臭氧与巴豆醛反应机理研究  

Study on the Reaction Mechanism of Ozone and Crotonaldehyde

作　　者：田文欣[1] TIAN Wen-xin(Shaanxi Radio&TV University,Xi'an 710119,China)

机构地区：[1]陕西广播电视大学,陕西西安710119

出　　处：《山东农业大学学报（自然科学版）》2018年第4期671-674,共4页Journal of Shandong Agricultural University：Natural Science Edition

基　　金：陕西广播电视大学科研课题(17D-07-A16)

摘　　要：本文在B3LYP/6-31+G(d,p)水平上优化了臭氧与巴豆醛反应体系各驻点物种的几何构型,采用G3//B3LYP方法对所有驻点进行单点能计算,并构建了O3+CH_3CHCHCHO反应体系的势能剖面。结果表明,巴豆醛的臭氧化反应符合Criegee机理,且存在两种反应路径,其中,生成产物CH_3CHOO和HC(O)CHO的反应是臭氧化物中间体(IM)裂解的优势路径。其Criegee自由基syn-CH_3CHOO单分子异构化反应具有环化和氢迁移两种反应通道,其中氢迁移通道为优势通道,anti-CH_3CHOO和HC(O)CHOO只能进行环化异构化反应。In this paper,the geometrical configurations of each resident species of the ozone-butaldehyde reaction system were optimized at the level of B3LYP/6-31+G(d,p),the single point energy of all stationary points was calculated by G3/B3LYP method,and the potential energy profile of O3+CH3CHCHCHO reaction system was constructed.The results showed that ozonization reaction of crotonaldehyde was in accord with Criegee mechanism.There were two kinds of reaction paths,the reaction between CH3CHOO and HC(O)CHO was the dominant pathway for the decomposition of ozonide intermediates(IM).Monomolecular isomerisation of Criegee free radical syn-CH3CHOO has two reaction channels:cyclizing and hydrogen migration,the hydrogen migration channel is the dominant channel.Anti-CH3CHOO and HC(O)CHOO can only be used for cyclization isomerization.

关 键 词：臭氧 巴豆醛 反应机理 

分 类 号：O623.512[理学—有机化学]