5,17,29-tri-tert-butyl-37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene | 156747-01-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,17,29-tri-tert-butyl-37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene
• 英文别名: 5,17,29-tris(1,1-dimethylethyl)-37,39,41-trimethoxycalix[6]arene-38,40,45-triol；5,17,29-Tritert-butyl-38,40,42-trimethoxyheptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(37),3,5,7(42),9,11,13(41),15(40),16,18,21(39),22,24,27(38),28,30,33,35-octadecaene-37,39,41-triol
• CAS: 156747-01-2
• 化学式: C₅₇H₆₆O₆
• 分子量: 847.147
• InChiKey: OEZZOMQOPFSTAJ-UHFFFAOYSA-N

物化性质

• 沸点：
  871.5±65.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  15.4
• 重原子数：
  63
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  88.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,17,29-tri-tert-butyl-37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 5,17,29-tri-tert-butyl-38,40,42-trimethoxy-11,23,35-tris(2-propenyloxy)calix<6>arene-37,39,41-triol
  参考文献：
  名称：

  在上部边缘部分官能化的杯[6]芳烃的合成

  摘要：

  报告了在上部边缘选择性功能化的杯[6]芳烃的一些新实例。从在下部边缘被烷基化的杯[6]芳烃1,3,5-三-，1,2,4,5-四-和1,2,3,4,5-五烷基开始，有可能分离出大环化合物2 ，4,6-三-，3,6-二-和6-单官能团在上缘被官能化（18-94％的产率），带有硝基，甲酰基，溴，氯甲基和2-丙烯基。这些部分的修饰允许合成带有氨基，酰胺基，羟甲基，羧基，氰基和氯甲基官能团的大环，这些环可以基于杯[6]芳烃（具有不同的几何结构）用于进一步转化和制备新的分子受体。还报道了六聚大环上的二醌和三醌的实例。

  DOI：

  10.1016/0040-4020(95)00826-t
• 作为产物：
  描述：

  1,3,5-trimethoxy-p-tert-butylcalix[6]arene 在 三氯化铝 作用下， 以 甲苯 为溶剂， 反应 0.17h， 以81%的产率得到5,17,29-tri-tert-butyl-37,39,41-trihydroxy-38,40,42-trimethoxycalix[6]arene
  参考文献：
  名称：

  Control of Calix[6]arene Conformations by Self-Inclusion of 1,3,5-Tri-O-alkyl Substituents: Synthesis and NMR Studies

  摘要：

  Hexa-O-alkylated p-tert-butylcalix[6]arenes with an alternate 1,3,5-R(1)-2,4,6-R(2)-substitution pattern have been prepared and studied by NMR spectroscopy. When R(1) = CH3 and R(2) is a bulky substituent, the calix[6]arene moiety adopts predominantly a flattened cone conformation. At room temperature this conformation slowly interconverts with a 1,2,3-alternate conformation (Delta G(double dagger) = 70-88 kJ mol(-1), T = 328 K, CDCl3). The Gibbs free energy between these two conformations at T = 303 K in CDCl3 varies from 2 to 7 kJ mol(-1). From quantitative NOE data (obtained for 1,3,5-trimethoxy-2,4,6-tris[(3-nitrobenzyl)oxyl-p-tert-butylcalix[6]arene (10) three-dimensional structures of the flattened cone and the 1,2,3-alternate conformers were calculated. In both conformers the methoxy groups are accommodated in the annulus of the calix [6] arene skeleton, indicating specific interactions with the aromatic calixarene moiety. Compared to the hexasubstituted analogues, this structural feature slightly increases the activation Gibbs free energy for the interconversion process (13-21 kJ mol(-1)). Even with substituents that are too large to rotate through the annulus, there is still slow interconversion (Delta G(double dagger) = 88 kJ mol(-1), T = 328 K, CDCl3). This is attributed to a very slow transannular motion of the p-tert-butyl moiety. Also the ethoxy (16) or propoxy (17) derivatives of 2,4,6-tris(N,N-diethylacetamido)-p-tert-butylcalix[6]arene predominantly adopt flattened cone (16) and 1,2,3-alternate (17) conformations, respectively. The self-inclusion of the larger alkyl groups also contributes to the overall conformational freezing of the p-tert-butylcalix[6]arenes.

