[1]李冠琼,林秋汉.铜粉催化叠氮与端炔1,3-偶极环加成反应研究[J].南京理工大学学报(自然科学版),2017,41(02):239.[doi:10.14177/j.cnki.32-1397n.2017.41.02.016]
 Li Guanqiong,Lin Qiuhan.1,3-Dipolar cycloaddition of azides and alkynescatalyzed by copper powder[J].Journal of Nanjing University of Science and Technology,2017,41(02):239.[doi:10.14177/j.cnki.32-1397n.2017.41.02.016]
点击复制

铜粉催化叠氮与端炔1,3-偶极环加成反应研究()
分享到:

《南京理工大学学报》(自然科学版)[ISSN:1005-9830/CN:32-1397/N]

卷:
41卷
期数:
2017年02期
页码:
239
栏目:
出版日期:
2017-04-30

文章信息/Info

Title:
1,3-Dipolar cycloaddition of azides and alkynescatalyzed by copper powder
文章编号:
1005-9830(2017)02-0239-06
作者:
李冠琼1林秋汉2
1.国家知识产权局专利局 专利审查协作广东中心,广东 广州 510530; 2.南京理工大学 化工学院,江苏 南京 210094
Author(s):
Li Guanqiong1Lin Qiuhan2
1.Patent Examination Cooperation Center of the Patent Office,State Intellectual PropertyOffice of the PRC,Guangzhou 510530,China; 2.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
关键词:
13-偶极环加成反应 铜粉 盐酸三乙胺 14-二取代-123-三唑
Keywords:
13-dipolar cycloaddition copper powder triethylamine hydrochloride 14-disubstituted 123-triazole
分类号:
O626.26
DOI:
10.14177/j.cnki.32-1397n.2017.41.02.016
摘要:
该文探讨了普通铜粉高效催化的叠氮化物与端炔的1,3-偶极环加成反应。研究结果表明,以铜粉为催化剂,盐酸三乙胺(Et3N·HCl)为助催化剂,体积比为1:1的水/叔丁醇(H2O/t-BuOH)为溶剂,将叠氮化物与端炔于室温常压下反应2 h,高收率合成1,4-二取代-1,2,3-三唑化合物,收率可达93.05%。该方法所用催化剂廉价易得,且用量少,反应条件温和,耗时短,收率高,后处理操作简单。
Abstract:
The 1,3-dipolar cycloaddition of azides and alkynes efficiently catalyzed by copper powder is studied.The reaction is efficiently performed in the presence of copper powder as the catalyst and the triethylamine hydrochloride(Et3N·HCl)as the promoter in the water/t-butyl alcohol(H2O/t-BuOH)(volume ratio 1:1)under the room temperature and the normal pressure for 2 h,and the yield ratio of the 1,4-disubstituted 1,2,3-triazoles is up to 93.05%.The procedure is characterized by the lower amount of the inexpensive catalyst,the mild reaction condition,the little time-consuming,the high productivity and the easy operation.

参考文献/References:

