新型酰胺型手性大环多胺的合成及光谱表征

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摘要：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[16.3.0.0^4,8]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[16.3.0.0^4,8]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。

关键词：酰胺型手性大环多胺;L-脯氨酸;合成;核磁共振波谱;红外光谱;质谱

Abstract：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[16.3.0.0^4,8]heneicosane-9,17-dione(2-a),reaction temperature 50 ℃,reaction time 10 d,in nitrogen atmosphere,absolute MeOH,yield 34.9%,and m.p. 278-280 ℃;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 ℃. 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.

Key words：Chiral macrocyclic dioxopolyamines;L-proline;Synthesis;NMR;IR;MS

收稿日期: 2006-10-28 修订日期: 2007-01-26

中图分类号:

O621.1

通讯作者: 傅恩琴 E-mail: fueq@whu.edu.cn

引用本文:

杨雪梅¹,傅恩琴^2*. 新型酰胺型手性大环多胺的合成及光谱表征[J]. 光谱学与光谱分析, 2007, 27(07): 1403-1407.
YANG Xue-mei¹,FU En-qin^2*. Synthesis and Spectral Characterization of Novel Chiral Macrocyclic Dioxopolyamines. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(07): 1403-1407.

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https://www.gpxygpfx.com/CN/Y2007/V27/I07/1403

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