5,11,17-Triformyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene | 136991-57-6

• 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-Triformyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
• 英文别名: 25,26,27,28-Tetrakis(2-ethoxyethoxy)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-dodecaene-5,11,17-tricarbaldehyde
• CAS: 136991-57-6
• 化学式: C₄₇H₅₆O₁₁
• 分子量: 796.955
• InChiKey: RDQFWFXJMPGUOA-UHFFFAOYSA-N

物化性质

• 沸点：
  918.9±65.0 °C(Predicted)
• 密度：
  1.160±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  58
• 可旋转键数：
  23
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  125
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  5,11,17-Triformyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene 在 palladium on activated charcoal 氢气 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 64.0h， 生成 5,11,17-tris<((6-hydroxymethyl)pyridin-2-yl-methyl)-N-methylaminomethyl>-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
  参考文献：
  名称：

  Dinuclear and Trinuclear Zn(II) Calix[4]arene Complexes as Models for Hydrolytic Metallo-Enzymes. Synthesis and Catalytic Activity in Phosphate Diester Transesterification

  摘要：

  Calix[4]arenes modified with two or three Zn(II)-2,6-bis(aminomethyl)pyridyl groups,. 3-[Zn](2) and (3)[Zn](3), respectively, were investigated as models for dinuclear and trinuclear metallo-enzymes that catalyze the cleavage of phosphate diesters. Under neutral conditions, 0.48 mM of 3-[Zn](2) causes a rate acceleration of 23 000 in the transesterification of the RNA model substrate 2-hydroxyproyl-p-nitrophenyl phosphate (HPNP, 0.19 mM). Comparison with the activities of a mononuclear complex 2-[Zn] and a reference complex lacking the calix[4]arene backbone 1-[Zn] shows that the catalysis is due to cooperative action of the Zn(II) centers and indicates that hydrophobic effects contribute to the catalysis. Saturation kinetics and pH variation studies demonstrate that the high catalytic activity of the flexible complex 3-[Zn](2) originates from a very high substrate binding affinity, affording a Michaelis-Menten complex in which the substrate is converted with a relatively moderate rate. A rigid analogue 4-[Zn](2) exhibits both a lower substrate binding strength and a lower catalytic rate. This demonstrates the importance of a certain flexibility between the cooperating catalytic centers. The trinuclear complex 5-[Zn](3) induces a rate acceleration of 32 000 times, and shows a decreased substrate binding and an increased catalytic rate compared to its dinuclear analogue 3-[Zn](2). In a possible mechanism two Zn(II) ions activate the phosphoryl group and another activates the beta-hydroxyl group of HPNP.

  DOI：

  10.1021/jo982201f
• 作为产物：
  描述：

  杯[4]芳烃 在 四氯化钛 、 sodium hydride 作用下， 以 四氢呋喃 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 5,11,17-Triformyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
  参考文献：
  名称：

  Synthesis and evaluation of deep cavity imidazolyl calix[n]arenes

  摘要：

  通过五步合成法（包括预成型钙[n]烯下缘的适当烷基化、上缘的甲酰化以及随后在醋酸铵和冰醋酸存在下与芳基二酮的缩合），从容易获得的起始材料中获得了一系列深腔二苯基咪唑钙[n]烯（4、6、8）。已对获得锥形构型的标题衍生物的优化反应条件以及通过光谱方法（红外光谱、紫外光谱、核磁共振和 FAB 质量）对其进行表征进行了界定。初步研究了合成的咪唑烷基萼片烯对一价金属离子（Li+、Na+、K+、Cs+、Ag+）的选择性识别能力。

  DOI：

  10.1007/s10847-010-9921-2

文献信息

• One-shot preparation of an inherently chiral trifunctional calix[4]arene from an easily available cone-triformylcalix[4]arene
  作者：Maria Ciaccia、Irene Tosi、Roberta Cacciapaglia、Alessandro Casnati、Laura Baldini、Stefano Di Stefano

  DOI：10.1039/c3ob40355f

  日期：——

  Via selective 1,3-distal intramolecular Cannizzaro disproportionation of an easily available cone-triformylcalix[4]arene, an inherently chiral trifunctional cone-calix[4]arene derivative has been prepared. The presence of three different functional groups (–CH2OH, –CHO and –COOH) at the upper rim of the calixarene scaffold makes this compound a versatile intermediate for the development of multifunctional

