perfluoroaryl tetrahedranes 的光异构化成 perfluoroaryl cyclobutadienes 的过程
Yusuke Inagaki1, Masaaki Nakamoto, Akira Sekiguchi
1Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
Journal of the American Chemical Society
|September 20, 2011
概括
研究人员通过光化学异构化合成了新的 perfluoroaryl-substituted 循环丁烯. 这些独特的化合物具有扭曲的矩形结构,具有异常长的碳-碳单键,为应力有机分子提供了新的见解.
科学领域:
- 有机化学 有机化学
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
背景情况:
- 循环丁是高度反应的,紧张的有机分子.
- 合成以基替代的环丁具有挑战性.
- perfluoroaryl 替代剂可以影响分子稳定性和反应性.
研究的目的:
- 为了合成和表征新的 perfluoroaryl-substituted 循环丁衍生物.
- 为了研究四面体的光化学异构化到环球丁.
- 阐明涉及这些化合物的敏感光化学反应的机制.
主要方法:
- 四面体 (4 和 5) 的光化学异构化为循环丁 (6 和 7).
- 9,10-二甲素敏感的光化学反应.
- 使用光谱数据进行表征 (NMR,质谱等). ) 的情况.
- 用X射线结晶学测定循环丁的结构 6.
主要成果:
- 成功合成了两种对空气和水分敏感的红色固体 perfluoroaryl-substituted 循环butanadienes (6 和 7).
- 四面体4和5的光化学异构化产生了环丁基6和7.
- 四面体4的9,10-二二甲敏感反应也产生了环丁 6.
- X射线晶体学揭示了6的扭曲矩形结构,具有异常长的C-C单键.
结论:
- 这项研究介绍了首次合成含有 perfluoroaryl 基的基替代环丁基.
- 光化学方法是产生这些应力环系统的有效方法.
- 独特的结构特征,包括延长的C-C键,提供了关于紧张有机分子中的结合的有价值数据.
相关概念视频
Thermal and Photochemical Electrocyclic Reactions: Overview
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[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.
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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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.
Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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