从二氯异苯甲酰和6-氨基烟酸甲酯衍生的新型三聚体和四聚体亚胺基大环酯的切入点。

IF 1.9 3区 化学 Acta Crystallographica Section B-structural Science Pub Date : 2013-02-01 Epub Date: 2012-12-20 DOI:10.1107/S0108768112047416
Pavle Mocilac, John F Gallagher
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引用次数: 6

摘要

二氯异苯甲酰与2-氨基吡啶衍生物(甲基6-氨基烟酸酯)的一步反应产生(i)基于三聚体的大环(EsIO)(3)和(ii)基于四聚体的大环(EsIO)(4),分离的合成产率中等(总产率为25%),以及(iii)更长的开链低聚物。大环化依赖于2-氨基(吡啶)官能团与两个酰氯官能团反应形成的半柔性亚胺铰链。大环合成的决定因素是:(a)利用杂芳邻氮官能团形成亚胺;(b)亚胺从平面扭曲85-115°的固有能力(通过CO···CO亚胺扭转角测量),从而为大环闭合或低聚物/聚合物形成中潜在的(非)螺旋组装提供铰链;(c)虽然在(EsIO)(3) (trezimide)和(EsIO)(4) (tennimide)大环中所有的异邻苯甲酰基在结构上都观察到同步构象,但异邻苯甲酰基与元相关羰基的构象灵活性可以扭曲并采用顺构象或反构象。
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Entry point into new trimeric and tetrameric imide-based macrocyclic esters derived from isophthaloyl dichloride and methyl 6-aminonicotinate.

The one-step reaction of isophthaloyl dichloride with the 2-aminopyridine derivative (methyl 6-aminonicotinate) yields (i) a trimer-based macrocycle (EsIO)(3) and (ii) a tetramer-based macrocycle (EsIO)(4) in modest isolated synthetic yields (total of 25%), together with (iii) longer open-chain oligomers. The macrocyclization relies on the semi-flexible imide hinge formed by reaction of the 2-amino(pyridine) functional group with two acyl chloride functional groups. The determining factors in macrocycle synthesis are: (a) imide formation using the heteroaromatic ortho-N functionality; (b) the inherent ability of the imide to twist by 85-115° from planarity (as measured by the CO···CO imide torsion angles), thereby providing a hinge for macrocyclic ring closure or potentially (non)helical assembly in oligomer/polymer formation; (c) the conformational flexibility of the isophthaloyl group with meta-related carbonyl groups to twist and adopt either syn or anti conformations, although the syn conformation is observed structurally for all isophthaloyl groups in both (EsIO)(3) (trezimide) and (EsIO)(4) (tennimide) macrocycles.

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来源期刊
自引率
5.30%
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0
审稿时长
6-12 weeks
期刊介绍: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.
期刊最新文献
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