Development of A Novel Non-Acid Methodology for Aromatic Nitratio

发展了一种新的非酸性硝化方法，以臭氧空气和第三种物质为促进剂，以较低的氮氧化物制备芳香族化合物。目前，这种新型硝化反应所产生的芳香族化合物包括苯和烷基衍生物；卤代苯；芳香族羰基化合物、缩醛、缩醛和蒽二酮；苯甲酸及其盐类、酯类、氯化酸、腈和酰胺类化合物；硝基苯和烷基衍生物；苯胺类和苯酚酯类化合物；吡啶和烷基衍生物；萘及其衍生物；对于这种新型的芳香族硝化反应，我们提出了一种依赖于芳香族底物氧化电位的双模式反应机理，二氧化氮与臭氧反应生成三氧化二氮，三氧化二氮氧化芳香族底物形成阳离子自由基，作为中间体到环的取代。在没有合适的可氧化底物的情况下，三氧化二氮被另一个二氧化氮分子捕获生成五氧化二氮，在酸催化下是一种强大的硝化剂。尽管在某些方面补充了现有的方法，但京代硝化是一种非常有希望的解决当今化学工业所面临的问题的方法。

A novel non-acid methodology for the preparative nitration of aromatic compounds with the lower oxides of nitrogen using a combination of ozonized air and some third substance as the promoter has been developed. The reaction, referred to as the kyodai-nitration, is now subject to industrially based research as the promising pollution-free and energy-saving substitute for the century-old, yet currently ongoing commercial process based on the use of nitric acid-sulfuric acid.Aromatic compounds sudjected to the present novel type of nitration include benzene and alkyl derivatives ; halogenobenzenes ; Aromatic carbonyl compounds, acetals, acylals and anthraguinones ; benzoic acid, its salts, ester, acid chloride, nitrile and amide ; nitrobenzene and alkyl derivatives ; anilides and phenolic esters ; pyridiue and alkyl derivatives ; naphthalene and derivatives ; benzyl cvanide and trifluoromethylbenzene.For this novel type of aromatic nitration, we have proposed a mechanism in which the reaction proceeds a dual mode depending on the oxidation potential of aromatic substrate ; nitrogen dioxide reacts with ozone to give nitrogen trioxide, which oxidizes aromatic substrate to form cation radical as an intermediate to ring substitution. In the absence of an appropriate oxidizable substrate, nitorgen trioxide is trapped by another molecule of nitrogen dioxide to form dinitrogen pentaoxide, which is a powerful nitrating agent in the presence of acid catalyst.Although in some respect complimentary to the existing methodology, the kyodai-nitration is highly promising to provide a solution to one of the nowadays problem which the chemical industry is facing.