基于乙酸为溶剂和催化剂的芳乙酮Mannich反应  

Mannich Reaction of Aromatic Ketones Based on Acetic Acid as Solvent and Catalyst

作　　者：卜辉娟[1] 张静[1] 穆博帅 李媛[1] 

机构地区：[1]河北师范大学化学与材料科学学院,石家庄050024

出　　处：《高等学校化学学报》2014年第9期1912-1918,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20972040)资助~~

摘　　要：采用乙酸作溶剂和催化剂,将芳乙酮与甲醛和二级胺进行Mannich反应及热解反应,并未得到预期的Mannich碱或α,β-不饱和酮(2),而是以较高产率(65%~73%)生成了乙酸(2-芳甲酰基)烯丙酯(3a^3o).通过核磁共振波谱、高分辨质谱和红外光谱表征了化合物3a^3o的结构,研究了此"异常"反应的发生条件,并提出了可能的反应机理.结果表明,芳乙酮的特殊结构及反应中过量的乙酸是产生化合物3a^3o的决定因素.Mannich reaction is one of the most important methods for preparation ofβ-amino ketones and alde-hydes and α,β-unsaturated carbonyl compounds, as well as one of the most important basic reaction types in organic chemistry and it is widely applied as a key step in the synthesis of numerous pharmaceuticals and natu-ral products. However, during the synthesis of 1-aryl acrylic ketone 2 by the Mannich reaction of aromatic ke-tones, formaldehyde and secondary amine using acetic acid as solvent and catalyst, the Mannich base and ex-pectedα,β-unsaturated ketones 2 were not obtained and another kind of compounds 3 , 2-aryl formyl allyl ace-tate were obtained in moderate to good yields（65%-73%） . The structure of compounds 3 was confirmed by 1 H NMR, 13 C NMR, HRMS and IR spectra. The reasons of producing compounds 3 were studied and the re-sults suggested that the special structure of aromatic ketones and excess acetic acid in reaction are responsible for the exceptional Mannich reaction. In addition, the reaction mechanism was postulated.

关 键 词：MANNICH反应 Α Β-不饱和酮 乙酸(2-芳甲酰基)烯丙酯 乙酸 

分 类 号：O626[理学—有机化学]