  DOI：

  10.1021/ja00092a036

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。
• 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。
• Guest inclusion properties of calix[6]arene-based unimolecular cage compounds. On their high Cs+ and Ag+ selectivity and very slow metal exchange rates
  作者：Hideyuki Otsuka、Yoshio Suzuki、Atsushi Ikeda、Koji Araki、Seiji Shinkai

  DOI：10.1016/s0040-4020(97)10261-7

  日期：1998.1

  groups of anisole units and the lower hemisphere is closed by a mesitylene cap and three anisole methoxy groups. The 1H NMR spectrum was scarcely changed at wide temperature range (30 ∼ 130°C), indicating that the structure is extremely rigidified. Both solvent extraction and spectroscopic studies established that this cavity shows the high selectivity toward Cs+ among alkali metal cations, the high

  1,3,5-三-O-烷基烷基杯[6]芳烃与1,3,5-三（溴甲基）苯的反应生成了封端的杯[6]芳烃（2个在上边缘带有叔丁基的芳烃）3个不含叔丁基的化合物），出乎意料的高收率（80 – 91％）。通过MM3计算，X射线分析和1 H NMR光谱对2和3进行的联合研究表明，这些杯[6]芳烃具有独特的结构，该结构由三个均三聚的均三甲苯基连接的苯基单元和三个直立的苯甲醚交替排列组成单位。特别地，化合物2具有封闭的离子载体腔：上半球被三个封闭苯甲醚单元和下半球的叔丁基被1，3，5-三甲苯基帽和三个苯甲醚甲氧基封闭。的1 H NMR谱在宽的温度范围（30〜130℃），几乎没有变化，这表明结构极其刚性化。溶剂萃取和光谱学研究均证实，该空腔在碱金属阳离子中显示出对Cs +的高选择性，与Ag +的高亲和力以及与RNH 3 +的中等亲和力。非常令人惊讶的是，2-苦味酸铯与铯的缔合-解离过程是如此缓慢，以致于传统
• A selective fluorescent probe for La3+ and Y3+ based on calix[6]arene
  作者：Jun-Min Liu、Chuan-Feng Chen、Qi-Yu Zheng、Zhi-Tang Huang

  DOI：10.1016/j.tetlet.2004.05.159

  日期：2004.7

  A new fluorescent probe based on calix[6]arene functionalized with three naphthoic acid groups was synthesized and showed selective fluorescence enhancement in the presence of La3+ and Y3+. In addition, the fluorescence enhancement behaviors depended on the pH values of the solution.

  合成了一种新的基于带有三个萘甲酸官能团的杯[6]芳烃的荧光探针，并在La 3+和Y 3+存在下显示出选择性的荧光增强作用。另外，荧光增强行为取决于溶液的pH值。
• Control of Calix[6]arene Conformations by Self-Inclusion of 1,3,5-Tri-O-alkyl Substituents: Synthesis and NMR Studies
  作者：John P. M. van Duynhoven、Rob G. Janssen、Willem Verboom、Sybille M. Franken、Alessandro Casnati、Andrea Pochini、Rocco Ungaro、Javier de Mendoza、Pedro M. Nieto

  DOI：10.1021/ja00092a036

  日期：1994.6

  Hexa-O-alkylated p-tert-butylcalix[6]arenes with an alternate 1,3,5-R(1)-2,4,6-R(2)-substitution pattern have been prepared and studied by NMR spectroscopy. When R(1) = CH3 and R(2) is a bulky substituent, the calix[6]arene moiety adopts predominantly a flattened cone conformation. At room temperature this conformation slowly interconverts with a 1,2,3-alternate conformation (Delta G(double dagger) = 70-88 kJ mol(-1), T = 328 K, CDCl3). The Gibbs free energy between these two conformations at T = 303 K in CDCl3 varies from 2 to 7 kJ mol(-1). From quantitative NOE data (obtained for 1,3,5-trimethoxy-2,4,6-tris[(3-nitrobenzyl)oxyl-p-tert-butylcalix[6]arene (10) three-dimensional structures of the flattened cone and the 1,2,3-alternate conformers were calculated. In both conformers the methoxy groups are accommodated in the annulus of the calix [6] arene skeleton, indicating specific interactions with the aromatic calixarene moiety. Compared to the hexasubstituted analogues, this structural feature slightly increases the activation Gibbs free energy for the interconversion process (13-21 kJ mol(-1)). Even with substituents that are too large to rotate through the annulus, there is still slow interconversion (Delta G(double dagger) = 88 kJ mol(-1), T = 328 K, CDCl3). This is attributed to a very slow transannular motion of the p-tert-butyl moiety. Also the ethoxy (16) or propoxy (17) derivatives of 2,4,6-tris(N,N-diethylacetamido)-p-tert-butylcalix[6]arene predominantly adopt flattened cone (16) and 1,2,3-alternate (17) conformations, respectively. The self-inclusion of the larger alkyl groups also contributes to the overall conformational freezing of the p-tert-butylcalix[6]arenes.