5,17-diamino-25,26,27,28-tetrakis(ethoxycarbonyl)methoxycalix[4]arene | 156874-48-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5,17-diamino-25,26,27,28-tetrakis(ethoxycarbonyl)methoxycalix[4]arene
• 英文别名: Ethyl 2-[[5,17-diamino-26,27,28-tris(2-ethoxy-2-oxoethoxy)-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
• CAS: 156874-48-5；180322-57-0
• 化学式: C₄₄H₅₀N₂O₁₂
• 分子量: 798.887
• InChiKey: FPMGLSPTHLQEBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  58
• 可旋转键数：
  20
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  194
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  5,17-diamino-25,26,27,28-tetrakis(ethoxycarbonyl)methoxycalix[4]arene 在 三乙胺 作用下， 以 氯仿 、 甲苯 为溶剂， 反应 6.0h， 生成 Ethyl 2-[[26,27,28-tris(2-ethoxy-2-oxoethoxy)-5,17-bis(phenylcarbamoylamino)-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：

  The Pinched Cone Conformation of Calix[4]arenes:  Noncovalent Rigidification of the Calix[4]arene Skeleton

  摘要：

  Calix[4]arenes at the upper rim substituted with two (thio)urea moieties, 2a-c and 4, or substituted with two acetamido groups, 5, adopt a pinched cone conformation in CDCl3 solution. The pinched cone conformation is the result of diametrical, intramolecular hydrogen bonds and was studied by H-1 NMR dilution and variable-temperature experiments, NOESY spectroscopy, and FTIR experiments. The pinched cone conformation in these novel calix[4]arenes is stable in C2D2Cl4 up to at least 120 degrees C. The bis(ureido)calix[4]arenes 2b,c give a hydrogen-bonded dimer in the pinched cone conformation.

  DOI：

  10.1021/jo9600262
• 作为产物：
  描述：

  25,27-bis[(ethoxycarbonyl)methoxy]-26,28-dihydroxycalix[4]arene 在 镍 盐酸 、 sodium nitrate 、 sodium carbonate 、 一水合肼 、 lanthanum(III) nitrate 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 8.0h， 生成 5,17-diamino-25,26,27,28-tetrakis(ethoxycarbonyl)methoxycalix[4]arene
  参考文献：
  名称：

  含有二茂铁酰胺作为羧酸根阴离子受体和传感器的杯[4]芳烃。

  摘要：

  合成了杯状[4]芳烃衍生物，其在宽边缘含有酰胺二茂铁单元，在窄边缘含有乙基酯基，L1-L3，并研究了它们的阴离子结合和传感性能。从（1）H NMR滴定中发现，L1-L3能够选择性地与羧酸根阴离子结合。此外，循环伏安法和方波伏安法表明，L1-L3可以作为羧酸根阴离子的电化学传感器。[结构：见文字]

  DOI：

  10.1021/ol034355+

文献信息

• Calix[4]arene-porphyrin Conjugates as Versatile Molecular Receptors for Anions
  作者：Miroslav Dudič、Pavel Lhoták、Ivan Stibor、Kamil Lang、Petra Prošková

  DOI：10.1021/ol027175t

  日期：2003.1.1

  see text] Appending tetraphenylporphyrin units to the calix[4]arene skeleton via the ureido function leads to novel anion receptors designed for anion and/or cation detection by UV-vis spectroscopy. Calixarenes in the cone or 1,3-alternate conformations bearing two ureido moieties on the upper rim represent well-preorganized cavities where the anion can be held by synchronous hydrogen bonding interaction

  [结构：见正文]通过脲基官能团将四苯基卟啉单元附加到杯[4]芳烃骨架上，可得到新颖的阴离子受体，该受体设计用于通过紫外-可见光谱检测阴离子和/或阳离子。在上边缘带有两个脲基部分的圆锥形或1,3-交替构型的杯芳烃代表预先组装好的空腔，在该空腔中，阴离子可通过与NH基团的同步氢键相互作用而保持阴离子。
• Synthesis of Novel Macrocyclic Peptido-calix[4]arenes and Peptidopyridines as Precursors for Potential Molecular Metallacages, Chemosensors and Biologically Active Candidates
  作者：Abd El-Galil El-Sayed Amr、Mohamed Abo-Ghalia、Mohamed M. Abdalah

  DOI：10.1515/znb-2006-1104

  日期：2006.11.1

  Novel macrocyclic dipicolinic acid acylated peptides based on upper rim bridged peptidocalix[ 4]arenes, peptido-pyridines or hybrid structures of both, were synthesized as potential molecular metallacages and chemosensors. While conventional azide or mixed anhydride (ethyl chloroformate) peptide couplings served well for assembling the L-tyrosine or L-ornithine peptide backbones, the acid chloride of pyridine-2,6-dicarboxylic acid (dipicolinic acid) acid served as the complementary acylating agent. The structure assignment of the new compounds was based on chemical and spectroscopic evidences. Some of these compounds exhibit antimicrobial activities.

