新型酰胺型手性大环多胺的合成及光谱表征

以L-脯氨酸为原料，通过酯化、桥连和关环三步反应合成了两种新的酰胺型手性大环多胺。它们可作为NMR手性溶解剂用于羧酸类手性化合物的手性识别。通过多因素正交实验，确定了最佳反应条件： (8S,18S)-1,4,10,13,16-五氮杂三环16.3.0.04,8]二十一烷-9,17-二酮(2-a)反应温度50 ℃，反应时间10 d，氮气保护，无水甲醇，产率为34.9%，熔点278～280 ℃;13-苯基-(8S,18S)-1,4,10,13,16-五氮杂三环16.3.0.04,8]二十一烷-9,17-二酮(2-b)反应温度为回流，反应时间20 d，氮气保护，无水甲醇，产率为2.6%，熔点243～245 ℃。通过红外光谱、质谱、元素分析、一维、二维核磁共振波谱等手段对目标化合物的分子结构进行了表征，对化合物的红外光谱吸收峰及核磁谱线进行了归属分析，为进一步研究主客体分子之间的相互作用机理，开发更多更有效的NMR手性溶解剂提供了光谱依据。

Synthesis and Spectral Characterization of Novel Chiral Macrocyclic Dioxopolyamines

Two novel chiral macrocyclic dioxopolyamines, which can be used as NMR chiral solvating agents (CSAs) for chiral carboxylic acids, were synthesized from L-proline through esterification, bridging and ring-closing reaction. With the aid of orthogonal experiments the optimum reaction conditions were determined: for (8S, 18S)-1, 4, 10, 13, 16-pentaaza-tricyclo 16.3. 0.04(4,8)] heneicosane-9,17-dione(2-a), reaction temperature 50 degrees C, reaction time 10 d, in nitrogen atmosphere, absolute MeOH, yield 34.9%, and m. p. 278-280 degrees C; for 13-phenyl-(8S, 18S)-1, 4, 10, 13,16-pentaaza-tricyclo 16.3. 0.0(4,8)] heneicosane-9,17-dione (2-b), reaction temperature at reflux, reaction time 20 d, in nitrogen atmosphere, absolute MeOH, yield 2.6%, and m. p. 243-245 degrees C. Their molecular structures were characterized by elemental analysis (EA), mass spectroscopy (MS), infrared spectroscopy (IR), and 1D and 2D nuclear magnetic resonance spectrometry (NMR). The main infrared absorption peaks and nuclear magnetic spectral bands of the compounds were assigned. The spectroscopic analytical result provides useful information for further study of the mechanism of host-guest interaction and for preparing new and effective CSAs.