5,17,29-trinitro-11,23,35-tri-tert-butyl-38,40,42-trimethoxy-37,39,41-tris[(1-methyl-2-imidazolyl)methoxy]calix[6]arene | 608129-83-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,17,29-trinitro-11,23,35-tri-tert-butyl-38,40,42-trimethoxy-37,39,41-tris[(1-methyl-2-imidazolyl)methoxy]calix[6]arene
• 英文别名: 1-Methyl-2-[[11,23,35-tritert-butyl-38,40,42-trimethoxy-39,41-bis[(1-methylimidazol-2-yl)methoxy]-5,17,29-trinitro-37-heptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(36),3,5,7(42),9,11,13(41),15,17,19(40),21(39),22,24,27(38),28,30,33(37),34-octadecaenyl]oxymethyl]imidazole
• CAS: 608129-83-5
• 化学式: C₇₂H₈₁N₉O₁₂
• 分子量: 1264.49
• InChiKey: QZDQPYRABPWBCF-UHFFFAOYSA-N

物化性质

• 熔点：
  273-274 °C(Solv: ethyl acetate (141-78-6); pentane (109-66-0))
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  14.7
• 重原子数：
  93
• 可旋转键数：
  15
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  246
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  5,17,29-trinitro-11,23,35-tri-tert-butyl-38,40,42-trimethoxy-37,39,41-tris[(1-methyl-2-imidazolyl)methoxy]calix[6]arene 在 palladium on activated charcoal 、 一水合肼 作用下， 以75%的产率得到5,17,29-tris-amino-11,23,35-tris-tert-butyl-37,39,41-trimethoxy-38,40,42-tris[(1-methyl-2-imidazolyl)methoxy]calix[6]arene
  参考文献：
  名称：

  壮观的诱导拟合过程的客杯结合杯[6]芳烃锌（II）漏斗复杂。

  摘要：

  描述了杯形[6]亚芳基锥的主体性质，该锥在小边缘上被Zn（II）三-咪唑核覆盖并在大边缘上被三个NH（2）取代基装饰，并与hexa-tBu母体复合物进行了比较。结果表明，由三个亲水性和小的NH（2）基团取代了三个笨重的tBu取代基具有三个主要影响：该受体现在可溶于水介质，它接受诸如二甲基多巴胺之类的大客体，而且最有趣的是，它经历了壮观的变化。来宾绑定的诱导拟合行为。

  DOI：

  10.1039/b809699f
• 作为产物：
  描述：

  5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38,40,42-tris[(1-methyl-2-imidazolyl)methoxy]calix[6]arene 在 硝酸 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到5,17,29-trinitro-11,23,35-tri-tert-butyl-38,40,42-trimethoxy-37,39,41-tris[(1-methyl-2-imidazolyl)methoxy]calix[6]arene
  参考文献：
  名称：

  杯状[6]芳烃芳香核中的（H3O2）-单元在大边缘和大边缘处被两个Zn（II）离子封闭。

  摘要：

  第一个Zn（II）离子与杯形[6]芳烃的配位在小边缘处具有三个咪唑基臂，在大边缘处具有三个苯胺部分，从而允许第二个Zn（II）离子结合，同时保留（H3O2） -在芳香腔中的单位。

  DOI：

  10.1039/b608203c

文献信息

• [EN] NEW CALIX ARENE COMPOUNDS, THEIR PROCESS OF PREPARATION AND THEIR USE, PARTICULARLY AS ENZYMATIC MIMES<br/>[FR] NOUVEAUX COMPOSES DE CALIX ARENES, LEUR PROCEDE DE PREPARATION ET LEUR UTILISATION, NOTAMMENT EN TANT QUE MIMES ENZYMATIQUES
  申请人：CENTRE NAT RECH SCIENT

  公开号：WO2004085441A1

  公开（公告）日：2004-10-07

  The present invention relates to new calix arene compounds of formula (I). It also relates to their process of preparation. The present invention also relates to complexes between a compound of formula (I) and an element chosen among a metal, an actinide, a radioelement, a cationic guest or an anionic guest. The present invention also relates to a pharmaceutical composition comprising a compound of formula (I) in association with a pharmaceutically acceptable carrier. The present invention also relates to a process of preparation of water-soluble compounds, comprising a reaction of nitration or sulfonation or nitration, particularly of compounds of formula (I), and also to the compounds such as obtained.

  本发明涉及公式(I)的新卡利克斯烷化合物。它还涉及它们的制备过程。本发明还涉及公式(I)化合物与金属、锕系元素、放射性元素、阳离子客体或阴离子客体之间的络合物。本发明还涉及一种包含公式(I)化合物与药用载体结合的药物组合物。本发明还涉及一种制备水溶性化合物的方法，包括硝化或磺化或硝化的反应，特别是公式(I)化合物的反应，以及所得到的化合物。
• A versatile strategy for appending a single functional group to a multifunctional host through host–guest covalent-capture
  作者：Jean-Noël Rebilly、Assia Hessani、Benoit Colasson、Olivia Reinaud

