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m-Diethynylbenzene宏循环:在溶液中的合成和自我结合行为
Yoshito Tobe1, Naoto Utsumi, Kazuya Kawabata
1Department of Chemistry, Faculty of Engineering Science, Osaka University, and CREST, Japan. tobe@chem.es.osaka-u.ac.jp
Journal of the American Chemical Society
|May 9, 2002
概括
合成了m-Diethynylbenzene宏循环 (DBM),并研究了它们的自我关联行为. DBMs在溶剂中表现出独特的聚合,通过核和宏循环结构增强,导致比相关化合物更强的pi-pi堆叠.
科学领域:
- 超分子化学 超分子化学
- 有机合成 有机合成
- 材料科学 材料科学 材料科学
背景情况:
- 宏环化合物具有独特的结构和功能性质.
- 了解自我组装对于设计先进材料至关重要.
- 乙基宏循环 (DBMs) 是一种新型的循环分子.
研究的目的:
- 合成具有不同侧链的m-二乙基宏循环 (DBMs).
- 为了研究DBM在不同溶剂中的自我结合行为.
- 阐明宏环结构对聚合性质的影响.
主要方法:
- 通过氧化合或分子内循环合成DBM的循环四相,六相和八相.
- 使用1H NMR光谱和蒸汽压力奥斯米度 (VPO) 调查聚合性质.
- 与非循环寡合体和相关的乙烯宏循环进行比较分析.
主要成果:
- DBMs在和等溶剂中表现出独特的聚合行为,具有增强协会的核化机制.
- 聚合在极性溶剂中更强,这是由于对溶剂的恐惧,而在芳香溶剂中则是由于pi-pi堆叠而引起的.
- 带有大腔的六米DBM在芳香溶剂中显示特别高的关联常数.
- 由于提取电子的布塔迪因链接,DBMs比 fenilacetylene macrocycles 更容易聚合.
结论:
- 宏观环形结构显著影响DBMs的自我聚合倾向.
- DBM显示了可调节的聚合行为,取决于溶剂的极性和芳香度.
- 在DBMs中的布塔迪因连接增强了pi-pi堆叠相互作用,促进了自我关联.
相关概念视频
Structure of Conjugated Dienes
Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Stability of Conjugated Dienes
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.

