丙酮氰醇与3,5-二甲基-N-α,β-不饱和酰基吡唑的反应研究  

Study on the Reaction of Acetone Cyanohydrin with 3,5-Dimethyl-N-α,β-unsaturated Acyl Pyrazole

作　　者：房观念 由君[1] 喻艳超 荆军凯 刘波[1] 武文菊 Fang Guannian;You Jun;Yu Yanchao;Jing Junkai;Liu Bo;Wu Wenju(Key Laboratory of Green Chemical Engineering and Technology of Heilongjiang Province,College of Chemical and Environmental Engineering,Harbin University of Science and Technology,Harbin 150040)

机构地区：[1]哈尔滨理工大学化学与环境工程学院黑龙江省绿色化工技术重点实验室,哈尔滨 150040

出　　处：《有机化学》2020年第9期2871-2878,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21908034);黑龙江省自然科学基金(No.LH2019B010)资助项目。

摘　　要：氰基化合物是一类具有重要价值的有机物.研究了以丙酮氰醇为反应试剂,以取代的3,5-二甲基-N-α,β-不饱和酰基吡唑为底物时发生在不同位点的两种反应.研究结果表明,芳香取代的3,5-二甲基-N-α,β-不饱和酰基吡唑为底物时,使用不同的碱性催化剂会发生两种不同类型的反应:MgBu2存在时体系发生Michael加成反应,产物收率最高可达95%;在四甲基胍(TMG)存在时体系发生酰胺的醇解反应,生成β-取代苯基丙烯酸氰醇酯,收率最高达84%.脂肪取代的3,5-二甲基-N-α,β-不饱和酰基吡唑与丙酮氰醇在Mg Bu2或TMG存在下均发生Michael加成反应,产率最高为99%.讨论了使用不同碱性催化剂时的反应机理.Cyano compounds are a class of organic compounds with great value. Two different kinds of reactions have been reported using acetone cyanohydrin as reagent and substituted 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole as substrate. The reaction pathway depends on the basic catalysts used when aromatic substituted 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole was used as the substrate. Michael addition reaction occurred in the presence of MgBu2 with the product yield up to 95%, while alcoholysis reaction of amide occurred in the presence of 1,1,3,3-tetramethylguanidine(TMG), producing β-substituted phenyl cyanoacrylates with 84% yield. However, fatty substituted 3, 5-dimethyl-N-α,β-unsaturated acyl pyrazole and acetone cyanohydrin underwent Michael addition reaction in the presence of MgBu2 or TMG, the product yield was up to 99%. The possible reaction mechanism when using different basic catalysts was discussed.

关 键 词：丙酮氰醇 3 5-二甲基-N-α β-不饱和酰基吡唑 MICHAEL加成反应 β-取代苯基丙烯酸氰醇酯 

分 类 号：O621.25[理学—有机化学]