  通过选择性地容易地获得的圆锥-三甲酰基杯[4]芳烃的1，3-远距离分子内坎尼扎罗歧化，制备了固有的手性三官能团圆锥-杯[4]芳烃衍生物。存在三个不同的官能团（–CH 2杯芳烃支架上缘的OH，–CHO和–COOH）使该化合物成为多功能设备开发的多功能中间体。观察到有趣的丝氨酸衍生物的手性鉴别，大概是由于涉及可逆亚胺键形成以及氨基酸侧链的羟基与上边缘官能团的氢键的多点相互作用。一致地，没有观察到手性歧视。丙氨酸 和缬氨酸衍生物，在侧链上缺少氢键基团。
• Selective formylation of calix[4]arenes at the ‘upper rim’ and synthesis of new cavitands
  作者：Arturo Arduini、Giuseppe Manfredi、Andrea Pochini、Anna Rita Sicuri、Rocco Ungaro

  DOI：10.1039/c39910000936

  日期：——

  The direct selective upper rim 1,3-formylation of conformationally rigid calyx[4]arenes is achieved for the first time; the diametrical bis(formyl)calix[4]arene 4 is used as a key intermediate for the synthesis of new cavitands.

  首次实现构象刚性花萼[4]芳烃的直接选择性上边缘1,3-甲酰化；径向双（甲酰基）杯[4]芳烃4被用作合成新空泡分子的关键中间体。
• New calix[4]arenes having electron donating groups at the upper rim as molecular platforms and host molecules
  作者：Arturo Arduini、Leonardo Mirone、Daniela Paganuzzi、Alessandra Pinalli、Andrea Pochini、Andrea Secchi、Rocco Ungaro

  DOI：10.1016/0040-4020(96)00238-4

  日期：1996.4

  a new and general synthetic procedure for the exhaustive and selective introduction of hydroxy groups at the upper rim of calix[4]arenes in the cone conformation is reported. The aldehyde-derivatives of tetraalkoxycalix[4]arenes have been oxidized by Baeyer-Villiger reaction. The introduction of amino and hydroxy groups on calix[4]arene having a rigid cone conformation has been achieved for the first

  报道了一种新的通用合成方法，用于在圆锥构象的杯[4]芳烃的上边缘完全和选择性地引入羟基。四烷氧基杯[4]芳烃的醛衍生物已被Baeyer-Villiger反应氧化。首次实现在具有刚性圆锥构象的杯[4]芳烃上引入氨基和羟基。
• Synthesis of selectively formylated calixarene ethers
  作者：Vandna Arora、H.M Chawla、Anuradha Santra

  DOI：10.1016/s0040-4020(02)00551-3

  日期：2002.7

  By careful choice of a catalyst (TiCl4 or SnCl4) temperature, reaction time and mole ratio of the substrate to dichloromethyl-methylether, it has been possible to obtain new functionalized formylated calix[n]arenes in the cone or partial cone conformation. Optimized general reaction procedures for obtaining mono-, di-, tri- and tetraformylated derivatives of calix[4]arenes as exemplified by formylation of tetramethoxy-, tetrakis(2-ethoxyethoxy)-, bis(ethoxycarbonylmethoxy)- and bis(hexadecyloxy)-calix[4]-arenes have been reported. (C) 2002 Published by Elsevier Science Ltd.
• Direct Regioselective Formylation of Tetraalkoxycalix[4]arenes Fixed in the Cone Conformation and Synthesis of New Cavitands
  作者：Arturo Arduini、Stefano Fanni、Giuseppe Manfredi、Andrea Pochini、Rocco Ungaro、Anna R. Sicuri、Franco Ugozzoli

  DOI：10.1021/jo00110a054

  日期：1995.3

  Regioselectivity of the formylation of tetraalkoxycalix[4]arene fixed in the cone conformation has been studied. Direct, diametrical (1,3) diformylation of calix[4]arenes having four chelating chains at the lower rim has been achieved. Simple tetraalkoxycalix[4]arenes produce a mixture of diametrical (1,3) and proximal (1,2) diformylated products. The (1,3) functionalized compounds have been used for the synthesis of double calix[4]arenes 12a,d linked via the upper rim. The residual mobility of these cone conformers is indicated by the X-ray crystal structure of compound 12d, which shows a flattened cone conformation, and by the reactive behavior of 1,3-bis(hydroxymethyl) derivatives 9a,d which give very distorted 1,3-bridged compounds 11a,d, through an intramolecular cyclization process.