α-亚甲基-β-氨基酮类化合物的合成和光谱特征  

Synthesis and Spectrometric Characteristic of α-Methylene-β-aminoketones

作　　者：牟丽媛 林紫云[2] 朱莉亚[2] 梁晓天[2] 

机构地区：[1]Center for Biophysical Science and Engineering, University of Alabama at Birmingham Birmingham, AL 35294, USA [2]中国协和医科大学中国医学科学院药物研究所,北京100050

出　　处：《有机化学》2008年第2期274-282,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.39970867)资助项目

摘　　要：以取代亚苄基丙酮、二级胺盐酸盐为底物,与多聚甲醛在无水乙醇中反应.除得到预期的Mannich碱产物外,还得到一个副产物,该副产物经IR,MS,1HNMR光谱及元素分析数据证明,为新一类结构的Mannich碱(IM).对影响Mannich反应的条件(如酸度、反应物的浓度、酮和胺盐的配比以及所用溶剂等方面)作了考察,并对该产物形成的机理作了探讨.还报道了14个α-亚甲基-β-氨基酮(IM)类化合物的质谱特征裂解方式及双键烯氢的δ值特征,并对其机理作了研究.During the synthesis of styryl ketonic Mannich bases, a one-pot method was used, in which ketone, secondary-amine hydrochloride and paraformaldehyde were refluxed together in ethanol. In most cases, the normal Mannich product （MA） was obtained, but the side-product α-methylene-β-aminoketones （IM）, instead of MA, was obtained when certain amines were used as the reactant. IR, MS and 1H NMR spectra confirmed that the compound IM was a new type of Mannich base which had a terminal double bond at α-position of the ketone group. This modified Mannich reaction was further explored and the formation mechanism of product IM was postulated and discussed based on the evidence of deuterium labeling. Fourteen IM were prepared by the modified Mannich reaction. Based on isotopic labeling, a plausible way of cleavage was proposed for the formation of M^＋ - 17 fragment signal in the mass spectra of the α-methylene-β-aminoketones. The characteristic chemical shift of the olefinic protons in ^1H NMR was also discussed.

关 键 词：α-亚甲基-β-氨基酮 取代亚苄基丙酮的Mannich碱 MANNICH反应 副产物 机理 

分 类 号：O623.7[理学—有机化学]