5,11,17,23-tetra-tert-butyl-25,27-bis((3,5-dinitrobenzoyl)oxy)-26,28-dihydroxycalix<4>arene | 142433-56-5

• 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: 5,11,17,23-tetra-tert-butyl-25,27-bis((3,5-dinitrobenzoyl)oxy)-26,28-dihydroxycalix<4>arene
• 英文别名: [5,11,17,23-Tetratert-butyl-27-(3,5-dinitrobenzoyl)oxy-26,28-dihydroxy-25-pentacyclo[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-dodecaenyl] 3,5-dinitrobenzoate
• CAS: 142433-56-5
• 化学式: C₅₈H₆₀N₄O₁₄
• 分子量: 1037.13
• InChiKey: KWMQTIHMHUILQG-UHFFFAOYSA-N

物化性质

• 沸点：
  1033.4±65.0 °C(Predicted)
• 密度：
  1.280±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  15.8
• 重原子数：
  76
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.34
• 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：

  5,11,17,23-tetra-tert-butyl-25,27-bis((3,5-dinitrobenzoyl)oxy)-26,28-dihydroxycalix<4>arene 在 咪唑 、 三氯化铝 作用下， 以 氯仿 为溶剂， 反应 25.0h， 生成 5,17-di-tert-butyl-11,23-diacryloyl-25,27-bis((3,5-dinitrobenzoyl)oxy)-26,28-dihydroxycalix<4>arene
  参考文献：
  名称：

  Calixarenes. 26. Selective esterification and selective ester cleavage of calix[4]arenes

  摘要：

  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.

  DOI：

  10.1021/jo00026a015
• 作为产物：
  描述：

  3,5-二硝基苯甲酸 、 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 吡啶 、 dichloro phenyl phosphate 、 N,N-二甲基甲酰胺 作用下， 生成 5,11,17,23-tetra-tert-butyl-25,27-bis((3,5-dinitrobenzoyl)oxy)-26,28-dihydroxycalix<4>arene
  参考文献：
  名称：

  Calixarenes. 26. Selective esterification and selective ester cleavage of calix[4]arenes

  摘要：

  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.

  DOI：

  10.1021/jo00026a015

文献信息

• Synthesis and C70 complexation studies of a fluorescent 5,5’-bi-p-tert-butylcalix[4]arene scaffold
  作者：Amos Golan、Israel Goldberg、Arkadi Vigalok

  DOI：10.1080/10610278.2015.1127374

  日期：2016.6.2

  Abstract In this paper, we report the synthesis and C70 complexation studies of a new fluorescent 5,5′-bi-p-tert-butylcalix[4]arene capsule with an extended hydrophobic cavity. The synthetic route required development of a series of selective protection and de-protection reactions, such as esterification and ester cleavage, as well as a cross-coupling reaction at the lower rim. The resulting 5,5′-

  摘要 在本文中，我们报告了具有扩展疏水腔的新型荧光 5,5'-双对叔丁基杯[4]芳烃胶囊的合成和 C70 络合研究。合成路线需要开发一系列选择性保护和脱保护反应，例如酯化和酯裂解，以及下缘的交叉偶联反应。得到的 5,5'-双-对-叔丁基杯芳烃被充分表征，包括通过 X 射线晶体学。在固态下，该化合物以“开放胶囊”方向存在，具有完美的平面桥联亚联苯单元，可产生高荧光，最大发射峰位于 390 nm。与 C70 富勒烯的初步基于荧光的络合实验没有为包合物的形成提供确凿的证据。