Development of A Novel Non-Acid Methodology for Aromatic Nitratio

开发一种新型非酸芳香硝化方法

• 批准号: 05554023
• 负责人: SUZUKI Hitomi
• 金额: $ 11.2万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05554023/
• 关键词: Nitration; Aromatics; Nitrogen dioxide; Ozone; Cation radical; Reaction mechanism; 置換ベンゼン; 五酸化二窒素; 三酸化窒素

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.

本文提出了一种新的非酸硝化方法，即以臭氧化空气和第三种物质为促进剂，用低氮氧化物硝化芳香族化合物。该反应被称为kyodai-硝化反应，目前正在工业上进行研究，作为一种有前途的无污染和节能的替代品，替代了基于硝酸-硫酸使用的已有百年历史但目前仍在进行的商业化工艺。芳族羰基化合物、缩醛、缩醛和蒽醌;苯甲酸、其盐、酯、酰氯、腈和酰胺;硝基苯和烷基衍生物;酰苯胺和酚酯;吡啶和烷基衍生物;萘和衍生物;对于这种新型的芳香硝化反应，我们提出了一种反应机理，其中反应进行的双模式取决于芳香底物的氧化电位;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底物形成阳离子自由基，作为环取代的中间体。在没有合适的可氧化底物的情况下，三氧化二氮被另一分子二氧化氮捕获，形成五氧化二氮，五氧化二氮在酸催化剂存在下是一种强有力的硝化剂。尽管在某些方面与现有方法互补，但kyodai硝化非常有希望为当今化学工业面临的问题之一提供解决方案。

项目成果

Hitomi Suzuki: "Ozone-mediated Reaction of Aromatic Acetals and Acylal with Nitrogen Dioxide: A Novel Methodology for the Nuclear Nitration of Acid-Sensitive Aromatic Com-..." J. Chem. Soc., Perkin Trans. 1. 1367-1369 (1994)

Hitomi Suzuki：“芳香族缩醛和酰醛与二氧化氮的臭氧介导反应：酸敏感芳香族化合物核硝化的新方法......”J. Chem。

Hitomi Suzuki, Atsuo Tatsumi, Taro Ishibashi: "Ozone-mediated Reaction of Anilides and Phenyl Esters with Nitrogen Dioxide. Enhanced Ortho Reactivity and Mechanistic Implications" J.Chem.Soc., Perkin Trans.1. 339-343 (1995)

Hitomi Suzuki、Atsuo Tatsumi、Taro Ishibashi：“臭氧介导的苯胺和苯酯与二氧化氮的反应。增强的邻位反应性和机理影响”J.Chem.Soc.，Perkin Trans.1。

Hitomi Suzuki: "Ozone-mediated Nitration of Benzoic Acid, its Alkaline and Alkaline-Earth Salts, Ester, Acid Chloride, Nitrile and Amide with Nitrogen Dioxide" J. Chem. Soc., Perkin Trans. 1. 2413-2416 (1994)

Hitomi Suzuki：“臭氧介导的苯甲酸、其碱性盐和碱土盐、酯、酰氯、腈和酰胺与二氧化氮的硝化”J. Chem。

Hitimi Suzuki: "Ozone-mediated Nitration of Aromatic Ketones and Related Compounds with Nitrogen Dioxide" J. Chem. Soc., Perkin TRans. 1,. 903-908 (1994)

Hitimi Suzuki：“臭氧介导的芳香酮及相关化合物与二氧化氮的硝化”J. Chem。

Hitomi Suzuki: "Ozone-mediated Reaction of Polychlorobenzenes and Some Related Halogeno Compounds with Nitrogen Dioxide. A Novel Non-acid Methodology for the Selective Mono-..." Synthesis. 841-845 (1994)

Hitomi Suzuki：“多氯苯和一些相关卤素化合物与二氧化氮的臭氧介导反应。一种用于选择性单...合成的新型非酸性方法。”