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Interactions of antithyroid drugs and their analogues with halogens and their biological implications

机译:抗甲状腺药物及其类似物与卤素的相互作用及其生物学意义

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The selenium analogue of antithyroid drug methimazole (MSeI) reacts with molecular bromine to produce two different types of novel complexes depending upon the molar ratio of MSeI to Br_2 in the reaction medium. Dicationic diselenide complex with two Br-ions as counterions is produced in the reaction of MSeI with 0.5 equiv of Br_2 (MSeI/Br _2, 1.0:0.5), whereas a stable 10-Se-3 hypervalent "T-shaped" complex featuring a linear Br-Se-Br moiety was produced when MSeI was treated with Br_2 in an equimolar ratio (MSeI/Br _2, 1.0:1.0). A substitution at the free N-H group in MSeI alters its reactivity toward iodine/bromine. For example, the N,N-disubstituted selones exclusively produce the corresponding 10-Se-3 hypervalent "T-shaped" complexes in the reaction with I_2. In the presence of the lectoperoxidase/H_2O_2/I~- system, N,N-dimethylimidazole-2-selone produces the corresponding dicationic diselenide with two I- counterions as the final metabolite. The formation of ionic species in these reactions is confirmed by single crystal X-ray diffraction studies and in some cases by Fourier transform-Raman spectroscopic investigations.
机译:取决于反应介质中MSeI与Br_2的摩尔比,抗甲状腺药Methimazole(MSeI)的硒类似物与分子溴反应生成两种不同类型的新型配合物。 MSeI与0.5当量的Br_2(MSeI / Br _2,1.0:0.5)反应生成带有两个Br离子作为抗衡离子的二阳离子二硒化物配合物,而稳定的10-Se-3高价“ T形”配合物具有当用等摩尔比(MSeI / Br _2,1.0:1.0)的Br_2处理MSeI时,产生线性Br-Se-Br部分。 MSeI中游离N-H基团的取代会改变其对碘/溴的反应性。例如,在与I_2的反应中,N,N-二取代的丝氨酸仅产生相应的10-Se-3高价“ T形”复合物。在存在过氧化物酶/ H_2O_2 / I-系统的情况下,N,N-二甲基咪唑-2-硒酮生成相应的二硒代二硒化物,其中两个I-抗衡离子为最终代谢产物。这些反应中离子种类的形成已通过单晶X射线衍射研究得以证实,在某些情况下,已通过傅里叶变换拉曼光谱研究得以证实。

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