5,11,17,23-tetra(tert-butyl)-25,27-bis-(3-hydroxypropoxy)-26,28-bis-hydroxycalix[4]arene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-tetra(tert-butyl)-25,27-bis-(3-hydroxypropoxy)-26,28-bis-hydroxycalix[4]arene
• 英文别名: 5,11,17,23-tetra-tert-butyl-25,27-bis(3-hydroxypropyloxy)-26,28-dihydroxycalix[4]arene；5,11,17,23-Tetratert-butyl-26,28-bis(3-hydroxypropoxy)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-dodecaene-25,27-diol
• 化学式: C₅₀H₆₈O₆
• 分子量: 765.086
• InChiKey: KKIVUPOWNQVKFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13
• 重原子数：
  56
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  99.4
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetra(tert-butyl)-25,27-bis-(3-hydroxypropoxy)-26,28-bis-hydroxycalix[4]arene 在 titanium(IV) chloride tetrahydrofuran 、 盐酸 、 水 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以70%的产率得到5,11,17,23-tetra-(tert-butyl)-25-(3-hydroxypropoxy)-26,27,28-tris-hydroxycalix[4]arene
  参考文献：
  名称：

  Easy and Selective Method for the Synthesis of Various Mono-O-functionalized Calix[4]arenes: De-O-functionalization Using TiCl₄

  摘要：

  An efficient and selective method for the monofunctionalization of p-tert-butylcalix[4]arene is described A mono-de-O-functionalization of disubstituted p-tert-butylcalix[4]arenes using titanium tetrachloride was developed to synthesize a series of monosubstituted p-tert-butylcalix[4]arenes with the pendant functions being ethoxycarbonylmethyloxy, 3-ethoxycarbonylpropyloxy, cyanomethyloxy, 3-cyanopropyloxy, 4-bromobutyloxy, 3-hydroxypropyloxy, propyloxy, 2-methylpropyloxy, 3-butynyloxy, and 3-cyanopropyloxy groups The reaction mechanism of the formation of 5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxy-25-(3-ethoxycarbonylpropyloxy) calix[4]arene was studied by H-1 NMR and GC/mass spectroscopy monitoring Reaction of TiCl4 with the disubstituted p-tert-butylcalix[4]arene produced the corresponding dioxocalix[4]arene titanium dichloride complex, which undergoes elimination of ethyl 4-chlorobutyrate, leading to a trioxocalix[4]arene titanium dichloride complex and to monosubstituted calix[4]arene after hydrolysis These two complexes were also synthesized, isolated, and fully characterized

  DOI：

  10.1021/jo101319s
• 作为产物：
  描述：

  p-tert-butylcalix[4]arene-bis-propylnalidixate 在 乙醇 、 silica gel 作用下， 以 氯仿 为溶剂， 反应 48.0h， 以62%的产率得到5,11,17,23-tetra(tert-butyl)-25,27-bis-(3-hydroxypropoxy)-26,28-bis-hydroxycalix[4]arene
  参考文献：
  名称：

  Molecular drug-organiser: Synthesis, characterization and biological evaluation of penicillin V and/or nalidixic acid calixarene-based podands

  摘要：

  Two well-known antibiotic heterocycles, the 'quinolone' nalidixic acid and the beta-lactam penicillin V, active at different levels of the bacterial growth process, have been attached via an ether-ester junction to the p-tert-butylcalix[4] arene lower rim, in alternate position. The resulting hydrophobic molecular drug-organisers were fully characterized, and evaluated over two Gram negative and three Gram positive reference strains, using disk diffusion assays with disks impregnated with solution of title compound in pure DMSO. An interesting activity was observed over Staphylococcus aureus ATCC 25923 with the dissymmetrical podand incorporating one penicillin and one nalidixic ester moieties. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.10.031

文献信息

• Azocalix[4]arene-Rhodamine Supramolecular Hypoxia-Sensitive Systems: A Search for the Best Calixarene Hosts and Rhodamine Guests
  作者：Diana Mironova、Vladimir Burilov、Farida Galieva、Mohamed Ali Mohamed Khalifa、Sofia Kleshnina、Alsu Gazalieva、Ramil Nugmanov、Svetlana Solovieva、Igor Antipin

  DOI：10.3390/molecules26185451

  日期：——

  spectrometry and fluorescence as well as 1D and 2D NMR techniques. It was found that all three calixarenes form a complex with rhodamine dyes with a 1:1 composition. The association constants of calixarene-dye complexes with sulfonate calixarenes, especially in the case of tetra-anionic calixarene, turned out to be higher compared with carboxyl calixarene due to the more intense electrostatic interactions. For

  一种潜在的缺氧敏感系统主客体复合物，由三个杯芳烃组成（包括两个在上缘有四个阴离子羧基和磺酸盐偶氮片段，以及新合成的锥体结构的杯芳烃双偶氮加合物，在下缘有偶氮片段）使用 UV-VIS 光谱法和荧光以及 1D 和 2D NMR 技术对最广泛使用的阳离子和两性离子罗丹明染料（123、6G 和 B））进行了研究。结果发现，所有三种杯芳烃与罗丹明染料以 1:1 的组成形成复合物。由于更强烈的静电相互作用，杯芳烃-染料复合物与磺酸盐杯芳烃的缔合常数，特别是在四阴离子杯芳烃的情况下，与羧基杯芳烃相比更高。首次使用 HRESI MS 技术表明，用连二亚硫酸钠 (SDT) 处理罗丹明 6G 和 123 会产生非荧光无色形式的染料，并且只有罗丹明 B 可以与 SDT 一起使用而不会发生这种情况。的侧面减少。此外，还发现除了偶氮基团的减少之外，SDT 还会导致芳基醚键部分断裂。当 SDT 用作偶氮还原酶模拟物时，应考虑
• Calix[4]arene-Linked Bisporphyrin Hosts for Fullerenes:  Binding Strength, Solvation Effects, and Porphyrin−Fullerene Charge Transfer Bands
  作者：Ali Hosseini、Steven Taylor、Gianluca Accorsi、Nicola Armaroli、Christopher A. Reed、Peter D. W. Boyd

