Center for Integrated Technology and Organic Synthesis (CiTOS), MolSys Research Unit, University of Liège, B6a, Room 3/19, Allée du Six Août 13, 4000, Liège, Sart Tilman, Belgium.
Angew Chem Int Ed Engl. 2022 Oct 10;61(41):e202210146. doi: 10.1002/anie.202210146. Epub 2022 Sep 2.
Dinitrogen trioxide (N O ) is a powerful and efficient nitrosating agent that comes with an unprecedented atom economy. However, the synthetic application of N O is still underdeveloped mostly due to its inherent instability and the lack of reliable protocols for its preparation. This paper presents an open-source setup and procedure for the on-demand generation of anhydrous N O solution (up to 1 M), which can be further used for reactions under batch and flow conditions. The accuracy and stability of N O concentration are guaranteed with the absence of head-space in the setup and with the synchronization of the gas flows. The reliability of this protocol is demonstrated by >30 worked examples in the nitrosative synthesis of heterocycles-a library of structurally diverse benzotriazoles and sydnones. Kinetic and mechanistic aspects of the N-nitrosative steps are also explored.
三氧化二氮（N 2 O 3 ）是一种强大且高效的亚硝化试剂，具有前所未有的原子经济性。然而，由于其内在的不稳定性以及缺乏可靠的制备方案，N 2 O 3 的合成应用仍欠发达。本文介绍了一种用于按需生成无水 N 2 O 3 溶液（最高 1M）的开源设备和方法，该溶液可进一步用于分批和流动条件下的反应。该设备不存在气相空间，气体流量同步，从而保证了 N 2 O 3 浓度的准确性和稳定性。通过 30 多个杂环氮芥合成的实例，证明了该方案的可靠性-这是一个结构多样的苯并三唑和 sydnones 库。还探索了 N-亚硝化步骤的动力学和机理方面。
