3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane-4,11,18,25-tetrol | 145572-23-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane-4,11,18,25-tetrol
• 英文别名: 4,6,10,12,16,18,22,24,25,26,27,28-dodecamethylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene-5,11,17,23-tetrol
• CAS: 145572-23-2
• 化学式: C₄₀H₄₈O₄
• 分子量: 592.819
• InChiKey: WAKLCZAHNJRGDW-UHFFFAOYSA-N

物化性质

• 沸点：
  310 °C
• 密度：
  1.137±0.06 g/cm3(Predicted)
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  44
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane-4,11,18,25-tetrol 在 sodium hydroxide 、 氯化亚砜 、 potassium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 丙酮 、 苯 为溶剂， 反应 12.0h， 生成 2-[[4,6,10,12,16,18,22,24,25,26,27,28-dodecamethyl-11,17,23-tris[2-oxo-2-[[(1S)-1-phenylethyl]amino]ethoxy]-5-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaenyl]oxy]-N-[(1S)-1-phenylethyl]acetamide
  参考文献：
  名称：

  Informational rigidity in mesitylene-based calix[4]arenes adopting a 1,3-alternate conformation

  摘要：

  Two chiral derivatives of a mesitylene-based calix[4]arene known to exist in the 1,3-alternate conformation were prepared by the attachment of homochiral residues to the four exo-hydroxy groups. Thus, the enantiotopic protons of the central scaffold became diastereotopic, leading to a doubling of their H-1 NMR signals in one example. From the temperature independence of the NR IR spectrum, a lower limit of 24.2 kcal/mol could be estimated for the barrier of ring inversion. MM3 calculations confirm the 1,3-alternate conformation as the energy minimum, and estimate a barrier of 25.7 kcal/mol for the 1,3-alternate-to-1,3-alternate* interconversion process. This high barrier is due to the repulsive steric interactions between exo-methyl groups at vicinal rings when these groups pass each other. (C), 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00177-4
• 作为产物：
  描述：

  2,4,6-三甲酚 在 四氯化锡 作用下， 生成 3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane-4,11,18,25-tetrol
  参考文献：
  名称：

  1,3-交替四巯基[1.1.1.1]间环phane的合成

  摘要：

  1,3-交替3,5,7,10,12,14,17,19,21,24,26,28-十二烷基甲基[1.1.1.1]间环phane-4,11,18,25-四硫醇的制备方法从四羟基间环己烯开始，分三步收率。

  DOI：

  10.1016/s0040-4039(00)61465-x

文献信息

• Sensing and Fixation of NO₂/N₂O₄ by Calix[4]Arenes
  作者：Grigory V. Zyryanov、Yanlong Kang、Dmitry M. Rudkevich

  DOI：10.1021/ja029166l

  日期：2003.3.1

  NO(+) is found encapsulated within the calixarene cavity, and stable charge-transfer complexes result with K(ass) > 10(6) M(-1) (CDCl(3)). The NO(+) encapsulation was also demonstrated in titration experiments with calixarenes 1, 2, and 5 and commercially available NO(+)SbF(6)(-) salt in chloroform. The complexation process is reversible, and the complexes dissociate upon addition of water and alcohol

  提出了一种对 NO(2)/N(2)O(4) 进行视觉检测和化学利用的方法，该方法采用简单的杯 [4] 芳烃。四-O-烷基化杯[4]芳烃 1 和 2，具有锥形或 1,3-交替构象，暴露于 NO(2)/N(2)O(4)，无论是在氯仿溶液中还是在氯仿溶液中固态，产生深颜色的杯芳烃-亚硝基鎓 (NO(+)) 络合物。在路易斯酸的存在下，如 SnCl(4)，稳定的杯芳烃-NO(+) 配合物 7 和 8 以定量产率分离出来，并通过紫外-可见光、FTIR、高分辨率 (1) H NMR 光谱表征和元素分析。NO(+) 被发现封装在杯芳烃腔内，稳定的电荷转移复合物导致 K(ass) > 10(6) M(-1) (CDCl(3))。NO(+) 包封也在杯芳烃 1、2、和 5 和市售的 NO(+)SbF(6)(-) 盐在氯仿中。络合过程是可逆的，加入水和醇后，络合物解离，回收母体杯芳烃。展示了功能化杯[4] 芳烃与硅胶的连接，这提供了一种固体材料
• Molecular tectonics: on the formation of tubular coordination networks
  作者：Guillaume Laugel、Ernest Graf、Mir Wais Hosseini、Jean-Marc Planeix、Nathalie Kyritsakas

