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Synthesis and Characterization of Unstable Organic Molecules Using Photochemical Process at Low Temperature

低温光化学过程不稳定有机分子的合成与表征

基本信息

批准号：
01303002
负责人：
TOMIOKA Hideo
金额：
$ 4.86万
依托单位：
Mie University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01303002/
关键词：
Matrix Isolation Spectroscopy Theoretical Prediction Analysis of Reaction of Unstable Molecules Direct Observation of Unstable Molecules Neutral Divalent Species Strained Molecules Peroxides 02Synthesis of precursors Generating Unstable Mole

项目摘要

This research is undertaken in order to design and generate unstable organic molecules by utilizing mainly matrix isolation techniques. Investigators involved in the project have been selected from the following four major fields of physical organic chemistry so as to attack the target molecules of mutual interests from multilateral standpoints. The results obtained in each research fields are summarized :(1) Design and Synthesis of Precursor for Generating Unstable Organic Molecules - Several new precursors generating oxonium ylide, oxirenium, thirenium, and azirinium ions are designed and synthesized and are shown to be not only very attractive in reactive intermediate chemistry but also useful on synthetic viewpoints.(2) Product Analysis of the Reactions Involving Unstable Molecules - Reactions involving radicals, 1,4-diradicals, and 1,4-radical cations are investigated not only in organic solvent but also in the solid state and many useful information concerning the reaction mechan … More ism and biological meanings is obtained.(3) Spectroscopic Detection and Characterization of Unstable Organic Molecules - Unstable molecules such as carbenes, nitrenes, silylenes, benzotropone, carbonyl oxides, carbonyl ylides are detected and characterized by matrix isolation techniques. Magnetic interaction of polycarbenes and polynitrenes are revealed. Oxidation reactions within matrix containing oxidants such as O_2 and NO_2 are analyzed and mechanisms including reactive intermediates are proposed. Conformational isomers which are convertible under IR irradiation within matrix are analyzed and the mechanisms for the isomerization are suggested.(4) New theoretical methods to evaluate the effect of steric repulsion on the electronic structure of unstable molecules are proposed. The stabilities of the reactive molecules such as those involved in the reaction of sililenes and O_2 and three membered cyclic compounds consisting of Si, Ge, Sn and Pb are evaluated by theoretical calculation.These new find are discussed comprehensively in the joint meetings including participants outside of the group and new "challenging" molecules to be attacked are suggested. Less

本研究主要是利用基质分离技术来设计和生成不稳定的有机分子。项目研究人员从物理有机化学四大领域中遴选，从多边立场出发，研究共同感兴趣的目标分子。(1)制备不稳定有机分子的前驱体的设计与合成——设计合成了几种新的生成氧鎓、氧鎓、钍和氮离子的前驱体，这些前驱体不仅在反应中间体化学中很有吸引力，而且在合成方面也很有用。(2)不稳定分子反应的产物分析——不仅研究了有机溶剂中涉及自由基、1,4-二自由基和1,4-自由基阳离子的反应，而且还研究了固体中涉及自由基、1,4-二自由基和1,4-自由基阳离子的反应，并获得了许多有关反应机理的有用信息，获得了更多的理论和生物学意义。(3)不稳定有机分子的光谱检测和表征——通过基质分离技术检测和表征不稳定分子，如碳烯、亚硝基、硅烯、苯并托酮、羰基氧化物、羰基酰化物。揭示了聚碳烯和聚亚胺的磁相互作用。分析了含氧化剂O_2和NO_2的基质中的氧化反应，并提出了反应中间体的机理。分析了红外照射下在基体内可转化的构象异构体，并提出了异构化的机理。(4)提出了新的理论方法来评价空间斥力对不稳定分子电子结构的影响。用理论计算方法评价了硅烯与O_2反应分子和Si、Ge、Sn、Pb三元环化合物的稳定性。这些新发现在小组外的联席会议上进行了全面的讨论，并提出了新的“具有挑战性”的分子。少