  基于上缘桥联的肽联四醚，肽-吡啶或两者混合结构的新型大环二吡啯酸酰化肽被合成为潜在的分子金属笼和化学传感器。传统的叠氮或混合酸酐（氯甲酸乙酯）肽偶联反应可用于组装L-酪氨酸或L-鸟氨酸肽骨架，而吡啶-2,6-二羧酸（二吡啯酸）的酸氯化物则用作补充酰化试剂。新化合物的结构鉴定基于化学和光谱证据。其中一些化合物表现出抗菌活性。
• Synthesis of Some New Chiral Tricyclic and Macrocyclic Pyridine Derivatives as Antimicrobial Agents
  作者：Abd El-Galil E. Amr、Ashraf M. Mohamed、Alhussein A. Ibrahim

  DOI：10.1515/znb-2003-0908

  日期：2003.9.1

  A series of chiral macrocyclic pyridines has been prepared starting from N²,N²-(pyridine- 2,6-dicarbonyl)diamino acid hydrazides (2a-c) and N,N-bis-(1-carboxy-2-substituted)-2,6- diaminocarbonyl)pyridines (3a,b). The coupling of (2a-c) with 2,6-pyridine dicarbonyldichloride (4) gave the compounds (5a-c). Compounds 2a-c were coupled with 2,6-diacetylpyridine (6) to yield compounds (7a-c) and with heterocyclic aldehydes (8) or (10) to give the compounds (9a-c) or (11a-c). In addition, the hydrazides (2a-c) were reacted with diformylcalix[4]arene 12 to afford the macrocyclic calix[4]arene hydrazone derivatives (13a-c) in reasonable yields. Finally, reaction of diaminocalix-[4]arene derivatives (14a,b) with hydrazides 2a,b or acids (3a,b), using azide or mixed anhydride methods afforded macrocyclic calix[4]arene derivatives 15a,b and 16a,b, respectively. The structure assignments of the new compounds are based on chemical and spectroscopic evidence. The biological activity screening tests showed that many of the obtained compounds exhibit high antimicrobial activity comparable to ampicillin and chloramphenicol which are used as reference compounds.

  一系列手性大环吡啶化合物是从N^2,N^2-(吡啶-2,6-二羧基)二氨基酸脒酰肼（2a-c）和N,N-双-(1-羧基-2-取代基)-2,6-二氨基羧基）吡啶（3a,b）出发制备的。将（2a-c）与2,6-吡啶二羧酰二氯化物（4）偶联得到化合物（5a-c）。将化合物2a-c与2,6-二乙酰基吡啶（6）偶联得到化合物（7a-c），与杂环醛（8）或（10）偶联得到化合物（9a-c）或（11a-c）。此外，将脒酰肼（2a-c）与二甲酰基杯[4]芳烃12反应，以合理产率得到大环杯[4]芳烃脒肼衍生物（13a-c）。最后，将二氨基杯[4]芳烃衍生物（14a,b）与脒酰肼2a,b或酸（3a,b）反应，使用叠氮化物或混合酐方法得到大环杯[4]芳烃衍生物15a,b和16a,b，分别。这些新化合物的结构鉴定基于化学和光谱证据。生物活性筛选测试显示，许多获得的化合物表现出高抗菌活性，与作为参考化合物的氨苄青霉素和氯霉素相媲美。
• Lower rim tetra-substituted and upper rim ferrocene amide calix[4]arenes: synthesis, conformation and anion-binding properties
  作者：Boosayarat Tomapatanaget、Thawatchai Tuntulani

  DOI：10.1016/s0040-4039(01)01722-1

  日期：2001.11

  Calix[4]arenes containing ferrocene amide at the upper rim and methoxy or ethoxycarbonylmethoxy (ethyl ester) groups at the lower rim (5a, 5b and 5c) have been synthesized. It was found that tetramethoxy 5a and dimethoxy diethyl ester 5c were conformationally labile and existed in both cone and partial cone conformation in solution. Anion-binding studies by 1H NMR titration in CDCl3 showed that 5b

  已经合成了在上边缘含有二茂铁酰胺并且在下边缘（5a，5b和5c）含有甲氧基或乙氧基羰基甲氧基（乙酯）基团的杯[4]芳烃。发现四甲氧基5a和二甲氧基二乙酯5c在构象上不稳定，并且在溶液中以锥和部分锥构型存在。阴离子结合由研究1个在CDCl 1 H NMR滴定3表明图5B的约束氯-选择性地与高稳定性。化合物5c中形成有Cl络合物-和H 2 PO 4 -前者更稳定。锥体在化合物局部锥形构象的比例5a中被发现在结合氯降低-和H 2 PO 4 -和在极性溶剂中。
• Calix[4]arene Salenes: A Bifunctional Receptor for NaH2PO4
  作者：Dmitry M. Rudkevich、Willem Verboom、David N. Reinhoudt

  DOI：10.1021/jo00092a031

  日期：1994.7