Calix[4]resorcinarene | 443770-31-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: Calix[4]resorcinarene
• 英文别名: 1,8,15,22-tetramethyl-[1.1.1.1]metacyclophan-3,5,10,12,17,19,24,26-octaol；C-methylresorcin-[4]arene；C-Methylcalix[4]resorcinarene；2,8,14,20-tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octol
• CAS: 443770-31-8
• 化学式: C₃₂H₃₂O₈
• 分子量: 544.601
• InChiKey: WGDNYTQTRISCMM-UHFFFAOYSA-N

物化性质

• 沸点：
  853.7±60.0 °C(Predicted)
• 密度：
  1.363±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  40
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  162
• 氢给体数：
  8
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Calix[4]resorcinarene 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 丁酮 为溶剂， 反应 4.0h， 以80%的产率得到5,11,17,23-tetrabromo-2,8,14,20-tetramethylpentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1-(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaen-4,6,10,12,16,18,22,24-octol
  参考文献：
  名称：

  Host-guest complexation. 46. Cavitands as open molecular vessels form solvates

  摘要：

  DOI：

  10.1021/ja00215a037
• 作为产物：
  描述：

  4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(p-tolylsulfonyloxy)-2,8-14,20-(tetramethyl)calix<4>arene 在 氢氧化钾 作用下， 以 甲醇 、 水 为溶剂， 生成 Calix[4]resorcinarene
  参考文献：
  名称：

  Synthesis, Conformation, and Binding Properties of Resorcarene Tetrasulfonates. Asymmetric Reorganization of Pendant Sulfonyl Groups via Intramolecular SO- - -H−O Hydrogen Bonds

  摘要：

  The regioselective reaction of resorcarene octaols 1 with 4 equiv of arylsulfonyl chlorides and Et3N in MeCN gives in 30-60% yield the C-2v symmetrical tetrasulfonates 3. The mild electrophilic substitution (aminomethylation, bromination) of resorcarene tetrasulfonates 3 and tetraphosphates 2 takes place only in the 2-positions of unsubstituted resorcinol rings yielding distally disubstituted resorcarenes 4. The acylation of hydroxy groups in compounds 2 and 3 gives C-2v symmetrical octaesters 5 including large resorcarene tetracrown-ethers. In the minimized boat conformation of tetrasulfonates 3 the two unsubstituted resorcinol rings are vertical and the sulfonyl fragments are arranged in a C-2 symmetrical manner via intramolecular S=O- - -H-O hydrogen bonds. This structure is proved by NMR and IR spectroscopy. In the case of tetrasulfonate 3c the two enantiomeric conformations interconvert in CDCl3 with Delta G* = 11.6 kcal/mol. This is in agreement with the Delta E* value predicted by molecular mechanics in vacuo.

  DOI：

  10.1021/jo981751a

文献信息

• Transformation of a C-methylcalix[4]resorcinarene-based host–guest complex from a wave-like to a novel triangular brick-wall architecture
  作者：Bao-Qing Ma、Philip Coppens

  DOI：10.1039/b212548j

  日期：2003.2.7

  A novel 2D triangular brick-wall framework based on CMCR and bpe with included ruthenocene guest molecules is formed with time by conversion of a 1D wave-like polymer structure with an accompanying bowl-to-boat conformational change of the CMCR molecules.

  一种基于CMCR和双二元脉冲编码调制（bpe）的新型二维三角形砖墙框架结构，随着时间的推移，通过一维波浪状聚合物结构的转化形成，同时伴随着CMCR分子从碗状到船状构象的改变，嵌入了二茂铁客体分子。
• Synthesis and Binding Properties of iiii (4i) Stereoisomers of Phosphonato Cavitands − Cooperative Effects in Cation Complexation in Organic Solvents
  作者：Pascale Delangle、Jean-Christophe Mulatier、Bernard Tinant、Jean-Paul Declercq、Jean-Pierre Dutasta

  DOI：10.1002/1099-0690(200110)2001:19<3695::aid-ejoc3695>3.0.co;2-9

  日期：2001.10

  solvent-dependent and is attributable to the capability of an ammonium guest to form an inclusion complex. Only the iiio (3io) stereoisomer of 3 was isolated otherwise, in low yield. These phosphonato cavitands, in their 4i configurations, are particularly efficient extractants for metal ions. The free energies of complexation of 3 with alkali metal and ammonium cations in chloroform solution are in the range from

  描述了在其 iiii (4i) 构型中四桥磷酸化空腔的合成和主客体特性，四磷酸化空腔 2 和 3 的四个 P=O 键向内取向（4i 立体异构体）分别以 25% 和 53% 的产率制备，来自相应的度假村[4]芳烃，二氯（苯基）氧化膦和碱。4i 立体异构体的形成依赖于溶剂，并且归因于铵客体形成包合物的能力。否则仅以低产率分离出3的iiio(3io)立体异构体。这些膦酸空腔在其 4i 构型中是特别有效的金属离子萃取剂。3 与碱金属和铵阳离子在氯仿溶液中络合的自由能范围为 -43.3 (Li+) 至 -52.4 kJ mol(-1) (CH3NH3+)。高结合常数、溶液中的 H-1、P-31 和 Cs-133 NMR 研究和单晶 X 射线分析清楚地表明，主体的芳香腔和四个硬供体 P=O 基团协同作用以确保阳离子客体的封装。在固体中， 2 。Cs+ 复合物在芳香腔内显示 Cs' 离子，与四个磷酰基相互作用强烈。2
• Conformational Behavior of Pyrazine-Bridged and Mixed-Bridged Cavitands: A General Model for Solvent Effects on Thermal “Vase–Kite” Switching
  作者：Pamela Roncucci、Laura Pirondini、Giuseppe Paderni、Chiara Massera、Enrico Dalcanale、Vladimir A. Azov、François Diederich

