25,27-bis(3-bromobutoxy)-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene | 444004-67-5

• 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-bromobutoxy)-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene
• 英文别名: 5,11,17,23-tetra-t-butyl-25,27-di(2-bromobutyl)-26,28-dihydroxycalix[4]arene；25,27-bis(4-bromobutoxy)-26,28-dihydroxy-5,11,17,23-tetra-(tert-butyl)calix[4]arene；1,3-bis(4-bromobutoxy)-p-tert-butyl-calix[4]arene；(1,3)-cone-5,11,17,23-tetra-t-butyl-25,27-dihydroxy-26,28-bis-(4-bromobutoxy)-calix[4]arene；1,3-bis-(butoxy-4-bromide)-tetrakis-p-tert-butylcalix[4]arene；tert-butylcalix[4]arene-1,3-bis(4-bromobutyl) ether；1,3-butyldibromo p-tert-butylcalix[4]arene；26,28-Bis(4-bromobutoxy)-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: 444004-67-5
• 化学式: C₅₂H₇₀Br₂O₄
• 分子量: 918.933
• InChiKey: HFOWVSDWOBVPAM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.6
• 重原子数：
  58
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  25,27-bis(3-bromobutoxy)-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene 在 titanium(IV) chloride tetrahydrofuran 、 盐酸 、 水 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以85%的产率得到5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxy-25-(4-bromobutyloxy)calix[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：

  4-叔丁基苯酚 在 potassium carbonate 、 sodium hydroxide 作用下， 以 丙酮 为溶剂， 反应 96.0h， 生成 25,27-bis(3-bromobutoxy)-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene
  参考文献：
  名称：

  紫罗兰-葫芦脲主/客体化学——二聚化与包合的氧化还原控制

  摘要：

  两个杯[4]芳烃系统，C23 4+和C24 4+ ——其中 2 对应于紫精单元的数量，3-4 对应于将紫精单元连接到大环核心的碳原子数——已经合成并导致与CB[7]或CB[8]结合时形成 [3] 假轮烷。由于两个面对面紫罗碱自由基阳离子的分子内二聚化，[3] 假轮烷在联吡啶鎓单元还原时自发解离。基于CB[7]和CB[8]的 [2] 假轮烷，含有单体紫罗碱客体模型化合物，MC3 2+和MC4+，在其联吡啶鎓单元的电化学还原后不会发生解络合和二聚化。

  DOI：

  10.1039/d1ra05488k

文献信息

• Synthesis of Distally Substituted Calix[4]arene Dialkyl Ethers in High Yield
  作者：Lakhbeer Singh Arora、Har Mohindra Chawla、Mohammad Shahid、Nalin Pant

  DOI：10.1080/00304948.2017.1320903

  日期：2017.5.4

  and bridged alkyl calix[4]arenes (VIII and IX) depending upon the base and the amount of alkyl halide used. The process often runs into low yield, no reaction, multiple product formation or change in the conformation of starting calixarenes. There is need for a simple high yield protocol for etherification of calix[4]arenes without undergoing change in conformational characteristics. From amongst numerous

  杯[4]芳烃是大环环芳烃，在离子识别、传感、药物输送、纳米技术、自组装和催化等方面有着广泛的应用。它们具有四个酚-OH 基团，它们在环状阵列中参与强分子内氢键，以产生显着的疏水和亲水区域，称为杯 [4] 芳烃的上缘和下缘。可以修改这些站点以用于目标应用程序。下缘杯[4]芳烃羟基的选择性醚化是实现分子受体进行化学和生物识别的重要方法。由于杯芳烃羟基的 pKa 值范围很窄，当使用不同的碱作为催化剂时，它们的醚化作用通常会导致产物的混合物（图 1）。使用二卤代烷烃进行烷基化也可能导致双杯[4]芳烃（VI和VII）和桥接烷基杯[4]芳烃（VIII和IX），这取决于所使用的烷基卤化物的碱和量。该过程通常会遇到产率低、无反应、形成多种产物或起始杯芳烃构象发生变化的情况。需要一种简单的高产率方案用于杯 [4] 芳烃的醚化，而不会改变构象特征。在众多已知的获得醚的方法中，只有少数可用于杯[4]芳烃化学。许
• Self-Assembling Calix[4]arene [2]Catenanes. Preorganization, Conformation, Selectivity, and Efficiency
  作者：Zhan-Ting Li、Guo-Zhen Ji、Cheng-Xue Zhao、Shen-Dong Yuan、Hui Ding、Chen Huang、Ai-Lin Du、Ming Wei

  DOI：10.1021/jo9824100

  日期：1999.5.1

  [2]catenanes were investigated, which reveal that incorporation of calix[4]arene into the tetracationic cyclophane reduces pi-stacking interactions between the donor and acceptor units and catenation has substantial influence on conformational distributions of the calix[4]arene moiety. The results demonstrate the versatility of calix[4]arene derivatives as building blocks in the construction of supramolecular

