5,11,17,23-tetra(chloromethyl)-25,26,27,28-tetra-hydroxycalix[4]arene

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,11,17,23-tetra(chloromethyl)-25,26,27,28-tetra-hydroxycalix[4]arene
• 英文别名: 5,11,17,23-Tetrakis(chloromethyl)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-25,26,27,28-tetrol
• 化学式: C₃₂H₂₈Cl₄O₄
• 分子量: 618.384
• InChiKey: IFSOACMKBSKJJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  5,11,17,23-tetra(chloromethyl)-25,26,27,28-tetra-hydroxycalix[4]arene 在 二(三甲基甲硅烷基)乙炔 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 5.0h， 生成 5,11,17,23-tetrakis(hydroxyphosphonoyl)methyl-25,26,27,28-tetrahydroxycalix[4]arene sodium salt
  参考文献：
  名称：

  Transportation of Poorly Soluble Drug Molecules from the Organic Phase to the Aqueous Phase by Using Phosphorylated Calixarenes

  摘要：

  This study is the first report on the extraction of poorly soluble drug molecules such as nifedipine, niclosamide, and furosemide from the organic phase to the aqueous phase by water-soluble p-phosphonate calix[n]arene receptors via a liquid-liquid phase extraction process. These water-soluble calixarene derivatives were easily obtained from the reaction between their corresponding chloromethylated derivatives and trimethyl phosphite. From the liquid-liquid phase extraction studies, it was observed that the size of the p-phosphonate calix[n]arenes changed the extraction percentage of selected drug molecules.

  DOI：

  10.1021/je2004319
• 作为产物：
  描述：

  4-叔丁基苯酚 在 aluminum (III) chloride 、 sodium hydroxide 作用下， 以 二苯醚 、 甲苯 、 苯酚 为溶剂， 反应 3.0h， 生成 5,11,17,23-tetra(chloromethyl)-25,26,27,28-tetra-hydroxycalix[4]arene
  参考文献：
  名称：

  Improvement of catalytic activity of Candida rugosa lipase in the presence of calix[4]arene bearing iminodicarboxylic/phosphonic acid complexes modified iron oxide nanoparticles

  摘要：

  In the present study, iron oxide magnetite nanoparticles, prepared through a co-precipitation method, were coated with phosphonic acid or iminodicarboxylic acid derivatives of calix[4]arene to modulate their surfaces with different acidic groups. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through sol-gel encapsulation. The catalytic activities and enantioselectivities of the two encapsulated lipases in the hydrolysis reaction of (R/S)-naproxen methyl ester and (R/S)-2-phenoxypropionic acid methyl ester were assessed. The results showed that the activity and enantioselectivity of the lipase were improved when the lipase was encapsulated in the presence of calixarene-based additives; the encapsulated lipase with the phosphonic acid derivative of calix[4]arene had an excellent rate of enantioselectivity against the (R/S)-naproxen methyl and (R/S)-2-phenoxypropionic acid methyl esters, with E = 350 and 246, respectively, compared to the free enzyme. The encapsulated lipases (Fe-Calix-N(COOH)) and (Fe-Calix-P) showed good loading ability and little loss of enzyme activity, and the stability of the catalyst was very good; they only lost 6-11% of the enzyme's activity after five batches. (C) 2015 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.bioorg.2015.12.001

文献信息

• Novel integrated sensing system of calixarene and rhodamine molecules for selective colorimetric and fluorometric detection of Hg2+ ions in living cells
  作者：Bahar Yilmaz、Mukaddes Keskinates、Mevlut Bayrakci

  DOI：10.1016/j.saa.2020.118904

  日期：2021.1

  Three novel and facile calixarene derivatives (5, 6 and 7), which were appended with four rhodamine units at the upper rim of calixarene skeleton, were firstly prepared and evaluated for selective detection of metal ions in solution. Receptors (5) and (7) indicated immediate turn on fluorescence output toward Hg2+ ions over other most competitive metal ions with the ultralow detection limits, indicating

  三个新的和容易的杯芳烃衍生物（5，6和7），将其在杯芳烃骨架的上缘所附四个罗丹明单位，被首先制备并评价在溶液中的金属离子的选择性检测。受体（5）和（7）表示，与其他最具竞争力的金属离子相比，具有超低检测限的荧光输出立即向Hg 2+离子输出，表明它们的高效率和可靠性。对Hg 2+的结合反应还通过发色变化（从无色到浅粉红色）观察到溶液中的离子。此外，还进行了MCF-7或MIA PaCa-2细胞系的体外和生物成像研究，以研究受体在生物系统中的使用，以监测汞离子。结果表明，新受体（5）或（7）具有细胞渗透性，适用于活细胞（MCF-7）或（MIA PaCa-2）中Hg 2+的实时成像，而不会损害健康细胞系（HEK） 293）。
• Entrapment of a dirhodium tetracarboxylate unit inside the aromatic bowl of a calix[4]arene: Unique catalysts for C–H amination
  作者：Benjamin H. Brodsky、J. Du Bois

  DOI：10.1039/b611280c

  日期：——

  Unique calix[4]arene-derived, tetracarboxylate dirhodium(II) inclusion complexes have been prepared and evaluated as catalysts for C–H amination.

