引用本文:
【打印本页】   【HTML】   【下载PDF全文】   View/Add Comment  【EndNote】   【RefMan】   【BibTex】
←前一篇|后一篇→ 过刊浏览    高级检索
本文已被:浏览 1549次   下载 1408 本文二维码信息
码上扫一扫!
分享到: 微信 更多
EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions
Tao Wang,An-an Wu,Li-guo Gao,Han-qing Wang
Author NameAffiliationE-mail
Tao Wang Department of Chemistry and Chemical Engineering, Heze University, Heze 274015, China  
An-an Wu State Key Laboratory of Physical Chemistry of Solid Surfaces, School of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China  
Li-guo Gao College of Chemistry and Chemical Engineering, Yulin College, Yulin 719000, China  
Han-qing Wang Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China whqwt@yahoo.com.cn 
Abstract:
Electron paramagnetic resonance and electron-nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel-Crafts alkylating sys-tem, with m-xylene, or p-xylene and alkyl chloride. The results indicate that the observed electron paramagnetic resonance spectra are due to polycyclic aromatic radicals formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel-Crafts alkylation reactions undergo Scholl self-condensation to give polycyclic aromatic hydrocarbons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl3. The identiˉcation of observed two radicals 2,6-dimethylanthracene and 1,4,5,8-tetramethylanthracene were supported by density functional theory calculations using the B3LYP/6-31G(d,p)//B3LYP/6-31G(d) approach. The theoretical coupling constantssupport the experimental assignment of the observed radicals.
Key words:  Electron paramagnetic resonance, Eelectron-nuclear double resonance, Density functional theory, Polycyclic aromatic radical cation
FundProject:
EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions
汪涛,吴安安,高立国,汪汉卿 *
摘要:
利用电子顺磁共振和电子核双共振技术在间二甲苯与氯代烷烃和对二甲苯与氯代烷烃进行付-克烷基化反应体系中分别检测到二个多核芳烃正离子自由基信号.研究结果表明,所观察到顺磁共振信号分别来自于2,6-二甲基蒽正离子和1,4,5,8-四甲基蒽自由基的贡献.提出了这二个自由基的生成是在付-克烷基化反应中生成的氯代芳基在AlCl3存在下发生Scholl缩合反应生成多核芳烃,后者发生单电子氧化转变为相应的多核芳烃正离子自由基。利用密度泛函理论计算了这两个自由基的超精细偶合常数,与实验值符合相当满意,从理论上支持了对实验超精细谱线的归属.
关键词:  电子顺磁共振,电子核双共振,密度泛函理论,多核芳烃正离子自由基
DOI:10.1088/1674-0068/22/01/51-56
分类号: