25,26,27,28-tetramethoxy-2,8,16,22-tetrathiacalix[4]arene | 219797-71-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 25,26,27,28-tetramethoxy-2,8,16,22-tetrathiacalix[4]arene
• 英文别名: 12,32,52,72-Tetramethoxy-2,4,6,8-tetrathia-1,3,5,7(1,3)-tetrabenzenacyclooctaphane；25,26,27,28-tetramethoxy-2,8,14,20-tetrathiapentacyclo[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
• CAS: 219797-71-4
• 化学式: C₂₈H₂₄O₄S₄
• 分子量: 552.76
• InChiKey: QNWHSJIICOJZBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  36
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  25,26,27,28-tetramethoxy-2,8,16,22-tetrathiacalix[4]arene 在 三甲基溴硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 168.0h， 以22%的产率得到26,27,28-Trimethoxy-2,8,14,20-tetrathiapentacyclo[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-dodecaen-25-ol
  参考文献：
  名称：

  部分O烷基化的硫杂杯[4]芳烃：合成，分子和晶体结构，构象行为

  摘要：

  核磁共振波谱，X射线衍射分析和量子化学计算被用于在下部边缘带有甲基（1），乙基（2）或丙基（3）基团的部分烷基化的硫杂杯[4]芳烃的构象行为研究。构象性质受两个基本作用支配：（i）通过分子内氢键的稳定作用，和（ii）在较低边缘的烷氧基的空间要求。尽管单取代的衍生物1A和3a中采用在溶液中，二取代的远侧化合物锥形构象1B，1 “ b，2B，2 ” b，图3b，和3 ' b表现出了一些有趣的构象特征。他们更喜欢捏锥形构象在溶液中，并且，除了3 ' b，它们也形成1,2-交替构象，这是两个相同的结构之间的柔性并经历相当快的过渡。的化合物的晶体结构1B，2B，2 ' b，和图3b显示又相当罕见1,2-交替构形成通过π-π相互作用维持在一起的分子通道。具有六角对称性的不同通道，宽度为0.26 nm在3b的收缩锥构象的晶体结构中形成了α- δ。一种不常见的氢键模式是在二甲氧基和二丙氧基衍生物发现1 “

  DOI：

  10.1021/jo070927i
• 作为产物：
  描述：

  25,26,27,28-tetrahydroxy-2,8,14,20-tetrathiacalix[4]arene 、 碘甲烷 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 以85%的产率得到25,26,27,28-tetramethoxy-2,8,16,22-tetrathiacalix[4]arene
  参考文献：
  名称：

  Conformational behaviour of tetramethoxythiacalix[4]arenes: solution versus solid-state study

  摘要：

  The conformational behaviour of simple thiacalix[4]arene derivatives was studied using a combination of NMR spectroscopy and X-ray diffraction analysis. The 25,26,27,28-tetramethoxythiacalix[4]arene was found to adopt an unprecedented solid-state structure, where the cone and 1,3-alternate conformers co-exist in the crystal lattice in the 3:1 ratio. This phenomenon reflects the basically distinct conformational behaviour of thiacalix[4]arene skeleton as compared with classical calixarenes. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)01171-2

文献信息

• Stereoselective oxidation of thiacalix[4]arenes with the NaNO3/CF3COOH system
  作者：P LHOTAK、J MORAVEK、T SMEJKAL、I STIBOR、J SYKORA

  DOI：10.1016/s0040-4039(03)01868-9

  日期：2003.9.22

  A series of alkyl substituted thiacalix[4]arene derivatives (being conformationally mobile or immobilised in the cone conformation) was used as the starting point for this study. It was demonstrated that the NaNO3/CF3COOH system can serve as an excellent oxidising agent. The oxidation of the bridging sulphur atoms smoothly leads to the corresponding tetrasulfoxides where alkyl and sulfoxide groups

  一系列烷基取代的硫杂杯[4]芳烃衍生物（构象可移动或固定在圆锥构象上）被用作本研究的起点。已证明NaNO 3 / CF 3 COOH体系可以用作优良的氧化剂。桥连的硫原子的氧化平稳地产生相应的四亚砜，其中烷基和亚砜基团以立体选择的方式在相反的方向上取向。
• NMR and X-ray analysis of 25,27-dimethoxythiacalix[4]arene: unique infinite channels in the solid state
  作者：Pavel Lhoták、Lukáš Kaplánek、Ivan Stibor、Jan Lang、Hana Dvořáková、Richard Hrabal、Jan Sýkora

  DOI：10.1016/s0040-4039(00)01696-8

  日期：2000.11

  The conformational behaviour of 25,27-dimethoxythiacalix[4]arene was studied using NMR techniques and X-ray analysis. The title compound prefers a cone conformation in solution, while in the solid state it adopts a unique 1,2-alternate conformation thus creating a novel type of molecular channel held together by π–π interactions.