  DOI：10.1039/c4ob01429d

  日期：——

  Mono-functionalization of a molecular host is a key step for the development of various efficient systems ranging from supramolecular fluorescent probes to supramolecular catalysts. The presence of several identical reactive groups on the host makes its selective mono-functionalization a challenge. We propose a general two-step strategy to achieve this, based on the receptor properties of the host. A guest bearing two orthogonal functions is first reacted with the host presenting itself a reactive function that is complementary to one of those of the guest. As a result, the host is selectively mono-functionalized by the covalent capture of the guest, which inhibits further reaction of the host. The second function that was present on the guest and which is now covalently linked to the host can be activated in the second step for the grafting of various objects. As a proof of concept, the strategy is described on a calix[6]arene scaffold presenting three identical reactive units. Using Huisgen thermal azide–alkyne cycloaddition for the host–guest covalent-capture step, three examples of post-functionalization are described, allowing cavities bearing a single redox tag, fluorescent probe or polydentate ligand through esterification, Schiff base formation or nucleophilic substitution to be obtained.

  分子宿主的单官能化是开发从超分子荧光探针到超分子催化剂等各种高效系统的关键步骤。由于宿主上存在多个相同的反应基团，因此对其进行选择性单官能化是一项挑战。我们根据宿主的受体特性，提出了实现这一目标的一般两步策略。首先，带有两种正交功能的客体与宿主发生反应，宿主呈现出的反应功能与客体的其中一种功能互补。结果，宿主通过共价俘获客体而被选择性地单官能化，从而抑制了宿主的进一步反应。客体上的第二种功能现在与宿主共价连接，可以在第二步中激活，用于嫁接各种物体。作为概念验证，我们介绍了一种具有三个相同反应单元的钙[6]炔支架。利用 Huisgen 热叠氮烷烃环加成法进行主客共价捕获步骤，描述了三个后官能化实例，通过酯化、席夫碱形成或亲核取代，可获得带有单一氧化还原标记、荧光探针或多齿配体的空腔。
• Spectacular induced-fit process for guest binding by a calix[6]arene Zn(ii) funnel complex
  作者：David Coquière、Jérôme Marrot、Olivia Reinaud

  DOI：10.1039/b809699f

  日期：——

  The host properties of a calix[6]arene cone capped by a Zn(II) tris-imidazole core at the small rim and decorated by three NH(2) substituents at the large rim are described and compared to the hexa-tBu parent complex. It is shown that the replacement of three bulky tBu substituents by three hydrophilic and small NH(2) groups has three major impacts: the receptor is now soluble in aqueous media, it

  描述了杯形[6]亚芳基锥的主体性质，该锥在小边缘上被Zn（II）三-咪唑核覆盖并在大边缘上被三个NH（2）取代基装饰，并与hexa-tBu母体复合物进行了比较。结果表明，由三个亲水性和小的NH（2）基团取代了三个笨重的tBu取代基具有三个主要影响：该受体现在可溶于水介质，它接受诸如二甲基多巴胺之类的大客体，而且最有趣的是，它经历了壮观的变化。来宾绑定的诱导拟合行为。
• Encapsulation of a (H₃O₂)⁻unit in the aromatic core of a calix[6]arene closed by two Zn(<scp>ii</scp>) ions at the small and large rims
  作者：David Coquière、Jérôme Marrot、Olivia Reinaud

  DOI：10.1039/b608203c

  日期：——

  of a first Zn(II) ion to a calix[6]arene presenting three imidazolyl arms at the small rim and three aniline moieties at the large rim allows the binding of a second Zn(II) ion while hosting a (H3O2)- unit in the aromatic cavity.

  第一个Zn（II）离子与杯形[6]芳烃的配位在小边缘处具有三个咪唑基臂，在大边缘处具有三个苯胺部分，从而允许第二个Zn（II）离子结合，同时保留（H3O2） -在芳香腔中的单位。
• Unprecedented Selective <i>ipso</i>-Nitration of Calixarenes Monitored by the <i>O</i>-Substituents
  作者：Sophie Redon、Yun Li、Olivia Reinaud

  DOI：10.1021/jo034557j

  日期：2003.9.1

  carboxylic acid), situated in the gamma or epsilon position of the phenoxy moieties, deactivates the corresponding aromatic ring by removing electron density through intramolecular hydrogen bonding. The high control operated by the O-substituents at the small rim even allowed the selective ipso-nitration of partially detertiobutylated calixarene 1(H3). Hence, these findings open new routes to a wide range of

  已经研究了在小边缘上存在交替的O-甲基和O-2-亚甲基-N-甲基-咪唑基的tBu-calix [6]芳烃的亲电ipso反应。1在硫酸中进行过磺化反应，但它与硝酸选择性反应生成三硝基衍生物。ipso硝化在杯芳烃苯甲醚单元上区域选择性地发生。已经用各种tBu-杯芳烃（2-11）研究了反应，所述tBu-杯芳烃具有交替的苯甲醚和苯酚醚单元。该过程的区域选择性似乎与O-取代基上质子化位点的存在有关。提出了位于苯氧基部分的γ或ε位置的相应的质子化杂原子（对于胺，N；对于酰胺和羧酸，O），通过分子内氢键消除电子密度，使相应的芳环失活。O-取代基在小边缘上的高度控制甚至允许部分叔丁基丁基化杯芳烃1（H3）的选择性异丙基硝化。因此，这些发现为大边缘的各种不对称取代的杯芳烃开辟了新途径。