Synthesis, Structure, and Synthetic Potential of Arenediazonium Trifluoromethanesulfonates as Stable and Safe Diazonium Salts
Synthesis, Structure, and Synthetic Potential of Arenediazonium Trifluoromethanesulfonates as Stable and Safe Diazonium Salts
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稳定安全的重氮盐三氟甲磺酸芳烃重氮盐的合成、结构和合成潜力
DOI：
10.1002/ejoc.201800887
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发表时间：
2018
影响因子：
2.8
通讯作者：
V. A. Kataeva
中科院分区：
文献类型：
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作者：
V. Filimonov;E. Krasnokutskaya;Assia Zh. Kassanova;V. Fedorova;Ksenia S. Stankevich;N. Naumov;Alexander A. Bondarev;V. A. Kataeva
芳香族重氮盐是有机合成的重要组成部分；然而，在大多数情况下，它们是不稳定的、不安全的、难溶的和/或昂贵的。本文证明了在三氟甲烷磺酸存在下，苯胺与亚丁基亚硝酸盐重氮化反应可以容易、高产地制备出多种稳定、安全的三氟氨重氮盐ArN2+ tfo。三氟化氨重氮在干燥状态下相对稳定。它们很好地溶于水，以及极性甚至非极性有机溶剂。这些盐在热分解过程中释放的能量小于800 J/g，表明它们具有爆炸安全性。在已知的重氮化学反应中，三氟化arennediazonium triflates具有很高的反应活性，并且可以与氯仿和CCl4进行不含金属的氯重氮化反应。
Aromatic diazonium salts are valuable building blocks for organic synthesis; however, in most cases, they are unstable, unsafe, poorly soluble, and/or expensive. In this paper, we have shown that a variety of stable and safe arenediazonium triflates ArN2+TfO–can be obtained easily and in high yields by diazotization of anilines withtert‐butyl nitrite in the presence of trifluoromethanesulfonic acid. Arenediazonium triflates are relatively shelf‐stable in the dry state. They dissolve well in water, as well as polar and even nonpolar organic solvents. Less than 800 J/g of energy is released during the thermal decomposition of these salts, which indicates their explosion safety. Arenediazonium triflates have a high reactivity in the known reactions of diazonium chemistry, and undergo an unusual metal‐free chlorodediazonization reaction with chloroform and CCl4.