5,11,17,23,29,35-Hexa-tert-butyl-37,38,40,41-tetrahydroxy-39,42-bis<(4-methylbenzyl)oxy>calix<6>arene | 140659-14-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23,29,35-Hexa-tert-butyl-37,38,40,41-tetrahydroxy-39,42-bis<(4-methylbenzyl)oxy>calix<6>arene
• 英文别名: 5,11,17,23,29,35-Hexatert-butyl-39,42-bis[(4-methylphenyl)methoxy]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(40),16,18,21(39),22,24,27,29,31(38),33(37),34-octadecaene-37,38,40,41-tetrol
• CAS: 140659-14-9
• 化学式: C₈₂H₁₀₀O₆
• 分子量: 1181.69
• InChiKey: UEPKYSJSNLDQSF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  23.8
• 重原子数：
  88
• 可旋转键数：
  12
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  99.4
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,11,17,23,29,35-Hexa-tert-butyl-37,38,40,41-tetrahydroxy-39,42-bis<(4-methylbenzyl)oxy>calix<6>arene 、 硫酸二甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 40.0h， 以100%的产率得到5,11,17,23,29,35-hexa-tert-butyl-38,39,41,42-tetramethoxy-37,40-bis<( 4-methylbenzyl)oxy>calix<6>arene
  参考文献：
  名称：

  De Mendoza; Carramolino; Cuevas, Synthesis, 1994, # 1, p. 47 - 50

  摘要：

  DOI：
• 作为产物：
  描述：

  4-叔丁基杯[6]芳烃 、 4-甲基苄溴 在 potassium trimethylsilonate 作用下， 生成 5,11,17,23,29,35-Hexa-tert-butyl-37,38,40,41-tetrahydroxy-39,42-bis<(4-methylbenzyl)oxy>calix<6>arene
  参考文献：
  名称：

  Calixarenes. 29. Aroylation and arylmethylation of calix[6]arenes

  摘要：

  Aroylations and arylmethylations of p-tert-butylcalix[6]arene have been carried out using a variety of parasubstituted aroyl chlorides and arylmethyl halides to determine the effect of para substituents on the structural and/or conformational outcome of the reactions. When an excess of derivatizing agent is used with NaH as the base the products in all cases are the 1,2,4,5-tetrasubstituted compounds in the 1,2,3-alternate conformation. However, with Me3SiOK as the base the products of arylmethylation are the 1,4-diethers. By varying the reaction conditions it is possible in some cases to prepare hexaethers as well as monoethers. By means of H-1 NMR spectral measurements it has been shown that any aroyl moiety or any para-substituted phenylmethyl moiety is large enough to prevent its rotation through the annulus of the calix[6]arene, thus partially, or in some cases completely, freezing the conformation. The unsubstituted benzyl moiety, however, is small enough to pass through the annulus fairly easily, thus allowing complete conformational interconversion to occur. The synthetic utility of these derivatives is adumbrated by the selective de-tert-butylation of a tetraester and the intramolecular bridging of a diether.

  DOI：

  10.1021/jo00037a037

文献信息

• Synthesis and Conformational Studies on Hexa-<i>O</i>-alkyl p-Unsubstituted Calix[6]arenes
  作者：José C. Iglesias-Sánchez、Beatriz Souto、César J. Pastor、Javier de Mendoza、Pilar Prados

  DOI：10.1021/jo0516638

  日期：2005.12.1

  para-unsubstituted calix[6]arene 1 in rings 1 and 4 (2a−c) and the subsequent alkylation of phenol groups with α-haloesters (methyl esters 3a, 3c, and 3e; tert-butyl esters 3b, 3d, and 3f) to determine the effect of these groups on their conformational behavior. 2D NMR studies at 188 K reveal that compounds 2a−c, 3b, 3d, and 3f are less flexible, showing a 1,2,3-alternate conformation. The same conformation has been

  在本文中，我们描述了环1和4（2a - c）中对未取代的杯[6]亚芳基1的选择性O-苄基化，以及随后的α-卤代酸酯（甲酯3a，3c和3e）对苯酚基团的烷基化；叔丁基酯3b，3d和3f）来确定这些基团对其构象行为的影响。188 K的2D NMR研究表明，化合物2a - c，3b，3d和3f柔韧性较差，显示1,2,3-交替构象。在固态中已经观察到相同的构象。
• Influence of <i>exo</i>-Adamantyl Groups and <i>endo</i>-OH Functions on the Threading of Calix[6]arene Macrocycle
  作者：Veronica Iuliano、Carmen Talotta、Carmine Gaeta、Neal Hickey、Silvano Geremia、Ivan Vatsouro、Vladimir Kovalev、Placido Neri

  DOI：10.1021/acs.joc.0c01769

  日期：2020.10.2

  Calix[6]arenes bearing adamantyl groups at the exo-rim form pseudorotaxanes with dialkylammonium axles paired to the weakly coordinating [B(ArF)4]− anion. The exo-adamantyl groups give rise to a more efficient threading with respect to the exo-tert-butyl ones, leading to apparent association constants more than one order of magnitude higher. This improved stability has been ascribed to the more favorable

