白皮杉醇甲氧基衍生物与OOH自由基的反应机理-陕西师范大学学报期刊社网站

陕西师范大学学报（自然科学版）

化学与材料科学

白皮杉醇甲氧基衍生物与OOH自由基的反应机理

王渭娜*，王帅，王文亮

（陕西省大分子重点实验室，陕西师范大学化学化工学院，陕西西安 710119）

王渭娜，女，讲师，博士研究生。E-mail: wangwn@snnu.edu.cn

摘要:

采用M05-2X/6-311++G(d,p)水平对白皮杉醇甲氧基化衍生物的活性位点B环4′位清除OOH自由基的反应机理进行研究，并采用连续极化介质模型考察极性溶剂对该反应机理的影响。结果表明，白皮杉醇的A环3和5位被甲氧基取代得到的衍生物比白皮杉醇清除自由基能力强、水溶性好。PIC-R1-A5和PIC-R2-A3A5与OOH反应速率大于PIC与OOH反应速率，抽氢与加成反应均呈现正温度效应，且抽氢反应为优势通道。

关键词：

白皮杉醇；甲氧基衍生物； OOH自由基；反应机理

收稿日期：

2016-03-31

中图分类号：

O643.1

文献标识码：

文章编号：

1672-4291(2016)04-0060-06doi:10.15983/j.cnki.jsnu.2016.04.342

基金项目：

国家自然科学基金（21473108）；中央高校基本科研业务费专项资金(JK201603035)

Doi:

Theoretical study on the reaction mechanism of piceatannol methoxy derivatives with OOH radicals

WANG Weina*, WANG Shuai, WANG Wenliang

(Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi′an 710119, Shaanxi, China)

Abstract:

At M05-2X/6-311++G(d,p) level, the reaction mechanisms of piceatannol and its methoxy derivatives with OOH free radical were studied in gas phase, the effect of solvent polarity on the reaction mechanisms were also considered using the polarizable continuum model. The results showed that PIC-R1-A5 and PIC-R2-A3A5 have best reactivity and higher solubility among the derivatives. The reaction rates of PIC-R1-A5 and PIC-R2-A3A5 with OOH are higher than that of PIC with OOH，the more favorable channel is hydrogen atom transfer. Furthermore, the results also manifested that there is a positive correlation between the rate constants and temperature.

KeyWords:

piceatannol; methoxy derivatives; OOH free radical; mechanism