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摘要
针对氮杂环化合物氨基化反应中目标氨基化产物收率和选择性低的问题,以吡啶为模型化合物,通过理论计算和实验验证确定了吡啶氨基化反应机理,分别考察了6种不同的相转移催化剂以及8种不同的溶剂对氨基化反应的影响规律。结果表明,氮杂环化合物氨基化反应遵循单电子转移机理,反应主要包括加合、消除、水解3个步骤。当反应温度为105℃、反应物吡啶与氨基钠摩尔比为1∶2.5、相转移催化剂为N,N-二甲基苯胺、溶剂为十二烷时,可获得较高的目标产物2-氨基吡啶收率(87%)和选择性(93%)。
Abstract
Both the yield and selectivity of target amination products in the amination reaction of nitrogen heterocyclic compounds are low.In order to solve this problem, the mechanism of pyridine amination is theoretically determined and experimentally verified through taking pyridine as model compound.The impact rules of six kinds of phase transfer catalysts and eight kinds of solvents are investigated in the pyridine amination.It is indicated that the amination of nitrogen heterocyclic compounds follows the single electron transfer mechanism involving three steps such as addition, elimination, and hydrolysis.The yield and selectivity of 2-aminopyridine, the target product, reach 87% and 93%, respectively when T=105℃, the molar ratio of pyridine to sodium amino is 1:2, N, N-dimethylaniline is served as phase transfer catalyst, and dodecane is used as solvent.
关键词
氮杂环
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溶剂
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相转移催化剂
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氨基化反应
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吡啶
Key words
nitrogen heterocycle
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solvent
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phase transfer catalyst
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amination reaction
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pyridine
Author summay
杜雪遥(1996-),女,硕士生,研究方向为煤焦油提质高效利用,duxueyao0812@link.tyut.edu。
吡啶氨基化反应及相转移催化剂与溶剂的影响规律研究[J].
现代化工, 2023, 43(12): 117-122,129 DOI:10.16606/j.cnki.issn0253-4320.2023.12.023