoxy]naphthalene bis(4-methylbenzenesulfonate)；2-[2-[2-[2-[5-[2-[2-[2-(2-Formylphenoxy)ethoxy]ethoxy]ethoxy]naphthalen-1-yl]oxyethoxy]ethoxy]ethoxy]benzaldehyde；2-[2-[2-[2-[5-[2-[2-[2-(2-formylphenoxy)ethoxy]ethoxy]ethoxy]naphthalen-1-yl]oxyethoxy]ethoxy]ethoxy]benzaldehyde
• CAS: 157720-62-2
• 化学式: C₃₆H₄₀O₁₀
• 分子量: 632.708
• InChiKey: YODNXUILKIFLPN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  46
• 可旋转键数：
  24
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,5-bis<2-<2-<2-(o-formylphenoxy)ethoxy>ethoxy>ethoxy>naphthalene bis(4-methylbenzenesulfonate) 在 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  Thermodynamic Synthesis of Rotaxanes by Imine Exchange

  摘要：

  [GRAPHICS]By utilizing the dynamic nature of imine bonds, it is possible to construct [2]rotaxanes from a ring and a preformed dumbbell under thermodynamic control, These dynamic [a]rotaxanes, which exhibit reversible supramolecular-like behavior in the presence of appropriate catalysts, can be "fixed" by reduction of their imine bonds.

  DOI：

  10.1021/ol991047w
• 作为产物：
  描述：

  1,5-二羟基萘 在 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 50.17h， 生成 1,5-bis<2-<2-<2-(o-formylphenoxy)ethoxy>ethoxy>ethoxy>naphthalene bis(4-methylbenzenesulfonate)
  参考文献：
  名称：

  Self-Assembling Porphyrin [2]-Catenanes

  摘要：

  Using the concepts of self-assembly developed for the construction of topologically complex molecules such as [2]-catenanes and rotaxanes, the syntheses of several prophyrin-catenanes are described. The successful insertion of the porphyrin subunit into [2]-catenanes has resulted from the adaptation of previously devised template-directed syntheses based primarily on pi-pi interactions and C-H...O and C-H...pi and hydrogen bonding. Several hydroquinol containing ether chains were successfully synthesized and subsequently strapped across a porphyrin ring; the X-ray crystal structures of two such molecules which vary in the length of the ether chain are reported. These strapped porphyrins were found to complex paraquat with a parallel orientation of the hydroquinol, paraquat, and porphyrin rings. The complexation of paraquat (K-a 1955 and 1640 M(-1), Delta G degrees = -4.5 and -4.4 kcal mol(-1) for 9 and 11, respectively) by these strapped porphyrins led to their subsequent inclusion, using template-directed self-assembly, into structures which represent the first examples of porphyrin-containing [2]-catenanes. The catenanes were subsequently characterized by FAB-MS and thoroughly examined using dynamic H-1 NMR. In the case of the hydroquinol-containing catenanes, a dynamic process was observed in solution in which the bipyridinium subunits of the tetracation were exchanged between ''inside'' and ''outside'' environments (rotation around the hydroquinol ring axis). The diethylene glycol containing catenanes 14 and 15 were observed to maintain an orientation of the tetracation in which the bipyridinium subunits are parallel to the porphyrin ring. The length of the ether strap in these catenanes influenced the rotation rates of the tetracation macrocycles (50 and 80 times per second for 14 and 15 and 2500 and 1500 times per second for 16 and 17, respectively) at ambient temperature. However, in air the catenanes, the overall orientation of the tetracation,with bipyridinium and porphyrin rings coparallel, is retained in solution. As an extension of the original concepts, an analogous strapped porphyrin containing a naphthoquinol moiety was synthesized and found to complex paraquat with K-a = 21 000 M(-1) and Delta G degrees = -5.9 kcal mol(-1). The general applicability of the template-directed synthetic procedure developed for porphyrin catenane synthesis was illustrated by the successful isolation of the naphthalene containing porphyrin [2]-catenane 23 in 45% yield. Tetracation exchange processes similar to those for the hydroquinol catenanes were observed, along with an additional process which was found to be the decomplexation/complexation of the naphthalene ring in what is termed an ''out, turn around, and in again'' process similar to that occurring in nonporphyrinic naphthalene [2]-catenanes.

