Wang Zhe-Chen, Li Ya-Ke, He Sheng-Gui, Bierbaum Veronica M
1 Department of Chemistry, University of Colorado, Boulder, CO, USA.
2 Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
Eur J Mass Spectrom (Chichester). 2019 Feb;25(1):82-85. doi: 10.1177/1469066718799732. Epub 2018 Sep 6.
The strategy of synthesizing diazeniumdiolates (X-N(O)=NO) through the coexistence of nitric oxide and alkoxides (RO) was introduced by Wilhelm Traube 120 years ago. Today, despite the wide use of diazeniumdiolate derivatives to release nitric oxide in the treatment of cancer, the first step of the reaction mechanism for diazeniumdiolate synthesis remains a mystery and is thought to be complex. We have studied the gas-phase reactions of nitric oxide with alkoxides at room temperature. An electron-coupled hydrogen transfer is observed, and the radical anion HNO is the only ionic product in these reactions. HNO can further react with nitric oxide to form NO and HO.
120年前，威廉·特劳贝提出了通过一氧化氮与醇盐（RO）共存来合成重氮二醇盐（X-N(O)=NO）的策略。如今，尽管重氮二醇盐衍生物在癌症治疗中广泛用于释放一氧化氮，但其合成反应机制的第一步仍然是个谜，且被认为很复杂。我们研究了室温下一氧化氮与醇盐的气相反应。观察到了电子耦合氢转移，并且自由基阴离子HNO是这些反应中唯一的离子产物。HNO可进一步与一氧化氮反应生成NO和HO。
