ClO_2氧化苯胺类有机物反应动力学的QSAR研究

QSAR study on kinetics of anilines oxidation with ClO_2

为研究苯酚类有机物与C lO2的反光动力学,采用高效液相色谱(HPLC)技术跟踪测定苯胺类有机物的浓度变化,结果表明,反应对于苯胺类有机物和C lO2均为一级反应,总反应级数为二级.获取了C lO2与10种苯胺反应的速率常数.分析了苯胺分子结构对氧化反应速率的影响,建立了QSAR模型.模型表明,C lO2氧化苯胺类有机物的反应速率logk与苯胺分子Hamm ett取代常数σ和分子折射率MR之间存在良好的线性相关关系,说明C lO2氧化苯胺的反应速率不仅与苯胺类有机物的电子结构有关,还与其立体效应有关.

Kinetics of reaction between ClO2 and 10 anilines were investigated by following concentrations of anilines with HPLC. Results showed that reactions were first -order in respect to both anilines and ClO2 and the overall reactions could be described as second -order. Rate constants of 10 anilines oxidation with ClO2 were obtained experimentally. Effects of molecular structures of anilines on reaction rates were analyzed and QSAR model was established. The model revealed that logk correlated linearly with Hammett constants σ and molecule refractive index MR, indicating that reaction rates were determined by both electronic and spatial effects of substituents.