5,11,17,23-tetrakis(chloromethyl)-25,26,27,28-tetrapropoxycalix[4]arene | 153651-86-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,11,17,23-tetrakis(chloromethyl)-25,26,27,28-tetrapropoxycalix[4]arene
• 英文别名: 5,11,17,23-tetra(chloromethyl)-25,26,27,28-tetrapropoxycalix[4]arene；25,26,27,28-tetra(n-propyloxy)-tetra-p-chloromethylcalix[4]arene；tetrakis-(chloromethyl)tetrapropoxy-calix[4]arene；tetrapropoxy-p-chloromethyl calix[4]arene；chloromethylcalix[4]arene；5,11,17,23-tetrakis(chloromethyl)-25,26,27,28-tetrapropoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene
• CAS: 153651-86-6；325814-49-1；163750-99-0
• 化学式: C₄₄H₅₂Cl₄O₄
• 分子量: 786.706
• InChiKey: XCYJNZCPDHLBRV-UHFFFAOYSA-N

物化性质

• 熔点：
  218-224°C
• 沸点：
  785.19°C (rough estimate)
• 密度：
  1.0171 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  12.7
• 重原子数：
  52
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetrakis(chloromethyl)-25,26,27,28-tetrapropoxycalix[4]arene 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 36.0h， 以85%的产率得到5,11,17,23-tetrakis-(3-azidomethyl)-25,26,27,28-tetrapropoxy-calix[4]arene
  参考文献：
  名称：

  A Stimulus-Responsive Shape-Persistent Micelle Bearing a Calix[4]arene Building Block: Reversible pH-Dependent Transition between Spherical and Cylindrical Forms

  摘要：

  A series of cationic calix[4]arene-based lipids with alkyl chains of varying length were newly synthesized, and the ones with propyl and hexyl tails, denoted by CaL[4]C3 and C6, respectively, were found to form spherical micelles at low pH (protonated state of the amine headgroup). Upon deprotonation with increasing pH, CaL[4]C3 showed a sphere-to-cylinder transition, while CaL[4]C6 changed from sphere, to cylinder, to monolayer vesicle. Synchrotron small-angle X-ray scattering (SAXS) patterns from both spherical and cylindrical CaL[4]C3 micelles exhibited a sharp intensity minimum, indicating shape monodispersity. The monodispersity of the CaL[4]C3 spherical micelles was further confirmed by analytical ultracentrifugation (AUC). SAXS, AUC, and static light scattering agreeingly indicated an aggregation number of 6. In contrast, CaL[4]C6 exhibited polydispersity with an average aggregation number of 12. When the number of carbons of the alkyl chain was increased to 9 (CaL[4]C9), cylinder formed at low pH, while at high pH, no clear morphology could be observed. The present results indicate that a very precise combination of tail length, head volume, and rigidity of the building block is required to produce shape-persistent micelles and that the shape-persistence can be maintained upon a structural transition. An attempt to reconstruct a molecular model for the spherical CaL[4]C3 micelle was made With an ab initio shape determining program.

  DOI：

  10.1021/la2037668
• 作为产物：
  描述：

  25,26,27,28-tetrapropyloxycalix[4]arene 生成 5,11,17,23-tetrakis(chloromethyl)-25,26,27,28-tetrapropoxycalix[4]arene
  参考文献：
  名称：

  Unusually high ionophoricity of 1,3-alternate-calix[4]arenes: π-Donor participation in the complexation of cations?

  摘要：

  It was found that 1,3-alternate-calix[4]arenes having cavities composed of two oxygens and two benzene rings show the metal affinity much higher than cone-calix[4]arenes having a cavity composed of four oxygens. The unexpected finding is most likely rationalized in terms of the "pi-donor participation" in the metal complexation.

  DOI：

  10.1016/s0040-4039(00)60194-6

文献信息

• Calix[4]arenes with 1,2- and 1,3-upper rim tetrathiafulvalene bridges
  作者：Matthias H. Düker、Felix Kutter、Thomas Dülcks、Vladimir A. Azov

  DOI：10.1080/10610278.2013.872245

  日期：2014.8.3

  Herein we report the synthesis of several calix[4]arene derivatives with tetrathiafulvalene bridges at the upper rim. Calix[4]arene-tetrathiafulvalene (TTF) conjugates 4a–d, fixed in cone conformation and comprising two smaller 1,2-bridges, were prepared by cyclisation of tetrakis-chloromethylated calix[4]arene 1 with 2,3-dithiolates of TTFs. Larger calix[4]arene-TTF macrocycles 14 and 15, also in

  在这里，我们报告了几种杯[4]芳烃衍生物的合成，在上缘具有四硫富瓦烯桥。杯[4] 芳烃-四硫富瓦烯 (TTF) 共轭物 4a-d，固定为锥形构象并包含两个较小的 1,2-桥，通过四氯甲基化杯 [4] 芳烃 1 与 2,3-二硫醇盐的环化制备TTF。较大的杯 [4] 芳烃-TTF 大环 14 和 15，同样为锥形构象，包含 1,3-桥，通过用双溴甲基化杯 [4] 环化 TTF 的 2,6- 和 2,7-二硫醇盐合成芳烃 7. 使用循环伏安法表征新杯[4]芳烃-TTF缀合物的氧化还原特性。
• Synthesis and metal extraction behavior of pyridine and 1,2,4-triazole substituted calix[4]arenes
  作者：Ashok Kumar、Pratibha Sharma、Bhagwan Lal Kalal、Lal Kumar Chandel

