25,27-bis(3-aminopropoxy)-5,11,17,23-tetra-tert-butyl-26,28-dihydroxycalix[4]arene | 182864-30-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 25,27-bis(3-aminopropoxy)-5,11,17,23-tetra-tert-butyl-26,28-dihydroxycalix[4]arene
• 英文别名: 26,28-Bis(3-aminopropoxy)-5,11,17,23-tetratert-butylpentacyclo[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
• CAS: 182864-30-8
• 化学式: C₅₀H₇₀N₂O₄
• 分子量: 763.117
• InChiKey: HLLDHUNYRRDDAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.4
• 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：
  111
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  25,27-bis(3-aminopropoxy)-5,11,17,23-tetra-tert-butyl-26,28-dihydroxycalix[4]arene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  杯形芳烃基带有不同受体位点的炔基烷基铂（II）吡啶吡啶配合物的合成和光物理研究，用于阴离子的比色和发光传感

  摘要：

  一系列的单核和双核的铂（II）三联吡啶络合物与酰胺，sulfonamide-，和含尿素配体（1 - 9）已被成功地设计并合成，和它们的光物理和阴离子结合性质进行了研究。通过电子吸收，发射和1 H NMR光谱研究了配合物的阴离子结合特性。在与阴离子结合，所述双核配合物1 - 3表现出大的电子吸收和发射光谱的变化，而对于单核类似物4 - 6观察到更小的光谱变化。在双核配合物中观察到对不同阴离子有趣的比色反应1 - 3。发现双核配合物7 – 9对阴离子结合不敏感，这可能归因于配合物中存在分子内Pt·⋅·Pt相互作用和/或π–π堆积，从而导致阴离子结合亲和力降低。

  DOI：

  10.1002/chem.201503401
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,27-di(2-bromopropyl)-26,28-dihydroxycalix[4]arene 在 肼 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 25,27-bis(3-aminopropoxy)-5,11,17,23-tetra-tert-butyl-26,28-dihydroxycalix[4]arene
  参考文献：
  名称：

  新型抗糖尿病药物可重复使用杯[4]芳烃键合硅胶吸附剂的合成与表征

  摘要：

  一种新型的杯[4]芳烃键合硅胶（C4BS）是通过将杯[4]芳烃衍生物通过硫醇-烯工艺共价连接到硅胶上而制备的。通过傅里叶变换红外 (FTIR) 光谱、热重分析 (TGA)、元素分析 (CHN)、扫描电子显微镜 (SEM) 和表面积分析 (BET) 研究了C4BS的结构和性质。此外，通过使用紫外-可见光谱定量测量水溶液中的药物，研究了一些抗糖尿病药物对C4BS的结合亲和力。结果表明，C4BS与普通硅胶相比，在中性 pH 条件下与恩格列净、达格列净和利格列汀的结合具有更高的亲和力，而使用C4BS或普通硅胶均不能有效吸附盐酸二甲双胍。因此，C4BS可以作为一种有前途的粘合剂被引入，用于选择性吸附药物流出物中引用的抗糖尿病药物，同时可通过水/乙腈 (1:1) 萃取重复使用。

  DOI：

  10.1039/d2ra04530c
• 作为试剂：
  描述：

  对三氟甲基苯甲醛 、 环己酮 在 L-脯氨酸 、 25,27-bis(3-aminopropoxy)-5,11,17,23-tetra-tert-butyl-26,28-dihydroxycalix[4]arene 作用下， 以 正己烷 为溶剂， 反应 24.0h， 以95%的产率得到
  参考文献：
  名称：

  Proline–calixarene thiourea host–guest complex catalyzed enantioselective aldol reactions: from nonpolar solvents to the presence of water

  摘要：

  A proline-calix[4]arene thiourea host-guest complex catalyzed intermolecular aldol reaction of aromatic aldehydes with cyclohexanone has been developed. The anti-configured products were obtained in good yields and with high enantioselectivities. The reaction is proposed to work via a modified Houk-List model, where the carboxylate part of the praline constitutes as a supramolecular system with the thiourea. The outcome of the study indicates the influence of the calix[4]arene thiourea on both the reactivity and selectivity in a non-polar reaction medium, even in the presence of water at moderate temperatures. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.01.015

文献信息

• Synthesis of new chiral calix[4]arene thiourea derivatives for enantiomeric recognition of carboxylate anions
  作者：Selahattin Bozkurt、Mustafa Burak Turkmen、Cengiz Soykan

