5,11,17,23-Tetra-p-tert-butyl-25,27-bis<(cyanopropyl)oxy>-26,28-dihydroxycalix<4>arene | 166804-10-0

• 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-p-tert-butyl-25,27-bis<(cyanopropyl)oxy>-26,28-dihydroxycalix<4>arene
• 英文别名: 5,11,17,23-tetra-tert-butyl-25,27-bis(3-cyanopropyloxy)-26,28-dihydroxy calix[4]arene；(CH2(C6H2)(t-Bu))4(O(CH2)3CN)2(OH)2；4-[[5,11,17,23-Tetratert-butyl-27-(3-cyanopropoxy)-26,28-dihydroxy-25-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-dodecaenyl]oxy]butanenitrile
• CAS: 166804-10-0
• 化学式: C₅₂H₆₆N₂O₄
• 分子量: 783.107
• InChiKey: CMWCKYTVVXFPAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.7
• 重原子数：
  58
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  107
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,11,17,23-Tetra-p-tert-butyl-25,27-bis<(cyanopropyl)oxy>-26,28-dihydroxycalix<4>arene 在 sodium tetrahydroborate 、 sodium hydride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 47.0h， 生成 5,11,17,23-Tetra-p-tert-butyl-25,26,27,28-tetrakis<(aminobutyl)oxy>calix<4>arene
  参考文献：
  名称：

  Topomimetics of Amphipathic β-Sheet and Helix-Forming Bactericidal Peptides Neutralize Lipopolysaccharide Endotoxins

  摘要：

  Release of lipopolysaccharide (LPS) endotoxin from Gram negative bacterial membranes triggers macrophages to produce large quantities of cytokines that can lead to septic shock and eventual death. Agents that bind to and neutralize LPS may provide a means to clinically prevent septic shock upon bacterial infection. Previously, we reported the design of antibacterial helix peptide SC4 and beta-sheet-forming beta pep peptides that neutralize LPS in vitro. We hypothesized that the ability of these and other such peptides to neutralize LPS rested in the common denominator of positively charged amphipathic structure. Here, we describe the design and synthesis of nonpeptide, calixarene-based helix/sheet topomimetics that mimic the folded conformations of these peptides in their molecular dimensions, amphipathic surface topology, and compositional properties. From a small library of topomimetics, we identified several compounds that neutralize LPS in the 10(-8) M range, making them as effective as bactericidal/permeability increasing protein and polymyxin B. In an endotoxemia mouse model, three of the most in vitro effective topomimetics are shown to be at least partially protective against challenges of LPS from different bacterial species. NMR studies provide mechanistic insight by suggesting the site of molecular interaction between topomimetics and the lipid A component of LPS, with binding being mediated by electrostatic and hydrophobic interactions. This research contributes to the development of pharmaceutical agents against endotoxemia and septic shock.

  DOI：

  10.1021/jm0610447
• 作为产物：
  描述：

  4-溴丁腈 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 17.0h， 以91%的产率得到5,11,17,23-Tetra-p-tert-butyl-25,27-bis<(cyanopropyl)oxy>-26,28-dihydroxycalix<4>arene
  参考文献：
  名称：

  [EN] CALIXARENE-BASED PEPTIDE CONFORMATION MIMETICS, METHODS OF USE, AND METHODS OF MAKING
  [FR] MIMETIQUES A CONFORMATION PEPTIDIQUE A BASE DE CALIXARENE, PROCEDES D'UTILISATION, ET PROCEDES D'ELABORATION

  摘要：

  公开号：

  WO2006042104A3

文献信息

• First Synthesis and Structure of β-Ketoimine Calix[4]arenes: Complexation and Extraction Studies
  作者：Hatem Halouani、Isabelle Dumazet-Bonnamour、Monique Perrin、Roger Lamartine

  DOI：10.1021/jo0495485

  日期：2004.10.1

  β-ketoimine calix[4]arene derivatives is described. The reaction of calix[4]arene or p-tert-butylcalix[4]arene with bromoacetonitrile or bromobutyronitrile afforded di-, tri-, and tetranitrile calixarene derivatives (3−8, 3a), which were then reduced into the corresponding amine (9−13, 3b). The condensation of these aminocalixarenes with acetylacetone led to six β-ketoimine calix[4]arene derivatives (14−18

  描述了一系列新的β-酮亚胺杯[4]芳烃衍生物的合成。杯的反应[4]芳烃或p -叔-butylcalix [4]芳烃与溴乙腈或溴丁腈，得到二- ，三- ，和四腈杯芳烃衍生物（3 - 8，图3a），然后将其还原成相应的胺（9 - 13，图3b）。这些aminocalixarenes与乙酰丙酮的缩合导致6β酮亚胺杯[4]芳烃衍生物（14 - 18，图3c），为类朝向过渡金属选择性受体。分子结构4，通过X射线衍射确定了图7和图17。17的堆积揭示了分子内和分子间氢键的网络。受体的络合性能15，17，和图3c朝向不同的金属离子已被通过在有机介质中的UV-vis滴定研究。通过摩尔比法和Job图确定了具有17的配合物的化学计量。这些新颖的受体选择性地复合Cu 2 +，Hg 2+和Ag +。而且17的萃取性能通过液-液萃取和原子吸收光谱研究了对阳离子的反应。化合物17对Pb 2+具有良好的亲和性和选择性。
• 1,3-Alternate calix[4]arenes, selectively functionalized by amino groups
  作者：Crenguta Danila、Michael Bolte、Volker Böhmer