  DOI：10.1021/ja066031x

  日期：2006.12.1

  hosts for supramolecular binding of fullerene guests. Fullerene affinities were optimized by varying the nature of the covalent linkage of the porphyrins to the calixarenes. Binding constants for C60 and C70 in toluene were explored as a function of substituents at the periphery of the porphyrin, and 3,5-di-tert-butylphenyl groups gave rise to the highest fullerene affinities (26,000 M(-1) for C60). The

  杯[4]芳烃支架已被用于构建双卟啉（“颚”卟啉）宿主，用于富勒烯客体的超分子结合。通过改变卟啉与杯芳烃的共价键的性质，优化了富勒烯的亲和力。研究了甲苯中 C60 和 C70 的结合常数作为卟啉外围取代基的函数，3,5-二叔丁基苯基基团产生了最高的富勒烯亲和力（C60 为 26,000 M(-1)） . 这种高富勒烯亲和力的起源可以追溯到不同的溶剂化效应而不是电子效应。作为溶剂函数的结合常数的研究（甲苯 < 苯甲腈 < 二氯甲烷 < 环己烷）与富勒烯溶解度成反比，表明富勒烯的去溶剂化是决定结合常数大小的主要因素。富勒烯结合的能量学已根据 DelatH 和 DeltaS 确定，并且与焓驱动、溶剂化依赖过程一致。已经建立了富勒烯客体与双卟啉主体的超分子结合与宽 NIR 吸收带的出现之间的直接关系。该能带的能量作为卟啉电子结构的函数以可预测的方式移动，从而确定其起源于卟啉到富勒烯的电荷转移。已经建
• New potential prodrugs of aciclovir using calix[4]arene as a lipophilic carrier: synthesis and drug-release studies at the air–water interface
  作者：Guillaume Sautrey、Igor Clarot、Ewa Rogalska、Jean-Bernard Regnouf-de-Vains

  DOI：10.1039/c2nj40338b

  日期：——

  Two tetra-p-tert-butyl-calix[4]arene species bearing one or two anti-HSV aciclovir units tethered via carbodiester linkages at the lower rim were synthesized as possible antiviral prodrugs. The amphiphilic properties of these derivatives were studied using Langmuir balance at the air–water and air–carbonate buffer interfaces; the monolayers formed were stable on both subphases. Monolayers formed with these molecules on a carbonate buffer subphase at pH 10 and 37 °C were then used for monitoring hydrolysis of the diester linkage. The release of free aciclovir of around 30% in 3 days was observed with both derivatives, as shown with HPLC.

  两种四对叔丁基杯[4]芳烃物种通过碳酯键在下缘连接着一个或两个抗HSV阿昔洛韦单元，被合成为可能的抗病毒前药。使用Langmuir平衡在空气-水和空气-碳酸盐缓冲界面研究了这些衍生物的两亲性；形成的单层在两个亚相上都是稳定的。然后在pH 10和37°C的碳酸盐缓冲亚相上用这些分子形成的单层来监测二酯键的水解。通过HPLC观察到两种衍生物在3天内释放出约30%的游离阿昔洛韦。
• Unprecedented Cyclizations of Calix[4]arenes with Glycols under the Mitsunobu Protocol, Part 2.¹ O,O-and O,S-Bridged Calixarenes
  作者：Viktor Csokai、Alajos Grün、Barbara Balázs、Gábor Tóth、Gyula Horváth、István Bitter

  DOI：10.1021/ol0359315

  日期：2004.2.1

  Cycloalkylations of p-tert-butylcalix[4]arene (CA) and p-tert-butylthiacalix[4]arene (TCA) with various aliphatic glycols were performed under the Mitsunobu protocol using the DEAD/TPP system. CA gave 1,3-dialkylated diols, while C-2-C-10 glycols gave 1,2- and 1,3-bridged calixarenes. The reaction of TCA with C-2 diols afforded sulfonium phenoxide betaines via O,S-cyclization, which is the first example for the alkylation of the sulfide bridge.
• Molecular drug-organiser: Synthesis, characterization and biological evaluation of penicillin V and/or nalidixic acid calixarene-based podands
  作者：Adel Ben Salem、Guillaume Sautrey、Stéphane Fontanay、Raphaël E. Duval、Jean-Bernard Regnouf-de-Vains

  DOI：10.1016/j.bmc.2011.10.031

  日期：2011.12

  Two well-known antibiotic heterocycles, the 'quinolone' nalidixic acid and the beta-lactam penicillin V, active at different levels of the bacterial growth process, have been attached via an ether-ester junction to the p-tert-butylcalix[4] arene lower rim, in alternate position. The resulting hydrophobic molecular drug-organisers were fully characterized, and evaluated over two Gram negative and three Gram positive reference strains, using disk diffusion assays with disks impregnated with solution of title compound in pure DMSO. An interesting activity was observed over Staphylococcus aureus ATCC 25923 with the dissymmetrical podand incorporating one penicillin and one nalidixic ester moieties. (C) 2011 Elsevier Ltd. All rights reserved.