  一类新型的预组织U形杯[4]芳烃裂口，指示盐3a，c，e.2Cl，3b.2PF（6）（）和3f.2Br，由一个圆锥杯[4]芳烃和两个通过脂肪族链连接的联吡啶残基已被设计和合成为利用水醌和联吡啶鎓单元之间的pi堆积相互作用自组装杯盖斯[4]亚芳基[2]邻苯二酚的前体。还研究了构型柔性的6.2PF（6）（）和圆锥10.2Cl（其构象由下缘的两个丙氧基固定），以研究杯形[4]芳烃部分的构象和氢键对自组装。对于所有反应，使用双对亚苯基-34-冠醚-10（11）作为供体组分。从掺入乙烯的3a的反应中，以8％的产率获得了交替的[2]环戊烷13.4Cl。2Cl和1，4-双（溴甲基）苯（12a）。通过掺丙烯的3b.PF（6）（）和3c.2Cl与12a，1,3-双（溴甲基）苯（12b）的反应，以中等至良好的产率获得了三个锥和一个构象柔性的[2]邻苯二酚。或4,4'-（溴甲基）联苯（12c）。圆锥和部分圆锥[
• Novel bis(phenylselenoalkoxy)calix[4]arene molecular tweezer receptors as sensors for ion-selective electrodes
  作者：Xianshun Zeng、Xuebing Leng、Langxing Chen、Hao Sun、Fengbo Xu、Qingshan Li、Xiwen He、Zheng-Zhi Zhang

  DOI：10.1039/b109238c

  日期：2002.3.25

  Four tweezer-like 25,27-dihydroxy-26,28-bis(phenylselenoalkoxy)-5,11,17,23-tetra-tert-butylcalix[4]arenes 5–8 were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes (ISEs). For investigation of the influences of the coordinate atoms on the ion-selectivity, 25,27-dihydroxy-26,28-bis(alkylthiaalkoxy)-5,11,17,23-tetra-tert-butylcalix[4]arenes 9–11 were also prepared and characterized. On the other hand, 1,3-bis(phenylseleno)propane 12 was synthesized for comparison of the influences of coordinate patterns of different ionophores on the ion-selectivity of ISEs. ISEs based on 5–12 as neutral ionophores were prepared, and their selectivity coefficients for Ag+ (log KpotAg,M) were investigated against alkali metal, alkaline-earth metal, lead, and ammonium ions and some transition metal ions using the fixed interference method (FIM). These ISEs showed excellent Ag+ selectivity over most of the interfering cations examined, except for Hg2+, which had relatively smaller interference (log KpotAg,Hg ≤ −1.6).

  合成了四种类似镊子的25,27-二羟基-26,28-双(苯基硒烯氧基)-5,11,17,23-四-tert-丁基环四烯 5–8，用于评估其在离子选择性电极（ISEs）中的离子选择性。为了研究配位原子对离子选择性的影响，还合成并表征了25,27-二羟基-26,28-双(烷基硫醇烯氧基)-5,11,17,23-四-tert-丁基环四烯 9–11。另一方面，合成了1,3-双(苯基硒烯)丙烷 12，以比较不同离子载体的配位模式对ISEs离子选择性的影响。以5–12为中性离子载体的ISEs被制备，并使用固定干扰法（FIM）研究了其对Ag+的选择性系数（log KpotAg,M），与碱金属、碱土金属、铅、铵离子以及一些过渡金属离子进行比较。这些ISEs在大多数干扰阳离子中表现出优异的Ag+选择性，除了Hg2+，其干扰相对较小（log KpotAg,Hg ≤ −1.6）。
• Anion complexation. A ditriphenylphosphonium calix[4]arene derivative as a novel receptor for anions
  作者：Abdelwaheb Hamdi、Kye Chun Nam、Byung Ju Ryu、Jong Seung Kim、Jacques Vicens

  DOI：10.1016/j.tetlet.2004.04.133

  日期：2004.6

  A novel anionic receptor 2 consisting of a calix[4]arene bearing two alkytriphenylphosphonium has been prepared by two different procedures. The complexation occurred at the phosphonium sites probably due to electrostatic and/or π-anion forces.

  通过两种不同的方法制备了由带有两个烷基三苯基phosph的杯[4]芳烃组成的新型阴离子受体2。络合发生在the位点可能是由于静电力和/或π阴离子力引起的。
• Calix[4]arenes Substituted on the Narrow Rim with Malononitrile and Cobalt Bis(dicarbollide) Anion
  作者：Volker Böhmer、Junmei Zhao、Michael Bolte、Crenguţa Dordea、Bohumir Grüner

  DOI：10.1055/s-0029-1217061

  日期：2009.12

  Nitrile groups are suitable precursors for amino functions to which various other groups can be attached. Thus, the reaction of the 1,3-bis(3-bromopropyl ether) or 1,3-bis(4-bromobutyl ether) of tert-butylcalix[4]arene with methylmalononitrile has been studied in order to attach four nitrile groups to the narrow rim. Bimacrocyclic dinitriles were formed in 70% yield with malononitrile, and tetranitriles in 85% yield with methylmalononitrile. Subsequent alkylation of the tetranitriles with cobalt dioxane-bis(dicarbollide) gave dianionic calix[4]arenes, isolated as the cesium salts in 68% and 89% yield. Two compounds were characterized by single crystal X-ray analysis.

  腈基是适合用于氨基功能的前体，可以附加各种其它基团。因此，研究了叔丁基杯[4]芳烃的1,3-双(3-溴丙基醚)或1,3-双(4-溴丁基醚)与美克酸腈的反应，以便将四个腈基附加到狭边缘。与美克酸腈反应时，形成了70%收率的双宏环二腈，与美克酸腈反应时，形成了85%收率的四腈。随后，将四腈与钴二噁烷-双(二碳烯)进行烷基化反应，得到的二阴离子杯[4]芳烃以68%和89%的收率分离为铯盐。有两个化合物通过单晶X射线分析进行了表征。