  DOI：10.1039/b414173c

  日期：——

  synthesize calix[4]arenes which are fixed in the 1,3-alternate conformation and substituted selectively by amino groups. These derivatives are useful starting materials for the attachment of various groups via amide bonds, as demonstrated by several examples, but may be converted also to ureas, imides or azomethines. Four amino groups may be attached to the narrow rim via(several) methylene groups as spacer

  描述了合成杯盖[4]芳烃的一般策略，这些芳烃固定在1,3-交替构象中并被氨基选择性取代。这些衍生物是有用的起始原料，用于通过酰胺键连接各种基团，如几个实例所示，但也可以转化为脲，酰亚胺或偶氮甲碱。四个氨基可以通过（几个）亚甲基作为间隔基通过ω-溴邻苯二甲酰亚胺或ω-溴腈的O-烷基化连接到狭窄的边缘。从所得的四醚中，通过用肼裂解或通过水解获得氨基官能团，从而允许分子两侧的选择性官能化（酚单元A，C相对于B，D）。通过各自的叔丁基杯[4]芳烃衍生物的ipso-硝化和随后的还原反应，在宽边缘引入氨基官能团。1,3-二醚的选择性ipis硝化，然后用烯丙基溴进行O-烷基化，得到1,3-交替构象的四醚，烯丙基和硝基的氢化（一步），氨基的保护作用如下：邻苯二甲酰亚胺，然后剩余的叔丁基苯酚环进行异丙基硝化，可以再次区分分子的两面（A，C与B，D单元）。Boc-酸酐使宽边四胺以1,3-交替构型与Boc-酸酐
• Synthesis and cation complexation of p-tert-butyl-calix[4]arene bearing two 8-hydroxyquinoline units
  作者：Slim Mannai、Lasâad Dammak、Lassaad Baklouti、Abdelwaheb Hamdi

  DOI：10.1007/s10847-019-00909-7

  日期：2019.8.15

  A new p-tert-butyl-calix[4]arene receptor containing two 8-hydroxyquinoline unit was prepared and its complexing properties toward lanthanides ions were investigated in acetonitrile by means of UV/vis spectrophotometry and conductivity methods. The stoichiometry of the formed complexes and their stability constants were also determined.

  制备了一种新的含有两个8-羟基喹啉单元的对叔丁基杯[4]芳烃受体，并通过紫外/可见分光光度法和电导率方法在乙腈中研究了其对镧系元素离子的络合性能。还测定了形成的复合物的化学计量及其稳定性常数。
• Enantioselective recognition of amino acids by chiral peptido-calix[4]arenes and thiacalix[4]arenes
  作者：Joackim Bois、Isabelle Bonnamour、Christian Duchamp、Helene Parrot-Lopez、Ulrich Darbost、Caroline Felix

  DOI：10.1039/b907190c

  日期：——

  In order to prepare new molecular hosts able to discriminate enantiomers of amino-acid derivatives, we have synthesized chiral thiacalix[4]arenes. Extensive studies using NMR and mass spectrometry techniques allow us to determine the major supramolecular interactions involved in the recognition process. Moreover, a titration study enables us to determine the binding constant between these new hosts and a series of amino-acid derivatives. Finally, we have also demonstrated that these calixarenes are able to discriminate enantiomers of amino-acid guests.

  为了制备能够区分氨基酸衍生物对映体的新分子宿主，我们合成了手性硫杂[4]烷。通过对核磁共振和质谱技术的广泛研究，我们确定了识别过程中涉及的主要超分子相互作用。此外，通过滴定研究，我们还确定了这些新宿主与一系列氨基酸衍生物之间的结合常数。最后，我们还证明了这些钙钛矿能够区分氨基酸客体的对映体。
• Dihomooxacalix[4]arene-Based Fluorescent Receptors for Anion and Organic Ion Pair Recognition
  作者：Alexandre S. Miranda、Paula M. Marcos、José R. Ascenso、Mário N. Berberan-Santos、Rachel Schurhammer、Neal Hickey、Silvano Geremia

  DOI：10.3390/molecules25204708

  日期：——

  Fluorescent dihomooxacalix[4]arene-based receptors 5a–5c, bearing two naphthyl(thio)ureido groups at the lower rim via a butyl spacer, were synthesised and obtained in the cone conformation in solution. The X-ray crystal structures of 1,3- (5a) and 3,4-dinaphthylurea (5b) derivatives are reported. Their binding properties towards several anions of different geometries were assessed by 1H-NMR, UV-Vis

  合成并在溶液中以锥形构象获得荧光二高氧杂杯[4]芳烃受体 5a-5c，通过丁基间隔在下缘带有两个萘基（硫代）脲基。报道了 1,3- (5a) 和 3,4-二萘脲 (5b) 衍生物的 X 射线晶体结构。它们对几种不同几何形状的阴离子的结合特性通过 1H-NMR、UV-Vis 吸收和荧光滴定进行评估。还使用量子力学计算获得了萘脲 5a 和 5b 复合物的结构和能量见解。数据显示所有受体都遵循相同的趋势，结合常数随着阴离子碱度的增加而增加，与 F- 获得最强的复合物，其次是含氧阴离子 AcO- 和 BzO-。与远端尿素 5a 相比，近端尿素 5b 是更好的阴离子受体，并且两者都比硫脲 5c 更有效。还研究了化合物 5a 和 5b 作为生物相关烷基铵盐的异源受体，例如神经递质 γ-氨基丁酸 (GABA·HCl) 和甜菜碱脱氧肉碱·HCl。还测试了对客体仲丁胺·HCl 的手性识别，显示了对 (R)-sec-BuNH3+·Cl-