倪宇翔,许松林,刘硕,杨建国,应安国

• 1:天津大学化工学院
• 2:台州学院医药化工学院
• 3:台州学院应用化学研究所

摘要(Abstract)：

以甘油为溶剂介绍了一种绿色、高效的苯并三氮唑N-烷基化衍生物的合成方法。该方法简便有效,适用于一系列的烷基卤代物,均能得到相应的N-烷基化产物且收率较高。此外,这种方法对环境无害,产品易分离,且能实现甘油的回收利用。

关键词(KeyWords)： N-烷基化;苯并三氮唑;催化;甘油

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金项目(21106090);; 浙江省低碳脂肪胺工程技术研究中心开放基金项目(2012E10033)

作者(Author): 倪宇翔,许松林,刘硕,杨建国,应安国

参考文献(References)：

• [1]Swamy S N,Basappa,Sarala G.,Priya B S,et al.Microwave-assisted synthesis of N-alkylated benzotriazole derivatives:Antimicrobial studies[J].Bioorg Med Chem Lett,2006,16(4):999–1004.
• [2]Guida W C,Mathre D J.Phase-transfer alkylation of heterocycles in the presence of 18-crown-6 and potassium tert-butoxide[J].J Org Chem,1980,45(16):3172-3176.
• [3]Hoffmann H,Pooth R.Biotransformation von 1H-benzotriazol and N-1-alkylbenzotriazolen invitro[J].Arch Pharm,1982,315(5):422-428.
• [4]Sukata K.N-Alkylation of pyrrole,indole,and several other nitrogen heterocycles using potassium hydroxide as a base in the presence of polyethylene glycols or their dialkyl ethers[J].Bull Chem Soc Jpn,1983,56(1):280-284.
• [5]Le Z G,Chen Z C,Hu Y,et al.Organic reactions in ionic liquids:An efficient method for the N-alkylation of benzotriazole[J].J Chem Res,2004(5):344-346.
• [6]Khalafi-Nezhad A,Zare A,Parhami A,et al.Quaternary ammonium salts as highly efficient and green alkylating agents for N-alkylation of azaheterocycles under microwave irradiation[J].J Iran Chem Soc,2008,5:S40-S46.
• [7]Ballesteros P,Elguero J,Claramunt R M.Reactivity of azoles towards benzaldehyde and its dimethylacetal:Synthesis of N,N’-diazolylphenylmethanes[J].Tetrahedron,1985,41(24):5955-5963.
• [8]Eduardo R P,Andre L,Marion L,et al.Clean and efficient microwave-solvent-free synthesis of 1-(2’,4’-dichlorophenacyl)azoles[J].Tetrahedron,2003,59(6):865-870.
• [9]Le Z G,Zhong T,Xie Z B,et al.Green and efficient protocol for N-alkylation of benzotriazole using basic ionic liquid[Bmim]OH as catalyst under solvent-free conditions[J].Synthetic Communications,2010,40(17):2525-2530.
• [10]Pagliaro M,Ciriminna R,Kimura H,et al.From glycerol to value-added products[J].Angew Chem Int Ed,2007,46(24):4434-4440.
• [11]Zhou C H,Beltramini J N,Fan Y X,et al.Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals[J].Chem Soc Rev,2008,37(3):527-549.
• [12]Behr A,Eilting J,Irawadi K,et al.Improved utilisation of renewable resources:New important derivatives of glycerol[J].Green Chem,2008,10(1):13-30.
• [13]DONG Chao-qi(董超琦),GENG Yan-lou(耿艳楼),ZHAO Xin-qiang(赵新强),et al.Influence of glycerol on solubility ofγ-Al2O3in ionic liquid[emim]BF4(甘油对促进γ-Al2O3在[emim]BF4离子液体中溶解性能的影响)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2013,27(1):7-10.
• [14]Gu Y L,Barrault J,Jerome F.Glycerol as an efficient promoting medium for organic reactions[J].Adv Synth Catal,2008,350(13):2007-2012.
• [15]Wolfson A,Dlugy C.Palladium-catalyzed heck and suzuki coupling in glycerol[J].Chem Pap,2007,61(3):228-232.
• [16]Ying A G,Zhang Q H,Li H M,et al.An environmentally benign protocol:catalyst-free Michael addition of aromatic amines to a,b-unsaturated ketones in glycerol[J].J Res Chem Intermed,2013,39(2):517-525.
• [17]He F,Li P,Gu Y,et al.Glycerol as a promoting medium for electrophilic activation of aldehydes:catalyst-free synthesis of di(indolyl)methanes,xanthene-1,8(2H)-diones and 1-oxo-hexahydroxanthenes[J].Green Chem,2009,11(11):1767-1773.
• [18]Li M H,Chen C,He F,et al.Multicomponent reactions of 1,3-cyclohexanediones and formaldehyde in glycerol:stabilization of paraformaldehyde in glycerol resulted from using dimedone as substrate[J].Adv Synth Catal,2010,352(2-3):519-530.
• [19]Tan J N,Li M,Gu Y.Multicomponent reactions of 1,3-disubstituted 5-pyrazolones and formaldehyde in environmentally benign solvent systems and their variations with more fundamental substrates[J].Green Chem,2010,5(12):908-914.
• [20]Andrade L H,Piovan L,Pasquini M D.Improving the enantioselective bioreduction of aromatic ketones mediated by Aspergillus terreus and Rhizopus oryzae:the role of glycerol as a co-solvent[J].Tetrahedron Asymmetry,2009,20(13):1521-1525.
• [21]Wolfson A,Haddad N,Dlugy C,et al.Baker's yeast catalyzed asymmetric reduction of methyl acetoacetate in glycerol containing systems[J].Org Commun,2008,1(2):9-16.
• [22]Karam A,Villandier N,Delample M,et al.Rational design of sugar-based-surfactant combined catalysts for promoting glycerol as a solvent[J].Chem Eur J,2008,14(33):10196-10200.
• [23]Katritzky A R,Kuzmierkiewicz W,Greenhill J V.An improved method for the N-alkylation of benzotriazole and 1,2,4-triazole.Reel Trav Chim Pays-Bas,1991,110(9):369-373.
• [24]Khalafi-Nezhad A,Zare A,Parhami A,et al.Highly regioselective N-alkylation of benzotriazole under solvent-free conditions.J Iran Chem Soc,2007,4(3):271-278.