肼及其衍生物与HNO_(2)反应的定量构效关系

QSAR of Reaction Between Hydrazine and Its Derivatives With Nitrous Acid

对肼及其衍生物与HNO_(2)的半反应时间进行了测量,利用Gaussian09中的密度泛函B3LYP方法、6-311+(3d,3p)基组以及HyperChem软件包,选择了肼及其衍生物的部分分子描述符进行了定量计算。将计算得到的量化参数与实验测得的半反应时间结合,利用统计回归的方法建立了肼及其衍生物与HNO_(2)反应的定量构效关系模型。模型显示,分子总能量E是该反应最主要的影响因素,除烯丙基肼外,半反应时间随分子总能量E的增加而增加,也即反应速率随分子总能量E的增加而减小。

In this paper,the half-reaction time of the reaction between hydrazine and its derivatives with nitrous acid is measured using spectrophotometry and stopped-flow injection device.Using Gaussian09 and HyperChem,hydrazine and its derivatives have been structurally optimized and some quantization parameters are calculated.Combining the half-reaction time and the quantization parameters,and using statistical regression analysis,QSAR model of the reaction between hydrazine and its derivatives with nitrous acid is established.The results show that total energy of molecules is the most important influencing factor in the reaction,and the half-reaction time increases with total energy of the molecule except for allyl hydrazine,the reaction rate decreases with the increase of total energy of the molecule.