25,27-bis(hydroxy)-26,28-bis(tert-butoxycarbonylmethoxy)calix[4]arene | 164726-21-0

• 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(hydroxy)-26,28-bis(tert-butoxycarbonylmethoxy)calix[4]arene
• 英文别名: 25,27-dihydroxy-26,28-bis[(tert-butoxycarbonyl)-methoxy]calix[4]arene；25,27-bis[(tert-butoxycarbonyl)methoxy]-24,28-dihydroxycalix[4]arene；26,28-bis[(tert-butoxycarbonyl)methoxy]-25,27-dihydroxycalix[4]arene；Tert-butyl 2-[[26,28-dihydroxy-27-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethoxy]-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]oxy]acetate
• CAS: 164726-21-0
• 化学式: C₄₀H₄₄O₈
• 分子量: 652.785
• InChiKey: APIWEQSIYGPNKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  48
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  25,27-bis(hydroxy)-26,28-bis(tert-butoxycarbonylmethoxy)calix[4]arene 在 氢氧化钾 、 草酰氯 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 28.0h， 生成 tert-butyl 2-[[27-[2-(diethylamino)-2-oxoethoxy]-26,28-dihydroxy-25-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaenyl]oxy]acetate
  参考文献：
  名称：

  基于杯[4]芳烃的树枝状聚合物。

  摘要：

  描述了包含最多七个杯[4]芳烃基团的杯[4]芳烃基树枝状分子的合成，包括三-杯[4]芳烃支化衍生物的X射线晶体结构。

  DOI：

  10.1039/b202315f
• 作为产物：
  描述：

  25,27-bis(benzyloxy)-26,28-dihydroxycalix[4]arene 在 palladium 10% on activated carbon 、 氢气 、 potassium hydride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 20.0 ℃ 、344.75 kPa 条件下， 反应 50.0h， 生成 25,27-bis(hydroxy)-26,28-bis(tert-butoxycarbonylmethoxy)calix[4]arene
  参考文献：
  名称：

  具有1,3-交替，圆锥和部分圆锥构象的双离子化杯[4]芳烃-1,3-crown-4配体：合成和金属离子提取

  摘要：

  合成了以1，3-交替，圆锥和部分圆锥构象锁定的可离子化的杯[4]芳烃-1,3-冠-4化合物，用于金属离子分离中的评估。可电离的功能包括羧酸和N-（X）磺酰基羧酰胺基团，其中通过改变X的吸电子能力来调节酸度。采用类似的合成路线来制备视锥和1，3-交替配体系列。需要使用保护和脱保护的不同制备途径来获得部分锥体类似物。配体构象通过其质子和/或碳NMR谱证实。X射线衍射验证了一种合成中间体在固态中具有不同寻常的1,2-交替构象。评估了配体构象和可电离基团变化对竞争性溶剂萃取从水溶液到氯仿的碱金属和碱土金属阳离子的影响。Hg 2+和Pb 2+的单种溶剂萃取 也进行了。

  DOI：

  10.1016/j.tet.2012.01.051

文献信息

• The Synthesis of Diquinone and Dihydroquinone Derivatives of Calix[4]arene and Electrochemical Characterization on Au(111) surface
  作者：Boštjan Genorio

  DOI：10.17344/acsi.2016.2289

  日期：2016.9.15

  -OH groups with trimethylsilyl groups (TMS) either on lower-rim or on upper-rim was developed. Four selected molecules - with sulfide anchor groups and carboxylic anchor groups - were adsorbed onto Au(111) single crystal surface using ex-situ and insitu self-assembly methods. Adsorbed molecules were then electrochemically probed with cyclic voltammetry. All adsorbed molecules showed redox response which

  设计，合成和表征了几种带有锚固官能团的杯[4]芳烃的新的电活性二醌和二氢醌衍生物。开发了一种在下边缘或上边缘用三甲基甲硅烷基（TMS）选择性保护氢醌-OH基的方法。使用异位和原位自组装方法将四个选定的分子-具有硫化物锚定基团和羧基锚定基团-吸附到Au（111）单晶表面上。然后用循环伏安法对吸附的分子进行电化学探测。所有吸附的分子均显示出氧化还原反应，该反应在循环过程中发生了变化。调节后，CV稳定并显示所有分子的两个不同的电流峰。合成和电化学探测的分子对于以下方面很重要：
• Effect of conformation on metal ion extraction by calix[4]arene dicarboxylic acids
  作者：Chunkyung Park、Sangki Chun、Richard A. Bartsch

  DOI：10.1007/s10847-009-9650-6

  日期：2010.2

  Synthetic routes to four calix[4]arene stereoisomers with two distal methoxycarboxy groups and two distal butoxy groups are reported. Conformations of cone, partial cone (butyl up), partial cone (acid up), and 1,3-alternate were established by 1H and 13C-NMR spectroscopy. To probe the influence of ligand conformation on metal ion complexation, extractions from aqueous solutions into 1,2-dichloroethane were performed. These included competitive alkali metal cation extractions, competitive alkaline earth metal cation extractions, and single species extractions of Pb2+ and of Hg2+. Comparisons are also made with the results for a conformationally mobile analogue in which the two butoxy groups are replaced with methoxy groups.