  DOI：10.1007/s10847-010-9796-2

  日期：2010.12

  of heterocycle substituted calixarenes, derivatized at lower and upper rim, were synthesized and successfully evaluated for metal extraction towards alkali, alkaline, transition and heavy metal ions. The presence and placement of sulfur, heterocycle functionality at upper/lower rim played a crucial role toward the extractability and selectivity of metal ions. The lower rim substituted calixarenes have

  合成了三个系列的杂环取代杯芳烃，在下缘和上缘衍生化，并成功评估了对碱金属、碱金属、过渡金属和重金属离子的金属萃取。硫、杂环官能团在上/下边缘的存在和位置对金属离子的可萃取性和选择性起着至关重要的作用。下缘取代的杯芳烃表现出高可萃取性和差的选择性。与此相反，上缘取代的杯芳烃表现出良好的选择性。此外，与碱金属和碱金属离子相比，硫官能化杯芳烃对重金属离子显示出更好的选择性。在上缘取代的杯芳烃中，发现 17 和 18 适用于 Na+、K+ 和 Ag+，19,13 适用于重金属离子，即 Pb2+、Hg+、Hg2+ 和 Ag+，以及 11，
• Cationic amphiphilic calixarenes to compact DNA into small nanoparticles for gene delivery
  作者：Roman V. Rodik、Anne-Sophie Anthony、Vitaly I. Kalchenko、Yves Mély、Andrey S. Klymchenko

  DOI：10.1039/c4nj01395f

  日期：——

  Cationic amphiphilic calixarenes with longer alkyl chains are less cytotoxic and their virus-sized DNA nanoparticles exhibit higher transfection efficiency.

  带有较长烷基链的阳离子两性卡立克酮对细胞毒性较小，它们的病毒大小的DNA纳米颗粒表现出更高的转染效率。
• Influence of the Number and Geometry of Binding Sites on Host–Guest Affinity: Imidazolium-Substituted Receptor Molecules for Small Inorganic Anions
  作者：Tilmann Fahlbusch、Markus Frank、Jürgen Schatz、Harald Schmaderer

  DOI：10.1002/ejoc.200500825

  日期：2006.4

  The influence of the number and relative geometry of the binding sites on the binding of spherical and tetragonal inorganic anions (Cl–, Br–, H2PO4–, and HSO4–) has been studied by using imidazolium salts based on benzene and calix[4]arenes. Binding constants in DMSO were found to be in the range of 200–2000 L mol–1. Three or four binding sites (2b–4b) lead to the nonselective binding of all anions

  已经通过使用基于苯和杯的咪唑鎓盐研究了结合位点的数量和相对几何形状对球形和四方无机阴离子（Cl–、Br–、H2PO4– 和 HSO4–）结合的影响[4]芳烃。发现 DMSO 中的结合常数在 200-2000 L mol-1 的范围内。三个或四个结合位点 (2b–4b) 导致所有阴离子的非选择性结合，表明可能结合位置的数量具有决定性影响；H2PO4– 的结合常数约为 2000，HSO4– 约为 1000，Cl– 约为 900，Br– 约为 800 L mol–1。苯 (1b) 和杯芳烃基 (5b) 双（咪唑鎓）盐对 H2PO4–/HSO4– 和 Cl–/Br– 表现出高选择性，表明 H2PO4– 和 Cl– 的络合需要两个结合位点，对于 Br– 和 HSO4– 至少三个。
• Synthesis and optical resolution of naphthalene-containing inherently chiral calix[4]arenes derived by intramolecular ring closure or stapling of proximal phenyl units
  作者：Atsushi Ikeda、Makoto Yoshimura、Pavel Lhotak、Seiji Shinkai

  DOI：10.1039/p19960001945

  日期：——

  New methods for the preparation of inherently chiral calix[4]arenes have been developed. The molecular asymmetry in these calix[4]arenes is created by an asymmetrical disposition of naphthalene rings on the upper rim. In compound 1, monoformylcalix[4]arene 5 was transformed into naphthalene-containing calix[4]arene by ring closure. In compound 2, p-chloromethyl groups are intramolecularly cross-linked

  已经开发了制备固有手性杯[4]芳烃的新方法。这些杯[4]芳烃中的分子不对称是由于萘环在上缘上的不对称分布而造成的。在化合物1中，通过闭环将单甲酰基杯[4]芳烃5转化为含萘的杯[4]芳烃。在化合物2中，对氯甲基与3-羟甲基-2-萘酚分子内交联。该“装订反应”产生了顺式异构体2a和反式异构体2b，反式异构体2b被分类为固有的手性杯[4]芳烃。外消旋反2可用手性填充柱通过HPLC方法“完全”光学拆分。通过各种光谱方法对手性产物进行了彻底的表征。这些结果表明，萘骨架对于在杯[4]芳烃中产生分子不对称性非常有用。