  DOI：10.1007/s10847-015-0579-7

  日期：2016.2

  thiourea derivatives has been reported. The enantioselectivity of chiral receptors was investigated by using UV–Vis spectroscopy. All the chiral calix[4]arene derivatives exhibited certain chiral recognition towards the enantiomers of α-hydroxy isovaleric acid (HIVA), mandelic acid (MA), 2-chloromandelic acid (2-ClMA) and N-Boc-alanine (N-BocAl). The receptors with hydrogen bonding sites and aromatic groups

  摘要 氨基酸和羧酸化合物的对映体识别研究具有重要意义，因为这些化合物是生物分子的基本组成部分。这些化合物的对映体识别和分离是超分子化学的主要课题之一，因为它们是生物分子的基本组成部分，并且其中一些已知具有有效的生物活性。本研究报道了新型手性杯[4]芳烃硫脲衍生物的合成。通过使用紫外-可见光谱研究了手性受体的对映选择性。所有手性杯[4]芳烃衍生物对α-羟基异戊酸(HIVA)、扁桃酸(MA)、2-氯扁桃酸(2-ClMA)和N-Boc-丙氨酸(N-觯）。具有氢键位点和芳族基团的受体显示出相当高的立体选择性。作为手性受体，杯[4]芳烃2-羟基-1,2二苯醚硫脲衍生物在25°C下对2-氯扁桃酸（高达KR/KS = 2.80）具有对映体区分能力。还从热力学的角度讨论了对客体的对映体识别能力。
• Calixarene-based highly efficient primary amine–thiourea organocatalysts for asymmetric Michael addition of aldehydes to nitrostyrenes
  作者：Mustafa Durmaz、Abdulkadir Sirit

  DOI：10.1080/10610278.2013.773331

  日期：2013.5.1

  The synthesis of calix[4]arene-based chiral bifunctional primary amine–thiourea catalysts has been described from p-tert-butylcalix[4]arene for the first time. The calix[4]arene-based catalysts were successfully applied to promote Michael addition of aldehydes with nitroalkenes affording preferentially the (R)- or (S)-adducts in high yields (up to 95%) and excellent enantioselectivities (up to 99%

  首次描述了从对叔丁基杯[4]芳烃合成基于杯[4]芳烃的手性双功能伯胺-硫脲催化剂。杯[4]芳烃基催化剂被成功应用于促进醛与硝基烯烃的迈克尔加成，优先提供（R）-或（S）-加合物的高产率（高达95%）和优异的对映选择性（高达99%） es）。
• Synthesis of new calix[4]arene derivatives and evaluation of their cytotoxic activity
  作者：Mehmet Oguz、Ayse Yildirim、Irem Mukaddes Durmus、Serdar Karakurt、Mustafa Yilmaz

  DOI：10.1007/s00044-021-02813-7

  日期：2022.1

  the dihydrazide (3a and 3b) and diamino propyl (6a and 6b) derivatives of p-tert-butylcalix[4]arene and calix[4]arene were synthesized. Then the L-proline methyl ester substituted chlorocyclopropenium was reacted with the calix[4]arene derivatives (3a, 3b, 6a, and 6b) at room temperature in CH2Cl2 to obtain calix[4]arene superbase derivatives (4a, 4b, 7a, and 7b) in 75%, 60%, 70%, and 55% yield, respectively

  Since calixarenes are more easily synthesized and functionalized than other supramolecules, they are compounds of interest in organic chemistry. In this study, the dihydrazide (3a and 3b) and diamino propyl (6a and 6b) derivatives of p-tert-butylcalix[4]arene and calix[4]arene were synthesized. Then the L-proline methyl ester substituted chlorocyclopropenium was reacted with the calix[4]arene derivatives
• A highly efficient solvent system containing functionalized diglycolamides and an ionic liquid for americium recovery from radioactive wastes
  作者：Arijit Sengupta、Prasanta K. Mohapatra、Mudassir Iqbal、Jurriaan Huskens、Willem Verboom

