5,17-Bis(1,1-dimethylethyl)-25,27-dihydroxy-11,23-dinitro-26,28-dipropoxycalix<4>arene | 137571-07-4

• 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-Bis(1,1-dimethylethyl)-25,27-dihydroxy-11,23-dinitro-26,28-dipropoxycalix<4>arene
• 英文别名: 11,23-Di-tert-butyl-26,28-dihydroxy-5,17-dinitro-25,27-dipropoxycalix<4>arene；5,17-Ditert-butyl-11,23-dinitro-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-25,27-diol
• CAS: 137571-07-4
• 化学式: C₄₂H₅₀N₂O₈
• 分子量: 710.868
• InChiKey: ABYPWXUPMWVYMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.7
• 重原子数：
  52
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  151
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,17-Bis(1,1-dimethylethyl)-25,27-dihydroxy-11,23-dinitro-26,28-dipropoxycalix<4>arene 在 镍 氢气 、 caesium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 169.0h， 生成 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
• 作为产物：
  描述：

  25,27-dipropoxy-26,28-dihydroxy-p-t-butylcalix[4]arene 在 硝酸 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 0.17h， 以46%的产率得到5,17-Bis(1,1-dimethylethyl)-25,27-dihydroxy-11,23-dinitro-26,28-dipropoxycalix<4>arene
  参考文献：
  名称：

  Ipso nitration of p-tert-butylcalix[4]arenes

  摘要：

  DOI：

  10.1021/jo00030a050

文献信息

• MPV reduction using AlIII–calix[4]arene Lewis acid catalysts: Molecular-level insight into effect of ketone binding
  作者：Partha Nandi、Yuriy I. Matvieiev、Vyacheslav I. Boyko、Kathleen A. Durkin、Vitaly I. Kalchenko、Alexander Katz

  DOI：10.1016/j.jcat.2011.08.013

  日期：2011.11

  Catalytic Meerwein-Ponndorf-Verley (MPV) reduction using Al-III-calix[4]arene complexes is investigated as a model system that requires the bringing together of two different chemical species, ketone and alkoxide, within a six-membered transition state. Two-point versus one-point ketone binding is demonstrated to be the most salient feature that controls MPV catalysis rate. A 7.7-fold increase in rate is observed when comparing reactants consisting of a bidentate Cl-containing ketone and sterically and electronically similar but looser-binding ketones, which are substituted with H and F. The one-point and two-point nature of ketone binding for the various ketones investigated is independently assessed using a combination of structural data derived from single-crystal X-ray diffraction and OFT-based molecular modeling. Using MPV catalysis with inherently chiral calix[4]arenes, the effect of multiple point reactant binding on enantioselectivity is elucidated. A higher denticity of ketone binding appears to increase the sensitivity of the interplay between chiral active site structure and MPV reduction enantioselectivity. (C) 2011 Elsevier Inc. All rights reserved.
• Selective ipso-nitration of tert-butylcalix[4]arene 1,3-diethers: X-ray structure of an unexpected side product
  作者：Oliver Mogck、Volker Böhmer、George Ferguson、Walter Vogt

  DOI：10.1039/p19960001711

  日期：——

  1,3-Diether derivatives of tert-butylcalix[4] arene can be selectively nitrated at the para-position of the phenolic units, In this way calix[4]arenes bearing tert-butyl and nitro groups at the upper rim in alternating sequence are easily available in yields up to 75%, Ipso-attack may also occur ortho to the phenolic hydroxy group leading in a side reaction to macrocyclic compounds with two 6-nitrocyclohexa-2,4-dienone units. Both types of structures were established by single crystal X-ray analysis.