权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Analytical Study of the Combined Nitrogen Oxides and Ozone Systems and its Application to Organic Synthesis

氮氧化物和臭氧组合体系的分析研究及其在有机合成中的应用

基本信息

批准号：
08101003
负责人：
SUZUKI Hitomi
金额：
$ 64.64万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Specially Promoted Research
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1998
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08101003/
关键词：
Nitrogen oxides Nitration Ozone Nitro compounds Aromatic compounds Reaction mechanism Pollution Carcinogen 有機合成大気汚染

项目摘要

Lower nitrogen oxides such as nitrogen monoxide and dioxide are activated in the presence of ozone to react smoothly with a wide variety of aromatic compounds to give the corresponding mononitro or polynitro derivatives in good yield. Based on the kinetic studies as well as the product analyses, this novel type of aromatic nitration has been found to proceed via nitrogen trioxide, formed in situ from the interaction of nitrogen dioxide and ozone, as the initial electrophile. When aromatic substrates are of low oxidation potential, nitrogen trioxide oxidizes an aromatic substrate to generate a radical cation, which is trapped by nitrogen dioxide to form the nitroarenium ion, eventually leading to the expected nitro compound. When aromatic substrates have high oxidation potentials, nitrogen trioxide couples with nitrogen dioxide to form dinitrogen pentaoxide, which undergoes heterolysis to generate the nitronium ion and follow the course of conventional nitration. This non-acid methodology for preparative aromatic nitration is highly promising as a pollution-free substitute for the classical, yet currently ongoing, commercial process based on the use of nitric and sulfuric acid.From the airborne particulate collected in traffic-heavy urban area, a highly mutagenic and carcinogenic substance was isolated and identified as 3-nitrobenzanthrone. The reaction of nitrogen dioxide with benzanthrone adsorbed on inorganic support has been investigated in the presence or absence of ozone under artificial atmospheric conditions. The results suggest a possible role of nitrogen trioxide as an active species responsible for atmospheric nitration. As an extension of the present work, the nitration of bio-related aromatic species with peroxynitrite has also been investigated.

较低的氮氧化物如一氧化氮和二氧化氮在臭氧存在下被活化，与多种芳香族化合物顺利反应，以良好的收率得到相应的单硝基或多硝基衍生物。基于动力学研究和产物分析，发现这种新型芳香族硝化是通过二氧化氮和臭氧相互作用原位形成的三氧化氮作为初始亲电子试剂进行的。当芳香族底物氧化电位较低时，三氧化二氮氧化芳香族底物产生自由基阳离子，自由基阳离子被二氧化氮捕获形成硝基芳鎓离子，最终生成预期的硝基化合物。当芳香族底物具有高氧化电位时，三氧化二氮与二氧化氮偶联形成五氧化二氮，五氧化二氮发生异解生成硝鎓离子并遵循常规硝化过程。这种用于制备芳族硝化的非酸方法非常有希望成为一种无污染的替代品，替代基于使用硝酸和硫酸的经典但目前正在进行的商业工艺。从交通繁忙的城市地区收集的空气颗粒物中，分离出一种高度致突变和致癌物质，并鉴定为 3-硝基苯并蒽酮。在人造大气条件下，在存在或不存在臭氧的情况下，研究了二氧化氮与吸附在无机载体上的苯并蒽酮的反应。结果表明三氧化氮可能作为大气硝化的活性物质发挥作用。作为当前工作的延伸，还研究了过氧亚硝酸盐对生物相关芳香族物质的硝化。