  DOI：10.1002/chem.200600085

  日期：2006.6.14

  and NMR analysis of the "vase-kite" switching behavior of a fully pyrazine-bridged cavitand and five other mixed-bridged quinoxaline-bridged cavitands with one methylene, phosphonate, or phosphate bridge. The pyrazine-bridged resorcin[4]arene cavitand displayed an unexpectedly high preference for the kite conformation in nonpolar solvents, relative to the quinoxaline-bridged analogue. This observation

  适当桥接的间苯二酚[4]芳烃空洞在“花瓶”构象（具有能够容纳客体的腔）和“风筝”构象之间的可控切换，其特征是具有扩展的平坦表面，为动态分子受体的持续发展提供了基础，传感器和分子机器。本文描述了完全吡嗪桥接的cavitand和其他五种混合桥接喹喔啉桥接的cavitands与一个亚甲基，膦酸酯或磷酸酯桥的合成，x射线晶体学表征和“花瓶-风筝”转换行为的NMR分析。 。相对于喹喔啉桥联的类似物，吡嗪桥联的间苯二酚[4]芳烃cavitand对非极性溶剂中的风筝构象显示出乎意料的高度偏好。该观察结果导致了广泛的溶剂依赖性转换研究，这些研究提供了溶剂如何影响热花瓶-风筝平衡的详细图片。对于液相中的任何热力学过程，构象平衡受溶剂如何稳定两个单独状态的影响。适当大小的溶剂（苯和衍生物）可溶解花瓶模腔，并降低花瓶向风筝过渡的倾向。相应地，在不能渗透花瓶腔的大体积溶剂如均三甲苯中，风筝的几何形状变得优选。正如
• Multifold ring closing metathesis reactions in the formation of resorcin[4]arene cavitands
  作者：Sumedh Parulekar、Kirankirti Muppalla、Ali Husain、Kirpal S. Bisht

  DOI：10.1039/c5ra00760g

  日期：——

  the resorcin[4]arene cavitands using the ring closing metathesis reaction (RCM) in perallylated resorcin[4]arenes was investigated. The formation of resorcinarene cavitands offers unique molecular platforms for host–guest chemistries, sensor development, metal complexation, as well as new polymers and self-assembled systems, and as potential reaction sites, and novel catalytic platforms. In this manuscript

  研究了在高丙基化间苯二酚[4]芳烃中使用闭环易位反应（RCM）形成间苯二酚[4]芳烃空洞。间苯二甲烯空洞体的形成为客体化学，传感器开发，金属络合以及新型聚合物和自组装系统以及潜在的反应位点和新型催化平台提供了独特的分子平台。在该手稿中，我们显示了RCM反应形成的空泡在很大程度上取决于高渗间苯二酚[4]芳烃的上下边缘的构象和取代基。八羟基化合物的高丙基化破坏了分子内的氢键，导致构象异构体平衡的动态变化。
• Synthesis and Application of New Calix[4]Arenes‐Containing ( <i>R</i> )‐Phenylglycinol Chiral Stationary Phases for Enantioseparation
  作者：Kyu Sung Heo、Jae Jeong Ryoo

  DOI：10.1002/bkcs.12063

  日期：2020.7

  π‐acidic, π‐basic, and oxazolidinone chiral samples and was especially useful for separating chiral oxazolidinones. In comparison between CSP 2 and CSP 3, CSP 2 separated fewer chiral samples than CSP 3 because of poor cavity and steric interactions. The newly developed C‐methylcalix[4]resorcinarene derived CSP (CSP 3) will be a good model for the development of new stationary phase of this calixarene

  N -3,5-二硝基苯甲酰基-（R）-苯基甘氨醇甲硅烷基化产物用作高效液相色谱手性固定相（CSP 1），用于分离各种外消旋样品，并成功分离了一些外消旋样品。在这项研究中，代替常用的π-酸性酰氯，引入杯[4]芳烃来制备两种苯基甘醇CSP（CSP 2，CSP 3）。CSP 3的分离模式与CSP 1相似，但特定样品的特征不同。新制备的CSP 3分离了13个π-酸性，π-碱性和恶唑烷酮手性样品中的10个，特别适用于分离手性恶唑烷酮。在CSP 2和CSP 3之间进行比较，由于差的空腔和空间相互作用，CSP 2分离的手性样品少于CSP 3。新开发的C‐methylcalix [4]间苯二甲烯衍生的CSP（CSP 3）将是开发此杯芳烃系列新固定相的良好模型。