  报告了具有两个远端甲氧基羧基和两个远端丁氧基的四种钙[4]炔立体异构体的合成路线。通过 1H 和 13C-NMR 光谱确定了锥形、部分锥形（丁基向上）、部分锥形（酸向上）和 1,3- 异构体的构象。为了探究配体构象对金属离子络合的影响，我们从水溶液中萃取了 1,2-二氯乙烷。其中包括竞争性碱金属阳离子萃取、竞争性碱土金属阳离子萃取以及 Pb2+ 和 Hg2+ 的单种萃取。此外，还与一种构象移动性类似物的结果进行了比较，该类似物中的两个丁氧基被甲氧基取代。
• Electroactive Organic Molecules Immobilized onto Solid Nanoparticles as a Cathode Material for Lithium-Ion Batteries
  作者：Bostjan Genorio、Klemen Pirnat、Romana Cerc-Korosec、Robert Dominko、Miran Gaberscek

  DOI：10.1002/anie.201001539

  日期：——

  Active monomers: Grafting soluble organic molecules onto insoluble, high‐surface‐area substrates, e.g. calixquinones on nanoparticles (see pciture), allows the production of a wide range of very stable materials for lithium‐ion battery applications. Immobilization of the organic molecules avoids the problem of dissolution, which has previously led to performance degradation.

  活性单体：将可溶性有机分子接枝到不溶的高表面积基质上，例如纳米颗粒上的杯醌（请参阅pciture），可以生产出非常稳定的锂离子电池应用材料。有机分子的固定避免了溶解问题，该问题以前已导致性能下降。
• Self-Assembled Monolayer of a Redox-Active Calix[4]arene:  Voltammetric Recognition of the Ba²⁺ Ion in Aqueous Media
  作者：Taek Dong Chung、Jongseo Park、Jandee Kim、Hyunchang Lim、Mi-Jung Choi、Joo Ryun Kim、Suk-Kyu Chang、Hasuck Kim

  DOI：10.1021/ac001050p

  日期：2001.8.1

  The Redox-active monolayer of a novel calix[4]arene recognizing redox-inactive ionic species by voltammetry is reported. Calix[4]arene-disulfide-diquinone, which is not only redox-active but is also a highly selective ionophore for the Ba2+ ion, spontaneously forms a stable and dense monolayer film on gold. The redox-active calixarene monolayer selectively recognizes Ba2+ ion in aqueous media, and

  报道了一种新的杯[4]芳烃的氧化还原活性单层，通过伏安法识别氧化还原惰性离子。杯[4]芳烃-二硫键-二醌，不仅具有氧化还原活性，而且还是Ba2 +离子的高度选择性离子载体，自发地在金上形成稳定且致密的单层膜。氧化还原活性杯芳烃单层选择性识别水性介质中的Ba2 +离子，伏安信号与离子浓度成正比。通过添加浓度低至1.0 x 10（-6）M的含Ba2 +离子的稀溶液，可以通过方波伏安法检测到一个新的伏安峰。Langmuir图（1 / ip对1 / [Ba2 +]）显示线性斜率在1.0 x 10（-6）M到1.0 x 10（-4）M的范围内。除Sr2 +和Ca2 +外，此修饰电极对碱金属和碱土金属离子均无明显干扰。分别只有100倍和500倍浓度的Sr2 +和Ca2 +离子可导致与Ba2 +相当的伏安响应。
• Inclusion of Organic Cations by Calix[4]arenes Bearing Cyclohepta-2,4,6-trienyl Substituents
  作者：Marzena Orda-Zgadzaj、Volker Wendel、Matthias Fehlinger、Burkhard Ziemer、Werner Abraham

  DOI：10.1002/1099-0690(200104)2001:8<1549::aid-ejoc1549>3.0.co;2-x

  日期：2001.4

  Only very weak complexation of organic cations such as ammonium and iminium ions by simple calix[4]arenes has been reported to date. Newly designed calix[4]arenes, substituted with a different number of 1,3,5-cycloheptatrien-7-yl functions at the upper rim. can engender an improvement in the inclusion capability, due to an enlargement of the Jr-basic wall of the host cavity. The complexation capability of these calix[4]arenes for organic cations is studied in this paper, For the first time, aryl tropylium salts have been used as cationic guests in addition to ammonium and iminium salts. Three structural types of hosts can be distinguished, all of which exhibit remarkably different inclusion abilities towards the organic cations, Flexible hosts with an OK-unmodified lower rim undergoing ring inversion form complexes of modest stability, provided that the host lacks bulky tert-butyl substituents at the upper rim. Tetra-O-alkylated derivatives, which are assumed to exhibit a flexible cone conformation, do not bind organic cations. Among the calix[4]arenes bearing cycloheptatrienyl groups, the complexation requirements are best matched by hosts with four cycloheptatrienyl groups on the upper rim and two alkyl groups on the lower rim; these compounds are assumed to possess a more rigid cone conformation, due to intramolecular hydrogen bonds. The tropylium component of phenyl tropylium ions penetrates inside the pi -basic cavity of the host. The absorption coefficient of the longest wavelength absorption band of these guests in the visible region is drastically lessened upon inclusion.