Development of Novel Cyclic Structures Possessing Inclusion, Self-Assembly, and Self-Organization Properties

具有包含、自组装和自组织特性的新型环状结构的开发

• 批准号: 10440182
• 负责人: TSUJI Takashi
• 金额: $ 6.59万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10440182/
• 关键词: supramolecule; inclusion; self-organization; self-assembly; macrocycle

[l] Syntheses and Properties of Novel Receptors Possessing Hydrindacene Skeleton Hydrindacene skeleton is consisted of rigid central aromatic ring and flexible peripheral 5-membered rings, and its intermolecular interactions are expected to be adequately regulated by functionalizing those rings with suitable substituents. In this study, the development of title receptors was investigated on the basis of those expectations.The preparation of several substituted derivatives followed by their X-ray structural analyses revealed that the 5-membered rings prefer an envelope conformation and the less bulky substituents (Rs) are disposed nearly parallel to each other at a distance of ca. 7.0 Å, twice the interlayer distance in graphite. Those structural chacteristics were exploited to the design of novel multiply functionalized receptor molecules which preferentially associate with specific stubstrates. Thus, the (Z) Rs = arylethynyl/R_L = alkoxycarbonyl derivatives seem to incorporate aromatic substrates between the arylethynyl groups, facilitated by the π-π stacking interactions. The Rs = alkoxycarbonyl/R_L = aryl derivatives were also prepared and utilized to construct macrocyclic receptors in which the former substituents are oriented to the inside of the cycles.[2] Preparation of Functionalized Phenylene-ethynylene Macrocycles 1,4-Bridged dichloro-Dewar benzenes are accessible in 4 steps from DMAD and dichloroethylene. Functionalized m- and p-phenylene groups are conveniently incorporated into macrocycles by taking advantage of their equivalency to bent benzene derivatives. Thus, their alternating (2 : 2) coupling- cyclization with diethynylbenzenes followed by hydrolysis and aromatization provided functionalized phenylene-ethynylene macrocycles which were otherwise diffiucult to access.

[L]具有氢杂环骨架的新型受体的合成与性质氢杂环是由刚性的中心芳环和柔性的外围5元环组成，通过对这些环进行适当的取代基官能化，有望充分调节其分子间的相互作用。在这项研究的基础上，研究了TITLE受体的发展。几种取代衍生物的制备和X射线结构分析表明，5元环更倾向于包络构象，较小的取代基(Rs)几乎平行地排列在大约7.0Å的距离处，是石墨层间距的两倍。这些结构特征被用来设计新型的多功能化受体分子，这些分子优先与特定的残基结合。因此，在π-π堆积作用的促进下，(Z)Rs=芳乙炔/R_L=烷氧羰基衍生物似乎在芳乙炔基团之间结合了芳香族底物。还合成了Rs=烷氧羰基/R_L=芳基的大环受体，其中前取代基位于环的内侧。[2]官能化的苯乙炔大环1，4-桥联二氯杜瓦苯的制备由DMAD和二氯乙烯经4步反应即可完成。官能化的间苯基和对苯亚基通过与弯曲苯衍生物的等价性被方便地结合到大环中。因此，它们与二乙炔基苯交替(2：2)偶联-环化，然后水解和芳构化，提供了功能化的苯乙炔大环，否则很难获得。

项目成果

T.Tsuji: "Extremely Strained Paracyclophanes: Preparation,Structures,and Properties" Adv.Strained and Interesting Org.Mol.7(in press). (1999)

T.Tsuji：“极度紧张的对环芳烷：制备、结构和性质”Adv.Strained and Interesting Org.Mol.7（印刷中）。

T.Suzuki: "Supramolecular Aggregation of m-Nitrobenzoic Acid by C-H・・・O and O-H・・・O Hydrogen Bondings in the Crystalline Charge-Transfer Complexes with Aromatic Hydrocarbons"J.Org.Chem. 64. 7103-7113 (1999)

T.Suzuki：“芳香烃晶体电荷转移配合物中 C-H…O 和 O-H…O 氢键对间硝基苯甲酸的超分子聚集”J.Org.Chem. 64. 7103-7113 (1999)

H.Kawai: "Kinetic Stabilization of [1.1] Paracyclophane System. Isolation and X-ray Structural Analysis of a [1.1] Paracyclophane Derivative and its Interconversion with the Transannular Adduct"Chem.Eur.J.. (in press). (2000)

H.Kawai：“[1.1] 对环芳烷系统的动力学稳定性。[1.1] 对环芳烷衍生物的分离和 X 射线结构分析及其与跨环加合物的相互转化”Chem.Eur.J.（出版中）。

H.Kawai: "A Kinetically Stabilized[1.1]Paracyclophane : Isolation and X-Ray Structural Analysis" Angew.Chem.,Int.Ed.Engl.37・6. 817-819 (1998)

H.Kawai：“动力学稳定的[1.1]对环芳烷：分离和 X 射线结构分析”Angew.Chem.，Int.Ed.Engl.37・6（1998）。

T.Suzuki: "Biphenyl-Type Electron Acceptors Exhibiting Dynamic Redox Properties : a Novel Electrochromic System with "Write Protect" Option"J.Chem.Soc., Chem.Commun.. 1331-1332 (1998)

T.Suzuki：“展现动态氧化还原特性的联苯型电子受体：具有“写保护”选项的新型电致变色系统”J.Chem.Soc.、Chem.Commun.. 1331-1332 (1998)