REQUIMTE, CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal.
Eur J Med Chem. 2010 Jun;45(6):2258-64. doi: 10.1016/j.ejmech.2010.01.071. Epub 2010 Feb 2.
The pyrazolone derivatives antipyrine and 4-(N,N-dimethyl)-aminoantipyrine (aminopyrine) have long been used as analgesic, antipyretic and anti-inflammatory drugs. However, in spite of its recognized therapeutic benefits, the use of pyrazolones has been associated with agranulocytosis. Though the oxidation of aminopyrine by neutrophil-generated hypochlorous acid (HOCl), leading to the formation of a cation radical, has been considered responsible for the potential bone marrow toxicity, the reaction mechanisms of pyrazolones against other reactive oxygen species (ROS) remains elusive. Thus, the reactions of 4-aminoantipyrine and methylated derivatives with hydroxyl radicals (HO*) were studied as a model of their reactivity against ROS. The results show that 4-(N,N-dimethyl)-aminoantipyrine (aminopyrine) undergoes demethylation when reacting with HO. radical, leading to 4-(N-methyl)-aminoantipyrine, which is further demethylated to 4-aminoantipyrine. In addition, it was also observed that another favorable reaction of 4-aminoantipyrines in these conditions is the hydroxylation on the aromatic ring, a reaction that is common to aminopyrine, 4-(N-methyl)-aminoantipyrine, and 4-aminoantipyrine. Whether these reaction mechanisms give rise to harmful reactive intermediates requires further chemico-biological evaluation.
吡唑酮衍生物安替比林和 4-(N,N-二甲基)-氨基安替比林(氨基比林)长期以来一直被用作镇痛药、解热药和消炎药。然而,尽管其具有公认的治疗益处,但吡唑酮的使用与粒细胞缺乏症有关。尽管中性粒细胞产生的次氯酸(HOCl)氧化氨基比林,导致阳离子自由基的形成,被认为是潜在的骨髓毒性的原因,但吡唑酮与其他活性氧(ROS)的反应机制仍然难以捉摸。因此,研究了 4-氨基安替比林和甲基化衍生物与羟基自由基(HO*)的反应,作为它们对 ROS 反应性的模型。结果表明,4-(N,N-二甲基)-氨基安替比林(氨基比林)与 HO 反应时会脱甲基。自由基,生成 4-(N-甲基)-氨基安替比林,进一步脱甲基生成 4-氨基安替比林。此外,还观察到在这些条件下 4-氨基安替比林的另一种有利反应是芳环上的羟化,这是氨基比林、4-(N-甲基)-氨基安替比林和 4-氨基安替比林的共同反应。这些反应机制是否会产生有害的活性中间体需要进一步的化学-生物学评估。