5,17-diamino-11,23-di-tert-butyl-25,26,27,28-tetrapropoxycalix[4]arene | 201288-26-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,17-diamino-11,23-di-tert-butyl-25,26,27,28-tetrapropoxycalix[4]arene
• 英文别名: 5,17-Diamino-11,23-bis(1,1-dimethylethyl)-25,26,27,28-tetrapropoxycalix[4]arene；11,23-Ditert-butyl-25,26,27,28-tetrapropoxypentacyclo[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-5,17-diamine
• CAS: 201288-26-8
• 化学式: C₄₈H₆₆N₂O₄
• 分子量: 735.063
• InChiKey: RBDGPHCXDAOMEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.1
• 重原子数：
  54
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  89
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,17-diamino-11,23-di-tert-butyl-25,26,27,28-tetrapropoxycalix[4]arene 在 氨 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 5,17-N,N'-Bis(4-amino-6-chloro-1,3,5-trazin-2-yl)diamino-11,23-bis(1,1-dimethylethyl)-25,26,27,28-tetrapropoxycalix[4]arene
  参考文献：
  名称：

  Noncovalent Assembly of Functional Groups on Calix[4]Arene Molecular Boxes

  摘要：

  AbstractCalix[4]arenes diametrically substituted at the upper rim with two melamine units spontaneously form well‐defined box‐like assemblies in the presence of two equivalents of 5,5‐diethylbarbituric acid. These assemblies, consisting of nine different components, are held together by 36 hydrogen bonds and are stable in apolar solvents at concentrations of up to 10−4M. This paper reports the first X‐ray crystal structure, and the MALDI TOF mass spectra together with the complete 1H NMR spectroscopic characterization of these hydrogen‐bonded assemblies. The crystal structure clearly shows that the assemblies are stereogenic, as a result of the antiparallel orientation of the two rosette motifs. Furthermore, the synthesis of twelve new 1,3‐bis(melamine)calix[4]arenes carrying different numbers and types of functionalities at the upper rim is described. Detailed 1H NMR spectroscopic studies on the assembly behavior of these functionalized calix[4]arenes shows that 1) polar substituents (e.g. nitro, cyano) hardly affect the stability of the hydrogen‐bonded assembly; 2) hydrogen bond donating or accepting groups, like amino and acetamido, can disturb assembly of the boxes under certain conditions by destabilizing the calix[4]arene pinched cone conformation as a result of intramolecular hydrogen bond formation; and 3) sterically bulky groups (e.g. tBu) can significantly inhibit the formation of the hydrogen‐bonded assembly, but this effect very much depends on the exact positions of the groups.

  DOI：

  10.1002/chem.19970031115
• 作为产物：
  描述：

  5,17-Ditert-butyl-11,23-dinitro-25,27-bis(prop-2-enoxy)-26,28-dipropoxypentacyclo[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 在 镍 氢气 作用下， 以 四氢呋喃 为溶剂， 以45%的产率得到5,17-diamino-11,23-di-tert-butyl-25,26,27,28-tetrapropoxycalix[4]arene
  参考文献：
  名称：

  1,3-交替杯[4]芳烃，被氨基选择性地官能化。

  摘要：

  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

  DOI：

  10.1039/b414173c

文献信息

• Anion receptors based on ureidocalix[4]arenes immobilised in the partial cone conformation
  作者：Oldřich Hudeček、Jan Budka、Hana Dvořáková、Petra Cuřínová、Ivana Císařová、Pavel Lhoták

  DOI：10.1039/c2nj40724h

  日期：——

  A novel method enabling the synthesis of receptors based on the calix[4]arenes immobilized in the partial cone conformation is reported. The application of a protection/deprotection strategy using nosyl groups enables the regioselective introduction of functional groups (NO2 and NH2) into the upper rim of calix[4]arenes, leading finally to the substitution pattern so far inaccessible to calixarene chemistry. The introduction of two ureido functions at the para positions of the partial cone conformer yields a novel type of receptor which can bind anions even in a highly competitive solvent (DMSO). This revealed that the partial cone conformation, so far rather ignored in supramolecular chemistry, can be also very useful in design of novel anion receptors.

  报道了一种基于固定在部分锥体构象中的杯[4]芳烃合成受体的新方法。使用nosyl基团的保护/脱保护策略的应用使得能够将官能团（NO2和NH2）区域选择性地引入到杯[4]芳烃的上边缘，最终导致迄今为止杯芳烃化学无法达到的取代模式。在部分锥体构象异构体的对位引入两个脲基官能团产生了一种新型受体，即使在高度竞争性溶剂（DMSO）中也可以结合阴离子。这表明，迄今为止在超分子化学中被忽视的部分圆锥构象在新型阴离子受体的设计中也非常有用。
• A calixarene dendron with surface congestion at the first generation
  作者：Hitos Galán、M. Teresa Murillo、Roberto Quesada、Eduardo C. Escudero-Adán、Jordi Benet-Buchholz、Pilar Prados、Javier de Mendoza

  DOI：10.1039/b921465h

  日期：——

  The X-ray structure of a dendrimeric receptor based on calixarenes showed a packed periphery in the first generation. The presence of urea groups as linkers between the calix[4]arene core and the calix[6]arene dendrons makes it a good model as an endo-receptor which is able to coordinate squarate dianions with a high association constant.

  基于钙[4]烯的树枝状受体的 X 射线结构显示，第一代受体的外围是密集的。在钙[4]炔核心和钙[6]炔树枝之间存在脲基团作为连接体，这使其成为一个良好的内受体模型，能够以较高的结合常数协调方形二元离子。