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首页> 外文期刊>Journal of Physical Organic Chemistry >Kinetic study of nitrosation of guaniclines
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Kinetic study of nitrosation of guaniclines

机译:鸟髓苷碱氮化的动力学研究

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摘要

The kinetics of the nitrosation reaction of three guaniclines, dicyandiamide, NN'-dimethyl-N ''-cyanoguanidine and guanidine have been studied. The nitrosation rate is first order with respect to both the guanicline and acid concentration. The absence of catalysis by nucleophilic anions, the observed general acid-base catalysis and the observed deuterium isotope effect lead us to propose mechanism for the nitrosation of guaniclines similar to that which operates in the case of the amides and ureas, in which a slow proton transfer is the rate determining step. From this mechanism we were able to obtain the values of the rate constants for the nitrosation and clenitrosation processes. The catalytic constants in presence of buffers were also obtained and the analysis of the Bronsted slopes suggests a process with a transition state more similar to reactants than products.
机译:研究了三个胍,双氰胺,NN'-二甲基-N' - 胞嘧啶和胍的亚硝化反应的动力学。 亚硝化率是关于胍碱和酸浓度的第一阶。 通过亲核阴离子的催化,观察到的一般酸碱催化和观察到的氘同位素效应导致我们提出了类似于在酰胺和尿布的情况下操作的鸟髓石的亚硝化机制,其中 转移是速率确定步骤。 从这种机制来看,我们能够获得亚硝化和栓铬过程的速率常数的值。 还获得了缓冲剂存在下的催化常数,并且对伪造斜面的分析表明,与产物更类似于反应物的过渡状态的过程。

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