Department of Chemistry, Universidade Federal do Paraná, CP 19081, CEP 81531-990, Curitiba-PR, Brazil.
Departamento Acadêmico de Química e Biologia, Universidade Tecnológica Federal do Paraná, Curitiba, PR, ZIP, 81280-340, Brazil.
Chemistry. 2019 Jan 14;25(3):817-822. doi: 10.1002/chem.201804107. Epub 2018 Dec 11.
Organophosphates (OPs) constitute many toxic agrochemicals and warfare and can undergo a wide spectrum of mechanisms, some which are fairly unexplored. In this sense, concise mechanistic elucidation stands out as a strategic tool for achieving efficient detoxification and for monitoring processes. Particularly intriguing is the effect of substituting the oxygen atom of the phosphoryl moiety (P=O) in OPs with a sulfur atom to give the thio-derived OPs (i.e., OTPs, P=S). In general, imidazole (IMZ) reacts very efficiently with OPs by targeting the phosphorus atom, although herein we evidence a thio-driven shift with OTPs: IMZ undergoes unusual nucleophilic attack at the aliphatic carbon atom of methyl parathion. Alkylation of IMZ under mild conditions (aqueous weakly basic medium) is also novel and should be applicable to other novel IMZ-based architectures, and thereby, it can be a great ally for organic synthesis. Overall, a broader understanding of the mechanistic trend involved in such highly toxic agents is provided.
有机磷酸酯 (OPs) 是许多有毒的农用化学品和军用化学品，它们可以通过多种机制发生作用，其中一些机制还尚未得到充分探索。在这个意义上，简洁的机制阐明是实现高效解毒和监测过程的战略工具。特别有趣的是，用硫原子取代有机磷酸酯中磷酰基（P=O）上的氧原子来生成硫代衍生的有机磷酸酯（即 OTPs，P=S）的效果。通常，咪唑 (IMZ) 通过靶向磷原子非常有效地与 OPs 反应，尽管在这里我们证明了与 OTPs 的硫驱动转移：IMZ 在甲基对氧磷的脂肪碳原子上经历了不寻常的亲核攻击。IMZ 在温和条件下（弱碱性水介质）的烷基化也是新颖的，应该适用于其他新型 IMZ 基架构，因此，它可以成为有机合成的得力助手。总的来说，为理解此类剧毒物质涉及的机制趋势提供了更广泛的认识。
