【作者】 宋鑫波；

【导师】 郭建平；

【作者基本信息】 山西大学 ， 有机化学， 2012， 硕士

【摘要】 有机磷化学的理论和应用研究是现代化学新思想、新技术发展的重要源头之一。依据其理论知识,设计并合成出富含П电子的氮磷类化合物进而制备出相应的超分子材料、成为开发新型实用型功能材料的方向之一。含磷超分子聚合结构及氮磷环状结构类物质的研究是近年来研究较多的一个领域。本课题设计并合成出系列由长程静电力结合而组装的离子型超分子聚合物及含磷环状类化合物,并探索具有特色结构的有机超分子聚合物及环状含磷化合物的合成路线和构效关系。本论文以不含α-H的腈为起始原料和二(三甲基硅基)胺基锂发生加成反应,再用一氯二苯基磷酰氯与之反应得到相应产物。在实验中得到了系列离子型超分子聚合物及氮磷环状化合物,并利用核磁、单晶X-射线衍射对这些化合物的晶体结构进行表征。同时也合成了几个农药中间体化合物,用核磁、液质联用仪对这几个化合物进行了表征,并得到了其中一个中间体的晶体结构。第一部分：主要介绍了有机磷化学、超分子聚合物及磷环状有机化合物的发展,总结了近年来有机磷化学及其在应用方面的一些研究成果,并介绍了本课题的研究进展。第二部分：以苯腈,2-、3-、4-吡啶腈和1,3-间苯二腈这些不含α-H的腈为起始原料,与二(三甲基硅基)胺基锂发生加成反应,然后与一氯二苯基磷酰氯进行取代反应,得到系列氮磷超分子聚合物以及5个含氮磷的新化合物。详细介绍了有机磷环状化合物2b、2d、2h、磷四价化合物2f、以及有机关环化合物2n的合成和表征,并对所合成化合物的荧光性能和紫外性能进行了测定。第三部分：首先简要介绍了磺酰磺隆、抗蚜威等农药的发展及近况,对磺酰磺隆及抗蚜威的衍生物3b、3d、3h的合成及反应条件创新之处进行了详细介绍,合成产物利用多种方法进行了表征,并报道了其中一个中间体3a的晶体结构。最后,在总结与展望中,对上述两章内容进行了总结,还展望了所得磷环状有机化合物在未来的应用前景,及生成磷四价化合物的可能方法。更多还原

【Abstract】 The theory and application research of organophosphorus is one of the important sources of the modern chemistry development. Based on the theory of phosphorus chemical knowledge, the self-assembly polymeric network of amidinium cations and diphenylphosphinate anions could be formed from the oxidative cleavage of N-P compounds. These π-electron-rich phosphorus-nitrogen compounds had been known as the potential precursors for inorganic polymers with unusual properties, and led to considerable interest in their syntheses and coordination chemistry toward transition metals.In this project, a series of charge-assisted supramolecular polymeric compounds and circular organophosphorus compounds were synthesized. The structure-function relationships of these compounds were investigated.In this paper, the research focused on the interaction of a-hydrogen-free nitriles with LiN(SiMe3)2followed the addition of diphenylphosphinic chloride gave the ionic supramolecular polymeric compounds or circular nitrogen phosphorus products. The molecular structures of these new compounds were characterized by X-ray single diffraction and NMR. In addition to these five novel compounds, some pesticides intermediate compounds were also prepared and characterized by LCQ, NMR. The crystal structure of an intermediate was obtained.Part1:The development of study and application of the organophosphorus chemistry, charge assisted hydrogen bond supramolecular polymeric chemistry was introduced. The subject and progress of this work was summarized.Part2:Benzonitrile,2-,3-,4-cyanopyridine and1,3-dicyanobenzene using as a starting material were reacted with LiN(SiMe3)2, followed by diphenylphosphinic chloride, five novel nitrogen phosphorus compounds and five charge assisted hydrogen bond supramolecular polymeric compounds were produced. The synthesis and characterization of circular organophosphorus compounds2b and2d,2h, P4+compound2f and new circular organic compound2n was described. The fluorescence and ultraviolet properites of the compounds was reported.Part3:The synthesis and characterization of sulfosulfuron and pirimicarb derivatives3b、3d、3h were reported. And one of the intermediate was confirmed by single crystal structure.Finally, the content of part2and3was summarized. The potential application of circular organophosphorus compounds and the possible synthetic method of P4+compounds were reviewed.更多还原