  杯[6]芳烃轴承金刚烷基在外型与二烷基车轴-rim形式pseudorotaxanes配对至弱配位[B（AR ˚F）4 ] -的阴离子。所述外切金刚烷基团产生更有效的螺纹相对于所述外-叔丁基的，导致明显的结合常数超过一个数量级高。这种改进的稳定性已被归因于更有利范德瓦的耳斯相互作用外型-adamantyls与外切-叔与阳离子轮轴-butyls。杯[6]芳烃轴承内相对于内-OR基团，-OH官能团导致效率较低的穿线，这与从碱金属阳离子的络合中已知的一致。
• Chiral 1,10-Phenanthroline-Bridged Calix[6]arenes
  作者：Serge Konrad、Michael Bolte、Christian Näther、Ulrich Lüning

  DOI：10.1002/ejoc.200600295

  日期：2006.10

  Several approaches to chiral derivatives of the 1,10-phenanthroline-bridged calix[6]arene 3 have been investigated, and seven new chiral calix[6]arenes have been synthesized. The C2-symmetric axially chiral bimacrocycle 5 has been synthesized as racemic mixture; calixarenes 8, 14, 18, 19, 20 and 21 carrying chiral substituents (camphorsulfonyl, myrtanyl) have been prepared using enantiomerically pure

  研究了 1,10-菲咯啉桥接杯 [6] 芳烃 3 手性衍生物的几种方法，并合成了 7 种新的手性杯 [6] 芳烃。C2 对称轴手性双大环 5 已合成为外消旋混合物；使用对映体纯试剂制备了带有手性取代基（樟脑磺酰基、肉豆蔻酰基）的杯芳烃 8、14、18、19、20 和 21。三个手性双大环 5、19 和 20 也已通过 X 射线分析进行了分析。在 CuI 催化的苯乙烯和茚环丙烷化反应中，所有化合物都作为铜离子的配体进行了测试。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Synthesis and conformational properties of calix[6]arenes bridged on the lower rim: self-anchored rotaxanes
  作者：Suseela Kanamathareddy、C. David Gutsche

  DOI：10.1021/ja00068a014

  日期：1993.7

  p-tert-butylcalix[6]arene can be converted to transannularly bridged esters by treatment with diacid chlorides ranging from succinoyl to suberoyl and including terephthaloyl. The parent compounds p-tert-butylcalx[6]arene and p-H-calix[6]arene can also be transannularly bridged by treatment with bis-halomethylaryl compounds by using KOSiMe 3 as the base. Methylation of the resulting calix[6]arenes containing

  对叔丁基杯[6]芳烃的 1,4-二-对甲苯基醚可以通过用范围从琥珀酰基到辛二酰基（包括对苯二酰基）的二酰氯处理而转化为环环桥连酯。母体化合物对叔丁基钙[6]芳烃和pH-杯[6]芳烃也可以通过使用KOSiMe 3 作为碱用双卤代甲基芳基化合物处理而跨环桥连。所得含有1,4-CH 2 ArCH 2 桥连部分的杯[6]芳烃的甲基化产生相应的四甲基醚。当Ar为蒽时，原料的构象保持不变，但当Ar为亚苯基时，构象发生变化；当 Ar 是 duryl 时，得到构象异构体的混合物。1 H NMR 分析和分子模型研究表明，当 Ar 为苯基或双二甲苯时，该系统能够进行构象转变，其中桥接部分穿过大环的环以产生自锚定轮烷。采用一种新的方案来表示杯芳烃构象，这被设计为 (u,u,u,u,u,u) 到 (u,u,d,d,d,u) 的转换。与 (u,u,u,u,u,u) 构象相比，构象变化的明显驱动力是 (u,u,d,d
• Microwave-Assisted Synthesis of a Nitro-m-xylylenedioxycalix[6]arene Building Block Functionalized at the Upper Rim
  作者：Hitos Galán、Javier de Mendoza、Pilar Prados

  DOI：10.1002/ejoc.201000954

  日期：2010.12

  Microwave-assisted synthesis represents a new methodology to obtain calix[6]arene building blocks. The synthesis of compounds 1 and 2 is described. These compounds are A,D-m-xylylenedioxy-bridged calix[6]arenes in cone conformation, functionalized with potential amino groups in the lower rim spacer (5-position) and amino groups or their precursors in A,D-para positions at the upper rim. A conformational

  微波辅助合成代表了一种获得杯[6]芳烃结构单元的新方法。描述了化合物 1 和 2 的合成。这些化合物是锥形构象中的 A,Dm-苯二甲氧基桥接杯 [6] 芳烃，在下缘间隔区（5 位）中被潜在的氨基官能化，在上缘的 A,D-对位上用氨基或它们的前体进行了功能化。轮缘。对所有新合成的化合物进行了构象研究。