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Study of Organic Reaction Processes by the Use of Low-Temperature Matrix-Isolation Technique

利用低温基质分离技术研究有机反应过程

基本信息

批准号：
09440214
负责人：
MURATA Shigeru
金额：
$ 3.9万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440214/
关键词：
Matrix Isolation Technique Short-lived Reactive Intermediate Photochemistry Carbene

项目摘要

The object of this research is to establish the low-temperature matrix-isolation method as a general technique for the study of an organic reaction mechanism by the expansion of the application range of this technique. In order to make possible to apply this technique to less volatile substrates and to reactive intermediates generated by a large apparatus such as laser and flash vacuum pyrolysis, an inner-rotation mechanism was employed in the low-temperature matrix-isolation apparatus which was designed and set up with the aid of this grant. The ability of this new apparatus to make a low-temperature matrix satisfactory for spectroscopic observations was confirmed by the isolation of p-nitorophenyl azide in an argon matrix and comparison of its IR spectrum with that recorded previously using the other apparatus. The direct observation of the processes of the reaction of p-nitrophenylcarbene (1) with acetonitrile was examined next. Irradiation of (p-nitrophenyl)diazomethane matrix-isolated in argon doped with acetonitrile at 10K gave the carbene 1, which reacted with acetonitrile photochemically or thermally. The reactions were nicely monitored by IR and UV-Vis spectroscopy to find that the product formed by the further photolysis of 1 in an acetonitrile-doped matrix was different from that obtained thermally in the matrix. The structure of these products was estimated on the basis of the isotope experiment and DFT calculations. These preliminary results were suggested that the low-temperature matrix-isolation technique would be a powerful method for studying the reaction mechanism of organic reactive intermediates.

本研究的目的是通过扩大低温基质分离法的应用范围，使其成为研究有机反应机理的通用技术。为了使这一技术能够应用于不太挥发性的基板和反应性中间体产生的大型设备，如激光和闪速真空热解，内旋转机构采用的低温基质隔离装置，这是设计和建立的援助，该授权。这种新装置的能力，使低温矩阵满意的光谱观测证实了对硝基苯基叠氮在氩气矩阵中的分离和比较其红外光谱与以前记录的使用其他设备。接下来检查对硝基苯基卡宾（1）与乙腈反应过程的直接观察。对硝基苯基重氮甲烷在掺有乙腈的氩气中于10 K辐照得到卡宾1，卡宾1与乙腈发生光化学或热反应。通过IR和UV-Vis光谱很好地监测了反应，发现在乙腈掺杂的基质中通过1的进一步光解形成的产物不同于在基质中热获得的产物。根据同位素实验和密度泛函理论计算，对产物的结构进行了估算。这些初步结果表明，低温基质分离技术将是研究有机反应中间体反应机理的一种有力手段。