  DOI：10.1039/b607982m

  日期：——

  Upon combining the organic tecton based on the [1,1,1,1]metacyclophane bearing four pyridine groups with silver cation, a tubular coordination network formed by double bridging of consecutive macrocycles by metal centres is obtained and structurally characterised in the solid state by an X-ray diffraction method. The same tecton when combined with HgCl2 leads to the formation of a doubly interpenetrated 2-D coordination framework.

  将基于[1,1,1,1]四吡啶基元有机结构与银阳离子结合，通过金属中心双桥接连续大环形成管状配位网络，并通过X射线衍射方法在固态下进行结构表征。当该有机结构与HgCl2结合时，形成双互穿二维配位框架。
• Synthesis and solid state structural analysis exo-bisbidentate ligands based on [1.1.1.1]metacyclophane in 1,3-alternate conformation bearing 2,2′-bipyridine or bisquinoline chelates
  作者：Cédric Klein、Ernest Graf、Mir Wais Hosseini、Gilles Mislin、André De Cian

  DOI：10.1016/s0040-4039(00)01647-6

  日期：2000.11

  The synthesis and structural analysis of two new exoligands 1 and 2 based on a [1.1.1.1]-metacyclophane backbone bearing either 2,2'-bipyridine or bisquinoline chelating units have been achieved. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Covalently linked multi-calixarenes
  作者：O. Mogck、P. Parzuchowski、M. Nissinen、V. Böhmer、G. Rokicki、K. Rissanen

  DOI：10.1016/s0040-4020(98)00594-8

  日期：1998.8

  ipso-Nitration of t-butyl calix[4]arene tetraethers and subsequent hydrogenation provides an easy access to monoamino calix[4]arenes. Reaction with di- and triacid chlorides leads to various double- and triple-calix[4]arenes. With tetra-acid chlorides derived from calix[4]arenes in the cone- or 1,3-alternate-conformations penta-calix[4]arenes are available as molecularly uniform species, which may be regarded as the first generation of calix[4]arene based dendrimers. The structure of the mononitro tetraester derivative, which may serve as a general building block has been confirmed by single crystal X-ray analysis. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Mesitylene-derived 1,3-alternate [1.1.1.1]metacyclophanes
  作者：Sebastiano Pappalardo、George Ferguson、John F. Gallagher

  DOI：10.1021/jo00052a023

  日期：1992.12

  Synthetic procedures to conformationally immobile 1,3-alternate [1.1.1.1]metacyclophanes based on mesitylene units are described. Coupling of mesitol (19) with bis(chloromethyl)mesitol (20) and bis(chloromethyl)mesitylene (21) in nitroethane in the presence of SnCl4 affords metacyclophanes 6 and 7-10, respectively, possessing extra-annular hydroxyl groups. Metacyclophanes 12 and 14, which hold one or two pairs of carboxyl groups in the distal positions, have been obtained from the appropriate distal diol 8 and tetrol 6 by treatment with tert-butyl bromoacetate followed by basic hydrolysis. Functionalized molecular frameworks, such as 15 and 18, have been also prepared in high yield by direct methods. The H-1 NMR spectral characteristics of 1,3-alternate metacyclophanes synthesized are briefly discussed. The structures of mono-, tri-, and tetrahydroxy metacyclophanes 10, 7, and 6, respectively, have been determined by X-ray crystallography. All three macrocycles have very similar 1,3-alternate-biconic conformations with approximate 42mBAR symmetry. Molecules 10 and 7 are isomorphous, and the lone hydroxyl group in 10 and the three hydroxyl groups in 7 are disordered over four possible sites. A toluene of solvation is docked against the molecular cavity in both 10 and 7. Compound 6 has crystallographic 2-fold symmetry and what would have been voids in the crystal lattice are occupied by disordered solvent molecules.