Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
J Zhejiang Univ Sci B. 2010 Feb;11(2):94-101. doi: 10.1631/jzus.B0900293.
A novel tandem reductive amination/intermolecular nucleophilic aromatic substitution (S(N)Ar) sequence has been established for the synthesis of amine containing pyrimidine in formation of one carbon-oxygen and one carbon-nitrogen bonds in a one-pot fashion. Treatment of aldehyde with arylamine, 2-methanesulfonyl-4,6-dimethoxypyrimidine and sodium borohydride provides good overall yield. The p-toluenesulfonic acid (PTSA) can be used as activator and is generally needed in the reaction. Dioxane is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF), MeCN, toluene and dichloromethane. The procedure is carried out effectively in the presence of K(2)CO(3). The reaction proceeds smoothly with aromatic aldehydes and arylamines possessing electron-donating or -withdrawing groups. This method can be applied to the synthesis of the oilseed rape herbicide and is superior to the classical one in several aspects: cutting out several purification steps, minimizing solvent use and chemical waste, and saving time. Its advantages such as operational convenience, high-efficient synthesis, and starting material availability make it a desirable method for preparing amines with molecular diversity and biological activity.
建立了一种新型串联还原胺化/分子间亲核芳香取代(S(N)Ar)序列,用于合成含胺嘧啶,在一锅法中形成一个碳-氧和一个碳-氮键。醛与芳胺、2-甲磺酰基-4,6-二甲氧基嘧啶和硼氢化钠反应可得到良好的总收率。对甲苯磺酸(PTSA)可用作活化剂,通常需要在反应中使用。二氧六环是首选的反应溶剂,但反应也可以在四氢呋喃(THF)、乙腈、甲苯和二氯甲烷中进行。在 K(2)CO(3) 的存在下,该程序可有效进行。该反应可顺利进行,适用于具有供电子或吸电子基团的芳香醛和芳胺。该方法可应用于油菜除草剂的合成,在几个方面优于经典方法:省去了几个纯化步骤,最大限度地减少了溶剂使用和化学废物,节省了时间。其操作方便、高效合成和原料易得等优点使其成为制备具有分子多样性和生物活性的胺的理想方法。