  独特的杯[4]芳烃衍生四羧酸二铑(II)包合物已被制备，并被评估为C-H胺化反应的催化剂。
• Synthesis and metal extraction behavior of pyridine and 1,2,4-triazole substituted calix[4]arenes
  作者：Ashok Kumar、Pratibha Sharma、Bhagwan Lal Kalal、Lal Kumar Chandel

  DOI：10.1007/s10847-010-9796-2

  日期：2010.12

  of heterocycle substituted calixarenes, derivatized at lower and upper rim, were synthesized and successfully evaluated for metal extraction towards alkali, alkaline, transition and heavy metal ions. The presence and placement of sulfur, heterocycle functionality at upper/lower rim played a crucial role toward the extractability and selectivity of metal ions. The lower rim substituted calixarenes have

  合成了三个系列的杂环取代杯芳烃，在下缘和上缘衍生化，并成功评估了对碱金属、碱金属、过渡金属和重金属离子的金属萃取。硫、杂环官能团在上/下边缘的存在和位置对金属离子的可萃取性和选择性起着至关重要的作用。下缘取代的杯芳烃表现出高可萃取性和差的选择性。与此相反，上缘取代的杯芳烃表现出良好的选择性。此外，与碱金属和碱金属离子相比，硫官能化杯芳烃对重金属离子显示出更好的选择性。在上缘取代的杯芳烃中，发现 17 和 18 适用于 Na+、K+ 和 Ag+，19,13 适用于重金属离子，即 Pb2+、Hg+、Hg2+ 和 Ag+，以及 11，
• Calixarene-based phosphinic acids as inhibitors of protein tyrosine phosphatases
  作者：Vladyslav M. Buldenko、Viacheslav V. Trush、Oleksandr L. Kobzar、Andriy B. Drapailo、Vitaly I. Kalchenko、Andriy I. Vovk

  DOI：10.1016/j.bmcl.2019.01.026

  日期：2019.3

  MEG1, MEG2, and SHP2. The most potent sulfonylcalix[4]arene phosphinic acid displayed Ki value of 32 nM. The thiacalix[4]arene phosphinic acid was found to be a low micromolar inhibitor of PTP1B with selectivity over the other PTPs. The kinetic experiments showed that the inhibitors compete with the substrate for the active site of the enzyme. Molecular docking was performed to explain possible binding

  在本工作中，合成了在大环上缘带有四个亚甲基（苯基）次膦酸基团的杯[4]亚芳基，噻唑杯[4]亚芳基和磺酰基杯[4]亚芳基的衍生物，并作为人类抑制剂进行了研究。蛋白酪氨酸磷酸酶。三种化合物对PTP1B的抑制能力高于对蛋白质酪氨酸磷酸酶TC-PTP，MEG1，MEG2和SHP2的抑制能力。最有效的磺酰基杯[4]亚芳基次膦酸的Ki值为32 nM。发现噻唑烷[4]亚芳基次膦酸是PTP1B的低微摩尔抑制剂，具有比其他PTP更高的选择性。动力学实验表明抑制剂与底物竞争酶的活性位点。
• Self-inclusion structure of 5,11,17,23-tetrakis(azidomethyl)-25,26,27,28-tetrahydroxycalix[4]arene, and 5,11,17,23-tetra-<i>tert</i>-butyl-25,27-bis(chloroacetoxy)-26,28-bis(2-pyridylmethoxy)calix[4]arene
  作者：Mei Zhao、Xin-Yan Zhang、Jian-Ping Ma、Ru-Qi Huang、Dian-Shun Guo

  DOI：10.1107/s0108270109010609

  日期：2009.4.15

  of the two title calix[4]arene derivatives, C32H28N12O4, (I), and C60H68Cl2N2O6, (II), compound (I) adopts an open‐cone conformation in which there are four intramolecular O—H...O hydrogen bonds, while compound (II) adopts a distorted chalice conformation where the two pendant pyridyl rings, one of which is disordered, are almost mutually perpendicular, with an interplanar angle of 79.2 (2) or 71.4 (2)°

  在两个标题杯[4]芳烃衍生物的结构中，C 32 H 28 N 12 O 4，（I）和C 60 H 68 Cl 2 N 2 O 6，（II），化合物（I）采用开环构型，其中有四个分子内OH-H ... O氢键，而化合物（II）采用扭曲的圣杯构型，其中两个侧基吡啶基环是一个杂乱无章的物体几乎相互垂直，平面角度为79.2（2）或71.4（2）°。四个桥接亚甲基C原子定义的虚拟平面与苯酚环之间的二面角（I）为120.27（7），124.03（6），120.14（8）和128.25（7）°，以及95.99（8） （II）分别为135.93（7），97.21（8）和126.10（8）°。在（I）的超分子结构中，成对的分子通过自包含而缔合，其中分子的一个叠氮基团插入与转化相关的分子的腔中，并且缔合通过弱分子间的CH稳定。 .N氢键和π（N3）–π（芳香）相互作用。分子对通过弱分子间的CH-H ... N