  25,27-dimethoxythiacalix [4] arene的构象行为使用NMR技术和X射线分析进行了研究。标题化合物更喜欢溶液中的圆锥构象，而在固态时，它采用独特的1,2-交替构象，从而通过π-π相互作用形成了一种新型的分子通道。
• Tetraalkylated 2,8,14,20-tetrathiacalix[4]arenes: Novel infinite channels in the solid state
  作者：Pavel Lhota´k、Michal Himl、Svetlana Pakhomova、Ivan Stibor

  DOI：10.1016/s0040-4039(98)01950-9

  日期：1998.11

  The synthesis of new tetraalkylated derivatives of 2,8,14,20-tetrathiacalix[4]arenes was achieved by the refluxing of thiacalixarenes in acetone or acetonitrile with the alkylation agent (R-I, R-Br) in the presence of K2CO3 or Cs2CO3. The structure of the tetraalkylated thiacalix[4]arenes was studied hy means of H-1 NMR experiments proving the 1.3-alternate conformation under measurement conditions (CDCl3, room temperature). The same conformation was established by X-ray analysis in the solid state where these derivatives create nice infinite channels. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Partially O-Alkylated Thiacalix[4]arenes:  Synthesis, Molecular and Crystal Structures, Conformational Behavior
  作者：Hana Dvořáková、Jan Lang、Jiří Vlach、Jan Sýkora、Michal Čajan、Michal Himl、Michaela Pojarová、Ivan Stibor、Pavel Lhoták

  DOI：10.1021/jo070927i

  日期：2007.9.1

  3a adopt the cone conformation in solution, distally disubstituted compounds 1b, 1‘b, 2b, 2‘b, 3b, and 3‘b exhibit several interesting conformational features. They prefer pinched cone conformation in solution, and, except for 3‘b, they form also 1,2-alternate conformation, which is flexible and undergoes rather fast transition between two identical structures. The crystal structures of the compounds

  核磁共振波谱，X射线衍射分析和量子化学计算被用于在下部边缘带有甲基（1），乙基（2）或丙基（3）基团的部分烷基化的硫杂杯[4]芳烃的构象行为研究。构象性质受两个基本作用支配：（i）通过分子内氢键的稳定作用，和（ii）在较低边缘的烷氧基的空间要求。尽管单取代的衍生物1A和3a中采用在溶液中，二取代的远侧化合物锥形构象1B，1 “ b，2B，2 ” b，图3b，和3 ' b表现出了一些有趣的构象特征。他们更喜欢捏锥形构象在溶液中，并且，除了3 ' b，它们也形成1,2-交替构象，这是两个相同的结构之间的柔性并经历相当快的过渡。的化合物的晶体结构1B，2B，2 ' b，和图3b显示又相当罕见1,2-交替构形成通过π-π相互作用维持在一起的分子通道。具有六角对称性的不同通道，宽度为0.26 nm在3b的收缩锥构象的晶体结构中形成了α- δ。一种不常见的氢键模式是在二甲氧基和二丙氧基衍生物发现1 “
• Conformational behaviour of tetramethoxythiacalix[4]arenes: solution versus solid-state study
  作者：Pavel Lhoták、Michal Himl、Ivan Stibor、Jan Sýkora、Hana Dvořáková、Jan Lang、Hana Petřı́čková

  DOI：10.1016/s0040-4020(03)01171-2

  日期：2003.9

  The conformational behaviour of simple thiacalix[4]arene derivatives was studied using a combination of NMR spectroscopy and X-ray diffraction analysis. The 25,26,27,28-tetramethoxythiacalix[4]arene was found to adopt an unprecedented solid-state structure, where the cone and 1,3-alternate conformers co-exist in the crystal lattice in the 3:1 ratio. This phenomenon reflects the basically distinct conformational behaviour of thiacalix[4]arene skeleton as compared with classical calixarenes. (C) 2003 Elsevier Ltd. All rights reserved.