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[1]刘媛媛,李壹,张征林,等.N,N-二甲基甲酰胺催化的吡唑亲电/亲核氯代反应[J].南京工业大学学报(自然科学版),2014,36(05):36-41.[doi:10.3969/j.issn.1671-7627.2014.05.007]
 LIU Yuanyuan,LI Yi,ZHANG Zhenglin,et al.N,N-Dimethylformamide catalyzed electrophilic/nucleophilic chlorination of pyrazoles[J].Journal of NANJING TECH UNIVERSITY(NATURAL SCIENCE EDITION),2014,36(05):36-41.[doi:10.3969/j.issn.1671-7627.2014.05.007]
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N,N-二甲基甲酰胺催化的吡唑亲电/亲核氯代反应()
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《南京工业大学学报(自然科学版)》[ISSN:1671-7627/CN:32-1670/N]

卷:
36
期数:
2014年05期
页码:
36-41
栏目:
出版日期:
2014-09-30

文章信息/Info

Title:
N,N-Dimethylformamide catalyzed electrophilic/nucleophilic chlorination of pyrazoles
文章编号:
1671-7627(2014)05-0036-06
作者:
刘媛媛1李壹2张征林1徐光辉1李杰1高尚1
1.东南大学 成贤学院 化工与制药工程系,江苏 南京 210088; 2.南京工业大学 生物与制药工程学院,江苏 南京 211800
Author(s):
LIU Yuanyuan1LI Yi2ZHANG Zhenglin1XU Guanghui1LI Jie1GAO Shang1
1.Department of Chemical and Pharmaceutical Engineering,ChengXian College,Southeast University,Nanjing 210088,China; 2.College of Biotechnology and Pharmaceutical Engineering,Nanjing Tech University,Nanjing 211800,China
关键词:
吡唑 DMF 氯化亚砜 4-氯吡唑
Keywords:
pyrazoles DMF thionyl chloride 4-chloropyrazoles
分类号:
O626.21
DOI:
10.3969/j.issn.1671-7627.2014.05.007
文献标志码:
A
摘要:
N,N-二甲基甲酰胺(DMF)催化下,用氯化亚砜氯代1-苯基-5-(4-甲基苯基)-1H-3-羟基吡唑(1a),以83%的高产率获得了4-氯-1-苯基-5-(4-甲基苯基)-1H-3-羟基吡唑(2a),用高效液相色谱(HPLC)跟踪反应,得出最佳反应条件为:n(1a):n(DMF)=10:1,在SOCl2中回流4 h,并分离得到单质硫,提出了DMF催化的吡唑亲电/亲核氯代机制。通过合成系列吡唑底物1b~1h,研究了氯代机制的普适性,其氯代产物2b~2h经核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)和元素分析表征,并用X线衍射法测定了2d的晶体结构。该氯代反应操作简单、官能团相容性好。
Abstract:
With N,N-Dimethylformamide(DMF)as a catalyst,1-phenyl-5-(p-tolyl)-1H-pyrazol-3-ol(1a)was heated to reflux in thionyl chloride(SOCl2)and 4-chloro-1-phenyl-5-(p-tolyl)-1H-pyrazol-3-ol(2a)was obtained in the yield of 83%. High performance liquid chromatography(HPLC)analysis of the reaction mixture revealed that the optimized conditions were n(1a):n(DMF)of 10:1, and refluxing in SOCl2 for 4 h. During the column chromatographic purification,elemental sulfur was isolated. The DMF-catalyzed electrophilic/nucleophilic chlorination mechanism was proposed, and pyrazole substrates 1b-1h were prepared to explore the scope of the mechanism. The structures of chlorinated products 2b-2h were characterized by nuclear magnetic resonance hydrogen spectrum(1H NMR), nuclear magnetic resonance carbon spectrum(13C NMR), and elemental analysis. The structure of 2d was also determined by single-crystal X-ray diffraction analysis. This chlorination reaction was simple to be operated and had good functionality tolerance.

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备注/Memo

备注/Memo:
收稿日期:2013-07-04
基金项目:江苏省自然科学基金青年基金(BK20130749); 江苏省普通高校研究生科研创新计划(CXZZ11_0365); 江苏省大学生实践创新项目(scx1214); 东南大学成贤学院青年教师科研项目(7303600001)
作者简介:刘媛媛(1985—),女,江苏南京人,讲师,博士,主要研究方向为有机合成方法学,E-mail:liuyuanyuan@cxxy.seu.edu.cn..
更新日期/Last Update: 2014-09-20