[1] 白雪,周成合,米佳丽.三唑类化合物研究与应用[J].化学研究与应用,2007,19(7):721-729.
Bai Xue,Zhou Chenghe,Mi Jiali.Research and application of triazole[J].Chem Res Appl,2007,19(7):721-729.
[2]金林红,宋宝安,杨松,等.唑类农药研究进展[J].贵州大学学报(自然科学版),2003,20(1):91-96.
Jin Linhong,Song Baoan,Yang Song,et al.Research progress of azoles pesticide[J].Journal of Guizhou University(Natural Science),2003,20(1):91-96.
[3]Hong Xue,Ye Gao,Twamley B,et al.New energetic salts based on nitrogen-containing heterocycles[J].Chem Mater,2005,17(1):191-198.
[4]Sivabalan R,Anniyappan M,Pawar S J,et al.Synthesis,characterization and thermolysis studies on triazole and tetrazole based high nitrogen content high energy materials[J].Journal of Hazard Mater,2006,137(2):672-680.
[5]Tornoe C W,Christensen C,Meldal M.Peptidotriazoles on solid phase:[1,2,3]-Triazoles by regiospecific copper(I)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides[J].Journal of Org Chem,2002,67(9):3057-3064.
[6]Rostovstev V V,Green L G,Fokin V V,et al.A stepwise Huisgen cycloaddition process:Copper(I)-catalyzed regioselective “ligation” of azides and terminal alkynes[J].Angew Chem Int Ed,2002,41(14):2596-2599.
[7]Himo F,Lovell T,Hilgraf R,et al.Copper(I)-catalyzed synthesis of azoles.DFT study predicts unprecedented reactivity and intermediates[J].J Am Chem Soc,2005,127(1):210-216.
[8]Alonso F,Moglie Y,Radivoy G,et al.Copper nanoparticles in click chemistry:An alternative catalytic system for the cycloaddition of terminal alkynes and azides[J].Tetrahedron Lett,2009,50(20):2358-2362.
[9]Huang Lina,Liu Wei,Wu Juncheng,et al.Nano-copper catalyzed three-component reaction to construct 1,4-substituted 1,2,3-triazoles[J].Tetrahedron Lett,2014,55(14):2312-2316.
[10]Lipshutz B H,Taft B R.Heterogeneous copper-in-charcoal-catalyzed click chemistry[J].Angew Chem Int Ed,2006,45(48):8235-8238.
[11]Yan Jincan,Wang Lei.Synthesis of 1,4-disubstituted 1,2,3-triazoles by use of copper(I)and amino acids ionic liquid catalytic system[J].Synthesis,2010(3):447-452.
[12]Slimi R,Kalhor-Monfared S,Plancq B,et al.A-21·CuI as a catalyst for Huisgen’s reaction:About iodination as a side-reaction[J].Tetrahedron Lett,2015,56(29):4339-4344.
[13]Tajbakhsh M,Farhang M,Baghbanian S M,et al.Nano magnetite supported metal ions as robust,efficient and recyclable catalysts for green synthesis of propargylamines and 1,4-disubstituted 1,2,3-triazoles in water[J].New J Chem,2015,39(3):1827-1839.
[14]江云兵,王彦龙,韩骞,等.硅烷偶联化壳聚糖负载CuBr高活性催化合成1,2,3-三唑化合物[J].有机化学,2014,34(10):2068-2075.
Jiang Yunbing,Wang Yanlong,Han Qian,et al.Highly efficient synthesis of 1,2,3-triazoles catalyzed by silane coupled chitosan-CuBr catalyst[J].Chin J Org Chem,2014,34(10):2068-2075.
[15]Namitharan K,Kumarraja M,Pitchumani K.Cu-II-hydrotalcite as an efficient heterogeneous catalyst for Huisgen[3+2]cycloaddition[J].Chem Eur J,2009,15(12):2755-2758.
[16]Tale R H,Gopula V B,Toradmal G K.‘Click’ ligand for ‘click’ chemistry:(1-(4-methoxybenzyl)-1-H-1,2,3-triazol-4-yl)methanol(MBHTM)accelerated copper-catalyzed[3+2]azide-alkyne cycloaddition(CuAAC)at low catalyst loading[J].Tetrahedron Lett,2015,56(43):5864-5869.
[17]Zhang Weiwei,He Xing,Ren Baoqi,et al.Cu(OAc)2·H2O-an efficient catalyst for Huisgen-click reaction in supercritical carbon dioxide[J].Tetrahedron Lett,2015,56(19):2472-2475.
[18]Hosseinzadeh R,Abolfazli M K,Mohseni M,et al.Efficient synthesis and antibacterial activities of some novel 1,2,3-triazoles prepared from propargylic alcohols and benzyl azides[J].J Heterocycl Chem,2014,51(5):1298-1305.
[19]王景梅,李凌君,张贵生.1,2,3-三唑化合物的合成研究进展[J].有机化学,2009,29(1):13-19.
Wang Jingmei,Li Lingjun,Zhang Guisheng.Progress in syntheses of 1,2,3-triazoles[J].Chin J Org Chem,2009,29(1):13-19.
[20]李冠琼,李玉川,马巧丽,等.富氮唑环类化合物的环加成合成研究进展[J].有机化学,2010,30(10):1431-1440.
Li Guanqiong,Li Yuchuan,Ma Qiaoli,et al.Research progress in synthesis of nitrogen-rich zole-ring compounds by cycloaddition reaction[J].Chin J Org Chem,2010,30(10):1431-1440.
[21]刘世领,扈艳红,沈永佳,等.苄基叠氮化合物的合成[J].化学试剂,2005,27(1):39-40.
Liu Shiling,Hu Yanhong,Shen Yongjia,et al.Synthesis of benzyl azides[J].Chem Reagents,2005,27(1):39-40.
[22]扈艳红,刘世领,仝钦宇,等.1,3-偶极环加成反应合成1-(取代苄基)-1,2,3-三唑类化合物[J].有机化学,2004,24(10):1228-1232.
Hu Yanhong,Liu Shiling,Tong Qinyu,et al.Synthesis of 1-(substituted benzyl)-1,2,3-triazoles by 1,3-dipolar cycloaddition reaction[J].Chin J Org Chem,2004,24(10):1228-1232.
[23]Lee B Y,Park S R,Jeon H B,et al.A new solvent system for efficient synthesis of 1,2,3-triazoles[J].Tetrahedron Lett,2006,47(29):5105-5109.

相似文献/References:

[1]张 防,等.1,4-苯二甲酸镉的合成及其热分解制备CdO纳米晶[J].南京理工大学学报(自然科学版),2009,(01):137.
 ZHANG Fang,BEI Feng-li,LIU Xiao-heng,et al.Preparation of Nano-sized Crystal CdO by Thermal Decomposition of Cadmium Complex of 1,4-Benzene Dicarboxylic Acid[J].Journal of Nanjing University of Science and Technology,2009,(02):137.
[2]陆 明,汪水旺,李 剑.氯化亚铜-三乙醇胺催化合成1,1,1,3,3-五氯丙烷[J].南京理工大学学报(自然科学版),2007,(04):533.
 LU Ming,WANG Shui-wang,LI Jian.Synthesis of 1,1,1,3,3-pentachloropropane with Catalysis of Cu2Cl2 and Triethaolamine[J].Journal of Nanjing University of Science and Technology,2007,(02):533.
[3]宋华杰,董海山,郝莹,等.氟聚物与TATB界面作用的XPS评价[J].南京理工大学学报(自然科学版),2002,(03):303.
 SongHuajie DongHaishan HaoYing XiaoHeming.An Evaluation of Interfacial Interaction Between Fluoropolymer and TATB Using XPS Technique[J].Journal of Nanjing University of Science and Technology,2002,(02):303.

备注/Memo

备注/Memo:
收稿日期:2016-09-12 修回日期:2016-11-18
基金项目:国家自然科学基金(20772011)
作者简介:李冠琼(1986-),男,硕士,助理研究员,主要研究方向:富氮化合物合成,E-mail:20806070@163.com; 通讯作者:林秋汉(1985-),男,博士,主要研究方向:新型多氮含能材料的合成,E-mail:linqh@njust.edu.cn。
引文格式:李冠琼,林秋汉.铜粉催化叠氮与端炔1,3-偶极环加成反应研究[J].南京理工大学学报,2017,41(2):239-244.
投稿网址:http://zrxuebao.njust.edu.cn
更新日期/Last Update: 2017-04-30