Saraiva Marco A, Borges Carlos M, Florêncio M Helena
Centro de Química Estrutural, Instituto Superior Técnico, Campus Alameda, Av. Rovisco Pais, Torre Sul, 1049-001 Lisbon, Portugal.
Eur J Mass Spectrom (Chichester). 2012;18(4):385-97. doi: 10.1255/ejms.1191.
Aminoguanidine possesses extensive pharmacological properties. This drug is recognized as a powerful α-dicarbonyl scavenger. In order to better elucidate the reactivity of aminoguanidine with α-dicarbonyls, aminoguanidine was reacted with several aldehydic and diketonic α-dicarbonyls. Electrospray ionization mass spectrometry is a suitable technique to study chemical and biochemical processes, and was selected for the purpose. In aminoguanidine reactions, triazines were detected and, other compounds that have never been reported before were identified. Triazine precursor forms were detected, namely tetrahydrotriazines and singly dehydrated tetrahydrotriazines. Moreover, species with bicyclic ring structures, and dehydrated forms, were also identified in aminoguanidine reactions. These species appear to result from tetrahydrotriazines and triazines reactions with one dicarbonyl molecule. Experiments revealed that these bicyclic species, in particular the ones resulting from triazines reactivity, could exist in solution, since they were both identified in the reactions of aminoguanidine and of a selected triazine with the dicarbonyls studied. The results obtained, regarding aminoguanidine/triazines reactivities, appear to support the capability of triazines to condensate and form polycyclic ring structures, and also to support literature mechanistic data for dihydroimidazotriazines formation via dihydroxyimidazolidine-triazines. The data obtained in this study may prove to be valuable to complement solution information, concerning the reactivity of amines with α-dicarbonyls, in particular.
氨基胍具有广泛的药理特性。这种药物被认为是一种强大的α-二羰基清除剂。为了更好地阐明氨基胍与α-二羰基的反应活性，使氨基胍与几种醛类和二酮类α-二羰基化合物发生反应。电喷雾电离质谱是研究化学和生化过程的一种合适技术，为此被选用。在氨基胍反应中，检测到了三嗪，并鉴定出了其他以前从未报道过的化合物。检测到了三嗪前体形式，即四氢三嗪和单脱水四氢三嗪。此外，在氨基胍反应中还鉴定出了具有双环结构的物种及其脱水形式。这些物种似乎是由四氢三嗪和三嗪与一个二羰基分子反应产生的。实验表明，这些双环物种，特别是由三嗪反应产生的那些，能够存在于溶液中，因为它们在氨基胍以及选定的一种三嗪与所研究的二羰基化合物的反应中都被鉴定出来了。关于氨基胍/三嗪反应活性所获得的结果，似乎支持三嗪缩合形成多环结构的能力，也支持关于通过二羟基咪唑烷 - 三嗪形成二氢咪唑并三嗪的文献机理数据。本研究中获得的数据可能被证明对于补充溶液信息很有价值，特别是关于胺与α-二羰基反应活性的信息。
