NO donors, part 11 -: Synthesis of diazen-1-ium-1,2-diolates monitored by the "NOtizer" apparatus:: Relationship between formation rates, molecular structure and the release of nitric oxide
NO donors, part 11 -: Synthesis of diazen-1-ium-1,2-diolates monitored by the "NOtizer" apparatus:: Relationship between formation rates, molecular structure and the release of nitric oxide
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DOI：
10.1002/ejoc.200600662
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发表时间：
2007-02-01
影响因子：
2.8
通讯作者：
Lehmann, Jochen
中科院分区：
文献类型：
--
作者：
Konter, Joerg;Abuo-Rahma, Gamal El-Din A. A.;Lehmann, Jochen
氮结合的二氮烯-1-鎓-1，2-二醇盐（二醇二氮烯鎓盐，“NONOates”，“固体NO”）通常由仲胺和一氧化氮制备，并且是直接释放一氧化氮（NO）的首选化合物。首先，我们报告的胺的结构和相应的NONOates的形成速率之间的关系，第二NONOates的结构和NO的释放速率，最后NONOate的形成和NO从这些物种的释放速率之间的关系。一系列不同大小和取代的环状和脂肪族胺被用来量化胺对NO的反应性，通过监测NO压力的降低与NOtizer，本研究开发的装置。NO的释放用NO敏感电极安培法测量，并且通过UV光谱法测定新型二醇二氮烯鎓盐的半衰期。研究发现，胺侧链上的空间位阻和杂原子取代基降低了NONOates钠盐的形成速率，也减缓了NO的释放。发现哌啶-2-羧酸衍生物的反应速度比哌啶慢，但释放NO快得多，尽管有空间位阻。携带额外的伯胺的仲胺与NO快速反应，但相应的NONOate由于形成分子内NONOate盐以及钠盐衍生物而显示出较慢的NO分解。氮杂环丁烷与NO的反应比所有其他胺更快，但相应NONOate的分解被证明是出乎意料的慢。(C)Wiley-VCH Verlag GmbH & Co.
Nitrogen-bound diazen-1-ium-1,2-diolates (diazeniumdiolates, "NONOates", "solid NO") are generally prepared from secondary amines and nitric oxide and are compounds of first choice for the direct release of nitric oxide (NO). First, we report on the relationships between the structures of the amines and the formation rates of the corresponding NONOates, second on the structures of the NONOates and the rate of NO release and finally between the rates of NONOate formation and NO release from these species. A series of differently sized and substituted cyclic and aliphatic amines were used to quantify the reactivity of amines towards NO by monitoring the decrease in NO pressure with the NOtizer, an apparatus developed for this study. The release of NO was measured amperometrically with an NO-sensitive electrode and the half-lives of novel diazeniumdiolates were determined by UV spectroscopy. It was found that steric hindrance and heteroatomic substituents in the amines' side chains reduce the formation rates of the sodium salts of the NONOates and also slow down NO release from them. Exceptions were found with piperidine-2-carboxylic acid derivatives which react to give NONOates more slowly than piperidine but release NO much faster despite steric hindrance. A secondary amine carrying an additional primary amine reacted quickly with NO, but the corresponding NONOate showed slower releaser of NO owing to the formation of an intramolecular NONOate salt as well as the sodium salt derivative. Azetidine reacts faster with NO than all of the other amines, but decomposition of the corresponding NONOate proved to be unexpectedly slow. (C) Wiley-VCH Verlag GmbH & Co.