α,α,α,α-meso-tetramethyl-meso-tetra-4-hydroxyphenylcalix[4]pyrrole | 255389-22-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: α,α,α,α-meso-tetramethyl-meso-tetra-4-hydroxyphenylcalix[4]pyrrole
• 英文别名: αααα-tetra-(4-hydroxyphenyl)calix[4]pyrrole；meso-tetramethyltetrakis(hydroxyphenyl)calix[4]pyrrole；phenoxycalix[4]pyrrole
• CAS: 255389-22-1
• 化学式: C₄₈H₄₄N₄O₄
• 分子量: 740.902
• InChiKey: QDWWSQJZYYLCMY-JRRJZXJCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.55
• 重原子数：
  56.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  144.08
• 氢给体数：
  8.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  溴乙酸甲酯 、 α,α,α,α-meso-tetramethyl-meso-tetra-4-hydroxyphenylcalix[4]pyrrole 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 7.0h， 生成 tetramethyl 2,2',2'',2'''-((((5s,10s,15s,20s)-5,10,15,20-tetramethyl-5H,10H,15H,20H,22H,24H-porphyrin-5,10,15,20-tetrayl)tetrakis(benzene-4,1-diyl))tetrakis(oxy))tetraacetate
  参考文献：
  名称：

  Verdejo, Begonna; Gil-Ramirez, Guzman; Ballester, Pablo, Journal of the American Chemical Society, 2009, vol. 131, p. 3178 - 3179

  摘要：

  DOI：
• 作为产物：
  描述：

  吡咯 、 对羟基苯乙酮 在 甲烷磺酸 作用下， 以 甲醇 为溶剂， 生成 α,α,α,α-meso-tetramethyl-meso-tetra-4-hydroxyphenylcalix[4]pyrrole
  参考文献：
  名称：

  新型水不溶性苯氧基杯[4]吡咯-表氯醇聚合物从水性介质中固液萃取碘化物和溴化物。

  摘要：

  本研究描述了第一个基于苯氧基杯[4]吡咯-表氯醇的聚合物的合成。后者的优点在于它的快速单步合成方案，低成本，水不溶性和意外的阴离子提取能力。通过在水溶液中用卤化物进行各种固/液萃取和定量离子色谱分析对该聚合物进行的研究表明，与其他基于杯[4]吡咯的实体不同，由于存在大量萃取物，该聚合物萃取碘化物而不是溴化物和氟化物。口袋。还强调了优选包括氯和溴的阴离子交换过程的证据。

  DOI：

  10.1039/c9ob01306g

文献信息

• Calix[4]pyrroles Containing Deep Cavities and Fixed Walls. Synthesis, Structural Studies, and Anion Binding Properties of the Isomeric Products Derived from the Condensation of <i>p</i>-Hydroxyacetophenone and Pyrrole
  作者：Pavel Anzenbacher,、Karolina Jursíková、Vincent M. Lynch、Philip A. Gale、Jonathan L. Sessler

  DOI：10.1021/ja993195n

  日期：1999.12.1

  The acid-catalyzed condensation of 4-hydroxyphenylmethyl ketone (p-hydroxyacetophenone) with pyrrole affords a new type of calix[4]pyrrole derivative that contains deep cavities and fixed walls. These new systems, which can be readily converted into the corresponding 4-methoxyphenyl species, can exist in the form of four different configurational isomers, as well as in different conformational forms

  4-羟基苯甲基酮（对羟基苯乙酮）与吡咯在酸催化下缩合得到一种新型的杯[4]吡咯衍生物，它含有深腔和固定壁。这些新系统可以很容易地转化为相应的 4-甲氧基苯基物种，可以以四种不同的构象异构体的形式存在，也可以以不同的构象形式存在。三种构型异构体，即????、????和???? 异构体，其中的术语“？” 和 ”？” 指示庞大的官能化苯基取代基相对于平均杯吡咯平面是“向上”还是“向下”，通过柱色谱分离。然后使用 X 射线衍射分析进行结构证明和构型分配。使用标准 1 H NMR 滴定技术在溶液中（乙腈-d3:D2O；99.5:0.5 v./v.）研究内消旋芳基取代基对受体的阴离子结合亲和力的影响。令人惊讶的是，发现 4-羟基苯基和 4-甲氧基苯基衍生的系统都显示出对小阴离子的较低亲和力，即。Cl- 和 H2PO4- 比简单的未取代杯 [4] 吡咯（如内消旋八甲基杯吡咯）更有效。另一方面，观察到可归
• Fluoride recognition in ‘super-extended cavity’ calix[4]pyrroles
  作者：Salvatore Camiolo、Philip A. Gale

  DOI：10.1039/b003229h

  日期：——

  Extended cavity ester (4) and amide (5) calix[4]pyrrole macrocycles have been synthesised and shown to bind fluoride exclusively in deuteriated DMSO solution.

  我们合成了扩展空腔酯（4）和酰胺（5）钙[4]吡咯大环，并证明它们在脱脂 DMSO 溶液中只与氟化物结合。
• A mono-metallic Pd(<scp>ii</scp>)-cage featuring two different polar binding sites
  作者：Luis Escobar、David Villarón、Eduardo C. Escudero-Adán、Pablo Ballester

  DOI：10.1039/c8cc09195a

  日期：——

  aryl-extended tetra-pyridyl calix[4]pyrrole self-assembles into a mono-metallic Pd(II)-cage featuring two different and converging polar binding sites. Mono- and di-topic polar guests are bound reversibly in the cage. A mechanism for guest exchange in the cage complexes is proposed.

  超级芳基延伸的四吡啶杯杯[4]吡咯的四α异构体自组装成具有两个不同且会聚极性结合位点的单金属Pd（II）笼。单位和双位极地客人可逆地绑在笼子里。提出了一种在网箱综合体中进行来宾交换的机制。
• Quantitative Evaluation of Anion–π Interactions in Solution
  作者：Guzmán Gil-Ramírez、Eduardo C. Escudero-Adán、Jordi Benet-Buchholz、Pablo Ballester

  DOI：10.1002/anie.200800636

  日期：2008.5.19
• Fluoride-Selective Binding in a New Deep Cavity Calix[4]pyrrole:  Experiment and Theory
  作者：Christopher J. Woods、Salvatore Camiolo、Mark E. Light、Simon J. Coles、Michael B. Hursthouse、Michael A. King、Philip A. Gale、Jonathan W. Essex

  DOI：10.1021/ja025572t

  日期：2002.7.1

  A new "super-extended cavity" tetraacetylcalix[4]pyrrole derivative was synthesized and characterized, and X-ray crystal structures of complexes bound to fluoride and acetonitrile were obtained. The binding behavior of this receptor was investigated by NMR titration, and the complex was found to exclusively bind fluoride ions in DMSO-d(6). This unusual binding behavior was investigated by Monte Carlo free energy perturbation simulations and Poisson calculations, and the ion specificity was seen to result from the favorable electrostatic interactions that the fluoride gains by sitting lower in the phenolic cavity of the receptor. The effect of water present in the DMSO on the calculated free energies of binding was also investigated. Owing to the use of a saturated ion solution, the effect of contaminating water is small in this case; however, it has the potential to be very significant at lower ion concentrations. Finally, the adaptive umbrella WHAM protocol was investigated and optimized for use in binding free energy calculations, and its efficiency was compared to that of the free energy perturbation calculations; adaptive umbrella WHAM was found to be approximately two times More efficient. In addition, structural evidence demonstrates that the protocol explores a wider conformational range than free energy perturbation and should therefore be the method of choice. This paper represents the first complete application of this methodology to "alchemical" changes.