High Yield Synthesis, Separation and Structural Characterization of New [n+n]-Polyazamacrocycles
High Yield Synthesis, Separation and Structural Characterization of New [n+n]-Polyazamacrocycles
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新型[n n]-多氮杂大环化合物的高产率合成、分离和结构表征
DOI：
10.3987/com-02-9693
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发表时间：
2003
期刊：
影响因子：
0.6
通讯作者：
M. Klinga
中科院分区：
文献类型：
--
作者：
B. Rieger;M. Allmendinger;P. Zell;A. Amin;U. Thewalt;M. Klinga
以叔丁基和异丙基取代芳香二醛(1a-c)和二胺(2a-f)为原料合成了一系列亚胺大环(3a-m)。这种高度选择性的环化反应要么产生[2+2]化学计量比，要么产生不同的[n+n]环的混合物，这取决于二胺构建块。对于某些已定义的大环(3b、3d、3e)，其结构通过单晶X射线衍射法确定，表明大环在固体中呈柱状排列。用MALDI-TOF和分析GPC相结合的方法研究了大环的混合物，这在确定准确的粒度分布方面带来了显着的改进。首次通过制备性凝胶渗透色谱分离得到了聚亚胺环的高级同系物。通过还原两个含吡啶的环(4a-b)，证明了将亚胺大环定量还原为其相应的胺类似物的可能性。
t-Bu- and isopropyl-substituted aromatic dialdehydes (la-c) and diamines (2a-f) were used to synthesize a series of imine macrocycles (3a-m). The highly selective cyclization reaction resulted either in a [2+2] stoechiometry or in a mixture of different [n+n] cycles, depending on the diamine building block. For some defined macrocycles (3b, 3d, 3e) the structure was elucidated by single crystal X-Ray diffraction that revealed a column-like arrangement of the macrocycles in the solid state. Mixtures of macrocycles were investigated with a combination of MALDI-Tof and analytical GPC which brought significant improvements in the determination of the exact size distribution. Isolated higher homologues of polyimine cycles were made available by preparative GPC for the first time. The possibility to reduce the imine macrocycles quantitatively to their corresponding amine analogues was demonstrated exemplary by the reduction of two pyridine containing cycles (4a-b).