  DOI：10.1039/c2dt12364a

  日期：——

  Three room temperature ionic liquids (RTILs), viz. C4mim+·PF6−, C6mim+·PF6− and C8mim+·PF6−, were evaluated as diluents for the extraction of Am(III) by N,N,N′,N′-tetraoctyl diglycolamide (TODGA). At 3 M HNO3, the DAm-values by 0.01 M TODGA were found to be 102, 34 and 74 for C4mim+·PF6−, C6mim+·PF6− and C8mim+·PF6−, respectively. The extraction of Am(III) decreased with increasing feed acidity for all three diluents, indicating an ion exchange mechanism for the extraction. The stoichiometry of the extracted species suggested that two TODGA molecules were associated with Am(III) during the extraction for all three RTILs and the conditional extraction constants have been determined. The DM-values for different metal ions followed the order: 75 (Am(III)) > 30.7 (Pu(IV)) > 3.9 (Np(IV)) > 1.19 (Pu(VI)) > 0.52 (U(VI)) > 0.12 (Cs(I)) > 0.024 (Sr(II)). The distribution behaviour of Am(III) was also studied with a recently synthesized calix[4]arene-4DGA (C4DGA) extractant dissolved in C8mim+·PF6−. Using this extractant diluent combination, the DAm-value was 194 at 3 M HNO3 using 5 × 10−5 M C4DGA, suggesting a very high distribution coefficient at very low extractant concentrations. The stoichiometry of the extracted species containing Am was found to be 1 : 2 (M : L) in C8mim+·PF6−. The thermodynamics of the extraction was also studied for both extractants in C8mim+·PF6−. The use of RTILs gives rise to significantly improved extraction properties than the commonly used n-dodecane and an unusual increase in separation factor values was seen for the first time which can lead to selective separation of Am from wastes containing a mixture of U, Pu and Am.

  评估了三种室温离子液体（RTILs），即 C4mim+-PF6-、C6mim+-PF6- 和 C8mim+-PF6-，作为 N,N,N′,N′-四辛基二乙二醇酰胺（TODGA）萃取 Am(III)的稀释剂。在 3 M HNO3 条件下，0.01 M TODGA 对 C4mim+-PF6-、C6mim+-PF6- 和 C8mim+-PF6- 的 DAm 值分别为 102、34 和 74。在所有三种稀释剂中，Am(III)的萃取率随着进样酸度的增加而降低，这表明萃取过程中存在离子交换机制。萃取物的化学计量学表明，在所有三种 RTIL 的萃取过程中，都有两个 TODGA 分子与 Am(III) 结合，并确定了条件萃取常数。不同金属离子的 DM 值依次为75 (Am(III))> 30.7（Pu(IV)> 3.9 （Np(IV)1.19 (Pu(VI)) > 0.52 (U(VI))> 0.52（U(VI)> 0.12（铯（I）>0.024（Sr(II)）。我们还利用最近合成的溶于 C8mim+-PF6- 的钙[4]炔-4DGA（C4DGA）萃取剂研究了 Am(III) 的分布行为。使用这种萃取剂稀释剂组合，在3 M 中使用5 × 10-5 M C4DGA时，DAm值为194，这表明在萃取剂浓度很低的情况下，分布系数非常高。在 C8mim+-PF6- 中，含有 Am 的萃取物的化学计量为 1 : 2 (M : L)。还研究了 C8mim+-PF6- 中两种萃取剂的萃取热力学。与常用的正十二烷相比，RTILs 的使用大大提高了萃取性能，分离因子值也首次出现了不寻常的增长，从而可以从含有铀、钚和镅混合物的废物中选择性地分离出镅。
• Pyrazine-functionalized calix[4]arenes: synthesis by palladium-catalyzed cross-coupling with phosphorus pronucleophiles and metal ion extraction properties
  作者：Nicolai I. Nikishkin、Jurriaan Huskens、Seraj A. Ansari、Prasanta K. Mohapatra、Willem Verboom

  DOI：10.1039/c2nj40791d

  日期：——

  A series of pyrazine-based calix[4]arene extractants was prepared by a stepwise functionalization, comprising palladium-catalyzed exhaustive cross-coupling of di- and tetrasubstituted calix[4]arenes bearing chloropyrazine moieties. The extraction behavior of the synthesized ligands was studied on Am–Eu mixtures under acidic feed conditions similar to those prevailing in nuclear wastes. Phosphorylpyrazine-bearing extractants exhibited a very high acid resistivity and a high affinity for americium giving D values as high as 794 at pH 1. The synergistic effect of the chlorinated cobalt bis(dicarbollide) anion [(B9C2H8Cl3)2Co]− (CCD-anion), as well as the effect of the calix[4]arene platform compared to monovalent ligands, was investigated. The presence of 1 mM CCD resulted in a 105 times increase in the D value.

  通过钯催化含有氯吡嗪分子的二取代和四取代钙[4]炔的穷举交叉偶联，采用逐步官能化的方法制备了一系列吡嗪基钙[4]炔萃取剂。在类似于核废料中普遍存在的酸性进料条件下，对合成配体在氨-铀混合物中的萃取行为进行了研究。含磷吡嗪的萃取剂表现出极高的耐酸性和对镅的高亲和性，在 pH 值为 1 时，D 值高达 794。 研究了氯化钴双二碳环阴离子[(B9C2H8Cl3)2Co]-（CCD 阴离子）的协同效应，以及钙[4]炔平台与单价配体相比的效应。1 mM CCD 的存在使 D 值增加了 105 倍。