25,27-Bis(3,5-dinitrobenzoyloxy)calix[4]arene | 137258-49-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 25,27-Bis(3,5-dinitrobenzoyloxy)calix[4]arene
• 英文别名: [27-(3,5-Dinitrobenzoyl)oxy-26,28-dihydroxy-25-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] 3,5-dinitrobenzoate
• CAS: 137258-49-2
• 化学式: C₄₂H₂₈N₄O₁₄
• 分子量: 812.703
• InChiKey: PPSAZIKIRVMUGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  60
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  276
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  25,27-Bis(3,5-dinitrobenzoyloxy)calix[4]arene 在 N-甲基咪唑 作用下， 以 氯仿 为溶剂， 以81%的产率得到
  参考文献：
  名称：

  Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups

  摘要：

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。

  DOI：

  10.1139/v01-161
• 作为产物：
  描述：

  杯[4]芳烃 、 3,5-二硝基苯甲酰氯 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 以91%的产率得到25,27-Bis(3,5-dinitrobenzoyloxy)calix[4]arene
  参考文献：
  名称：

  Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups

  摘要：

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。

  DOI：

  10.1139/v01-161

文献信息

• Tuning conformations of calix[4]tubes by weak intramolecular interactions
  作者：Kirill Puchnin、Dmitry Cheshkov、Pavel Zaikin、Ivan Vatsouro、Vladimir Kovalev

  DOI：10.1039/c2nj40961e

  日期：——

  The conformational distribution in distally functionalized adamantylated calix[4]tubes was analyzed with NMR and quantum-chemical calculations. Without any intramolecular interactions, ester-, acid-, amino-, alcohol-, isocyanate-, phthalimide- and urea-substituted calixtubes preferred less sterically hindered flattened cone conformers in solution. In contrast, in a non-polar medium (CDCl3) for calixtubes bearing two 3-carboxymethyl-1-adamantyl or 3-(2-ureidoethyl)-1-adamantyl units, the less sterically preferable flattened cone conformation with bulky substituents connected by intramolecular hydrogen bonds was found to be more favorable. On the other hand, for a calixtube with two positively charged units, only the conformer with distanced substituents was exclusively detected. Thus, the conformational equilibrium in functionalized calix[4]tubes can be controlled by intramolecular hydrogen bonding between appropriately arranged carboxylic groups or urea moieties, or by electrostatic repulsion of positively charged substituents.

  在远端功能化的金刚烷基化的 calix[4] 管中，采用核磁共振（NMR）和量子化学计算分析了构象分布。在没有任何分子内相互作用的情况下，酯、酸、氨基、醇、异氰酸酯、酚肼和尿素取代的 calix 管在溶液中更倾向于选择立体阻碍较小的扁平锥形构象。相比之下，在非极性溶剂（CDCl3）中，带有两个 3-羧基甲基-1-金刚烷或 3-(2-脲乙基)-1-金刚烷基单位的 calix 管，其包含由分子内氢键连接的体积较大取代基的立体障碍较小的扁平锥拥形构象被发现更为有利。另一方面，对于一个拥有两个正电荷单位的 calix 管，仅检测到带有远离取代基的构象。因此，功能化的 calix[4] 管中的构象平衡可以通过适当排列的羧酸基团或尿素基的分子内氢键，或通过正电荷取代基的静电排斥来进行调控。
• Calix[4]tubes: An Approach to Functionalization
  作者：Kirill Puchnin、Pavel Zaikin、Dmitry Cheshkov、Ivan Vatsouro、Vladimir Kovalev

  DOI：10.1002/chem.201200247

  日期：2012.8.27

  Adamantylcalix[4]arenes decorated with ester groups and calix[4]arene tetratosylates were used to prepare a series of calix[4]tubes bearing 3‐methoxycarbonyl‐ and 3‐methoxycarbonylmethyl‐1‐adamantyl units (up to eight) in good yield. These compounds were subjected to further chemical transformations giving a wide set of novel ester‐, acid‐, hydroxy‐, amine‐, and urea‐functionalized calix[4]tubes. Introduction

  用酯基修饰的金刚烷基杯[4]芳烃和杯[4]芳烃四甲苯磺酸酯用于制备一系列带有3-甲氧羰基和3-甲氧羰基甲基-1-金刚烷基单元（最多八个）的杯[4]管。 。这些化合物经过进一步的化学转化，得到了一系列新颖的酯，酸，羟基，胺和尿素官能化的杯[4]管。杯形管核心引入尿素基团不仅导致了阴离子靶向受体，而且还提供了宿主的异位特性，这丰富了杯形管[4]的成熟的钾吸收能力。
• Kovalev; Shokova; Paraskevov, Russian Journal of Organic Chemistry, 1999, vol. 35, # 10, p. 1464 - 1471
  作者：Kovalev、Shokova、Paraskevov

  DOI：——

  日期：——
• ——
  作者：E. A. Shokova、A. N. Khomich、V. V. Kovalev

  DOI：10.1023/a:1012423128245

  日期：——

  Lower-rim mono- and diacylated calix[4]arenes [acyl = C6H5CO, 3,5-(NO2)(2)C6H3CO] undergo selective adamantylation with 3-Y-1-adamantanols (Y = H, i-Pr, 4-MeC6H4) in trifluoroacetic acid at the free phenolic fragments of the macroring. The reaction provides a convenient preparative route to di-, tri-, and tetraadamantylated calix[4]arenes.
• Calixarenes. 26. Selective esterification and selective ester cleavage of calix[4]arenes
  作者：Keat Aun See、Frank R. Fronczek、William H. Watson、Ram P. Kashyap、C. David Gutsche

  DOI：10.1021/jo00026a015

  日期：1991.12

  Methods have been developed for converting p-tert-butylcalix[4]arene (1a) in high yield to the 25-monoester 7, the 25,26-diesters 5 and 6, the 25,27-diester 4a, and the 25,26,27-triesters 2 and 3 in which the aryl groups are 3,5-dinitrophenyl moieties. Concomitantly, methods have emerged whereby these esters can be selectively cleaved or rearranged. By appropriate choice of reaction conditions the 25,27-diester 4a can be selectively cleaved with imidazole bases to the monoester 7 or rearranged to the 25,26-diester 5; the triesters 2 and 3 can be converted to their conformationally related 25,26-diesters 5 (a chiral compound) and 6. The effects of variations in solvent, organic base, and reaction time on the conversion of 4a to 7, along with semiquantitative kinetic data, suggest that two or more molecules of the imidazole are involved in the activated complex of the rate-determining step in the aminolysis. These syntheses provide easy access to the mono-, di-, and triesters, thus expanding the techniques for obtaining selectivity para-substituted calixarenes via selective de-tert-butylation. Thus, removal of three, two, or one tert-butyl group, respectively, from the monoester 7, the diesters 4a and 5, and the triester 2 yields the corresponding mono-, di-, and tri-tert-butylated analogues 12a-d. Acylation of 12b, for example, can be effected at the vacated para positions to produce the diacylcalix[4]arenes 15a and 15b. Collectively, the system provides an example of how careful control of reaction conditions can be used to advantage in determining product formation.