配位诱导的硝酸铜与水杨酸甲酯的高选择性自由基硝基化反应.pdf

第30卷第1期
元机化学学报
Vol30 No.1
2014年1月
CHINESE JOURNAL OF INORGANIC CHEMISTRY
121-126
配位诱导的硝酸铜与水杨酸甲酯的高选择性自由基硝基化反应
刘艳珠黄伊宁李霞张玲李永绣
(南昌大学理学院化学系,南昌330031)
摘要:硝酸铜与水杨酸酯的硝基化反应得到了高收率的对位产物。电子吸收光谱、循环伏安、电喷雾质谱的研究表明该反应经
历的是一个自由基硝基化机理。硝酸铜与水杨酸甲酯的配位促使硝酸根断裂氮氧键产生硝基自由基、氧自由基和配合物自由
基。硝基自由基与水杨酸甲酯或配合物反应得到硝基水杨酸甲酯或硝基化配合物。硝基化配合物经过水解将铜离子转化成氧化
铜沉淀而生成硝基水杨酸甲酯
关键词:水杨酸甲酯;硝酸铜;自由基硝基化;配位
中图分类号:0621.16
文献标识码:A文章编号:1001-4861(2014)01-0121-06
DI:10.11862/CJIC.2014.037
Coordination-mediated Radical Nitration of Methyl Salicylate by Copper( D
Nitrate with High Regioselectivity
LIU Yan-zhu HUANG Yi-ning LI Xia ZHANG Ling L Yong-xiu
(Department of Chemistry, School of Science, Nanchang University Jangi 330031, China)
Abstract: High yield and para-selective products were obtained by the nitration of methyl salicylate Mes)and
coper( )nitrate(UN).he results of electron absorption spectra(EAS), Cyclic Voltammetry(V)and electrospray
ionization mass spectra (ESIMS)reveal that the reaction favors a radical nitration mechanism. It is the
coordination of Mes with UN that promotes the split ting of N-O bonds of nitrate group in CUN, and results in the
formation of nitro radicals oxygen radicals and complex radicals. The nitro radicals can react with Mes or the
complexes of Mes to form nitration products. The nitrated complexes immediately turn to methyl nitrosalicylate by
Cu(l)ions being hydrolyzed to copper(ID)oxides
Key words: methyl salicylate; Cu(I) nitrate; radical nitration; coordination
0 ntroduction
study and many developments. However, the nitration
of aromatic compounds lacks positional selectivity
The serious effluent problems, created by nitration which mainly gives rise to ortho(o)isomersand the
processes based on mixed nitric and sulfuric acids
nitration mechanism has not come to a conclusion e9
have stimulated the search for alternative procedure
So seeking new standpoints for the explanation of
Over the past two decades, remarkable progress has nitration reaction process remains an Important
been made to improve the nitration procedure challenge for chemists
and synthesis efficiency by using various nitrating
Nitration is usually considered as an electrophilic
salts 0-17, The use of metal nitrates has received much aromatic substitution reaction Pierre Laszlo et al
收稿日期:2013-09-26。收修改稿日期:2013-11-04。
国家自然科学基金(No.2161014)资助项目。
通讯联系人。E-mail.liuyanzhu_79@163.com;vxi(@ncu.edu.cn:会员登记号:SO6N5032M1204。