  DOI：

  10.1021/ja00090a029

文献信息

• Neutral π-associated porphyrin [2]catenanes
  作者：Maxwell J. Gunter、Sandra M. Farquhar

  DOI：10.1039/b307383a

  日期：——

  A series of neutral porphyrin-containing catenanes has been synthesised, consisting of a zinc porphyrin strapped by a polyethylene glycol chain containing four or six ethylenoxy-units and incorporating a central naphthoquinol unit, interlinked with a naphthalene diimide macrocycle. The napthalene diimide precursor units exhibit only weak binding with the strapped porphyrins (Ka between 8 and 0.02 M−1), but good yields of the catenanes were obtained by Glaser coupling of the alkynyl napthalene diimide precursors in the presence of the porphyrins. Structures and solution conformations were determined by mass spectral and detailed 1H NMR studies. For the longer strapped porphyrins, the diimide macrocycle rotates around the central naphthoquinol unit at 420–450 times per second, while rotation is virtually prevented in the tighter strapped derivatives. A second dynamic process occurring in both sets of catenanes and described as ‘yawing’ leads to inequivalence in the naphthalene moieties. UV-Visible spectra indicate charge transfer interactions and electronic communication between the two components of the catenane.

  一系列中性含卟啉的链烷已经合成，由锌卟啉和含有四个或六个乙氧基单元的聚乙二醇链组成，并包含一个中心萘醌单元，与萘二酰亚胺大环相互连接。萘二酰亚胺前体单元与束缚卟啉的结合力较弱（Ka在8和0.02 M之间），但在卟啉存在的情况下，通过炔基萘二酰亚胺前体的格拉瑟偶联，获得了良好的链烷产量。通过质谱和详细的1H NMR研究确定了结构和溶液构象。对于较长的束缚卟啉，二酰亚胺大环以每秒420-450次的频率绕中心萘醌单元旋转，而在更紧密的束缚衍生物中，旋转实际上被阻止了。在两组链烷中发生的第二个动态过程被称为“偏航”，导致萘部分的不等价。紫外可见光谱表明链烷的两个成分之间存在电荷转移相互作用和电子通信。
• Self-Assembling Porphyrin [2]-Catenanes
  作者：Maxwell J. Gunter、David C. R. Hockless、Martin R. Johnston、Brian W. Skelton、Allan H. White

  DOI：10.1021/ja00090a029

  日期：1994.6

  Using the concepts of self-assembly developed for the construction of topologically complex molecules such as [2]-catenanes and rotaxanes, the syntheses of several prophyrin-catenanes are described. The successful insertion of the porphyrin subunit into [2]-catenanes has resulted from the adaptation of previously devised template-directed syntheses based primarily on pi-pi interactions and C-H...O and C-H...pi and hydrogen bonding. Several hydroquinol containing ether chains were successfully synthesized and subsequently strapped across a porphyrin ring; the X-ray crystal structures of two such molecules which vary in the length of the ether chain are reported. These strapped porphyrins were found to complex paraquat with a parallel orientation of the hydroquinol, paraquat, and porphyrin rings. The complexation of paraquat (K-a 1955 and 1640 M(-1), Delta G degrees = -4.5 and -4.4 kcal mol(-1) for 9 and 11, respectively) by these strapped porphyrins led to their subsequent inclusion, using template-directed self-assembly, into structures which represent the first examples of porphyrin-containing [2]-catenanes. The catenanes were subsequently characterized by FAB-MS and thoroughly examined using dynamic H-1 NMR. In the case of the hydroquinol-containing catenanes, a dynamic process was observed in solution in which the bipyridinium subunits of the tetracation were exchanged between ''inside'' and ''outside'' environments (rotation around the hydroquinol ring axis). The diethylene glycol containing catenanes 14 and 15 were observed to maintain an orientation of the tetracation in which the bipyridinium subunits are parallel to the porphyrin ring. The length of the ether strap in these catenanes influenced the rotation rates of the tetracation macrocycles (50 and 80 times per second for 14 and 15 and 2500 and 1500 times per second for 16 and 17, respectively) at ambient temperature. However, in air the catenanes, the overall orientation of the tetracation,with bipyridinium and porphyrin rings coparallel, is retained in solution. As an extension of the original concepts, an analogous strapped porphyrin containing a naphthoquinol moiety was synthesized and found to complex paraquat with K-a = 21 000 M(-1) and Delta G degrees = -5.9 kcal mol(-1). The general applicability of the template-directed synthetic procedure developed for porphyrin catenane synthesis was illustrated by the successful isolation of the naphthalene containing porphyrin [2]-catenane 23 in 45% yield. Tetracation exchange processes similar to those for the hydroquinol catenanes were observed, along with an additional process which was found to be the decomplexation/complexation of the naphthalene ring in what is termed an ''out, turn around, and in again'' process similar to that occurring in nonporphyrinic naphthalene [2]-catenanes.
• Thermodynamic Synthesis of Rotaxanes by Imine Exchange
  作者：Stuart J. Rowan、J. Fraser Stoddart

  DOI：10.1021/ol991047w

  日期：1999.12.1

  [GRAPHICS]By utilizing the dynamic nature of imine bonds, it is possible to construct [2]rotaxanes from a ring and a preformed dumbbell under thermodynamic control, These dynamic [a]rotaxanes, which exhibit reversible supramolecular-like behavior in the presence of appropriate catalysts, can be "fixed" by reduction of their imine bonds.