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N-取代基-1,2,3-三唑广泛应用于生物科学、材料化学和药物化学领域,近几年来引起了人们很大兴趣.N~1-取代基-1,2,3-三唑既可由加热催化,也可通过金属诱导的(铜(Ⅰ)催化的1,4-双取代和钌(Ⅱ)催化的1,5-双取代)1,3偶极子环加成反应制备得到,然而有关N~2-取代基-1,2,3-三唑的合成仍未获得太大进展.目前,高N~2选择性的N~2-芳基和N~2-烯丙基-1,2,3-三唑的合成方法是利用大位阻的膦配体配位钯催化偶联反应.2008年,史晓东课题组报道了烷基卤化物与大体积的C-4和C-5双取代基的NH-1,2,3-三唑通过亲核反应合成N~2-烷基-1,2,3-三唑,但其应用受到底物限制.我们设想N~1-烷基-1,2,3-三唑可否由N~1-取代1,2,3-三唑合成,由于N~1-取代基-1,2,3-三唑制备的研究较多,其合成方法将可很方便地构造N~2-烷基-1,2,3-三唑化合物.鉴于此,本文对单取代三唑、未取代三唑与包括乙烯基酯在内的多种烯烃的反应进行了研究.首先,我们用不同取代基的N~1-1,2,3-三唑与烯烃在不同的酸催化条件下进行反应,考察了酸效应对反应收率的影响,发现TsOH做Br?nsted酸为催化剂时,反应产率最高;而AuCl_3做Lewis酸为催化剂时反应几乎没有加成产物生成.然后,以TsOH为催化剂,改变三唑与烯烃的加入比例,发现加入比例为1:6时反应产率最高.当N~1取代基是Ts-时,反应产率最高.催化剂TsOH的加入量由1当量升至2当量时,反应产率没有明显变化.由此表明,N~1-1,2,3-三唑与烯烃的最佳反应条件为:催化剂为TsOH(1当量),N~1-1,2,3-三唑的取代基为Ts,N~1-1,2,3-三唑与烯烃的加入比例为1:6.在确定了最佳反应条件后,考察了三唑类底物的适用性.结果发现,N~2/N~1产物的比例均很高,说明该反应具有很高的N~2选择性.上述研究表明,TsOH酸催化N~1-对甲苯磺酰基-1,2,3-三唑与烯烃的加成反应是一种有效合成N~2-烷基-1,2,3-三唑的新方法,并通过单晶确定了最终的产物结构.单取代三唑和未取代三唑与包括乙烯基酯在内的多种烯烃反应合成N~2-烷基-1,2,3-三唑都有很好的反应效果.本文提供了一种简单有效的合成N~2-烷基-1,2,3-三唑的新方法.
N-substituted 1,2,3-triazole is widely used in the fields of biological sciences, material chemistry and medicinal chemistry and has attracted great interest in recent years.N 1 -substituted-1,2,3-triazole The oxazoles were either catalyzed by heating or by metal-induced 1,3-dipolar cycloaddition of copper (I) -catalyzed 1,4-disubstituted and ruthenium (II) catalysed 1,5-disubstituted However, much progress has not yet been made on the synthesis of N 2 -substituted-1,2,3-triazole.At present, high N 2 -selective N 2 -aryl and N 2 -allyl 1,3-triazole synthesis method is the use of sterically hindered phosphine ligand coordination palladium catalytic coupling reaction .2008, Shi Xiaodong task force reported alkyl halide and large volume of C-4 and N-2-alkyl-1,2,3-triazole was synthesized by nucleophilic reaction of NH-1,2,3-triazole with double substituents of C-5, but its application was limited by substrate. Alkyl-1,2,3-triazole can be N ~ 1-substituted 1,2,3-triazole synthesis, due to N 1-substituent -1,2,3-triazole Preparation of more , Its synthesis method will be easy to construct N ~ 2-alkyl-1,2,3-triazole compounds.In view of this, the monosubstituted triazole, unsubstituted triazole and including vinyl ester, The reverse of olefins First, we use different substituents of N ~ 1-1,2,3-triazole and olefin under different acid catalysis conditions, investigated the acid effect on the reaction yield, we found that TsOH do When Br? Nsted acid is used as catalyst, the yield of reaction is the highest, but when Lewis acid is used as catalyst, there is almost no addition product of AuCl_3 .Then TsOH is used as catalyst to change the addition ratio of triazole to alkene, and the addition ratio is 1 : 6, the reaction yield is the highest.When the N ~ 1 substituent is Ts-, the yield of the reaction is the highest.When the amount of the catalyst TsOH is increased from 1 equivalent to 2 equivalents, the yield of the reaction does not change obviously.Therefore, N ~ 1-1,2,3-triazole and olefins the optimum reaction conditions: the catalyst is TsOH (1 equivalent), N ~ 1-1, 2,3-triazole substituents Ts, N ~ 1- The ratio of 1,2,3-triazole to alkene was 1: 6. After determining the optimal reaction conditions, the suitability of triazole substrates was investigated. It was found that the ratio of N ~ 2 / N ~ 1 The ratio is high, indicating that the reaction has a high N ~ 2 selectivity.The above study shows that TsOH acid catalyzed N ~ 1-p-toluenesulfonyl-1,2,3-triazole and olefin addition reaction is a Effective synthesis of N ~ 2-alkyl-1,2,3-triazole Method and the final product structure was confirmed by single crystal.The synthesis of N 2-alkyl-1,2,3-triazole by the reaction of mono-substituted triazole and unsubstituted triazole with various olefins including vinyl ester Has a good reaction effect.This paper provides a simple and effective new method for the synthesis of N 2-alkyl-1,2,3-triazole.