【作者】 杜昕；

【导师】 王为；

【作者基本信息】 兰州大学 ， 有机化学， 2010， 博士

【摘要】 在过去的十年中,以List和MacMillan等为代表的研究工作推动了有机小分子催化的蓬勃发展,使其成为不对称催化领域中新兴的研究方向之一。但是有机小分子催化剂往往用量较大,并且造价昂贵,难于回收利用；而有机小分子催化剂的多相化则是解决这些问题的有效途径。有机小分子催化剂的多相化方式很多,大部分是将其固载到磁性纳米材料、介孔材料和高分子树脂上。另一方面,近年来发展起来的固有微孔聚合物和共轭微孔聚合物以其优异的孔性质、有机骨架的热稳定性和化学稳定性等优势得到了人们的关注。但是目前还没有将有机小分子催化剂与有机微孔材料相结合的研究工作见诸报道。如果可以将有机小分子催化剂植入有机微孔聚合物材料的骨架中或者孔道内,得到的材料将不仅具有优异的孔性质,利于多相催化反应的传质、提高催化反应效率；而且通过共价键连接的多相催化剂可以避免催化反应活性中心的流失,提高催化剂的稳定性。所以具有微孔性质的固体有机小分子催化剂将有可能在工业生产中具有应用前景。本论文的工作主要是设计合成了几种骨架杂原子化和官能团化的共轭微孔聚合物材料,并且在此基础上设计并合成了几种含有有机小分子催化剂的功能化有机微孔聚合物材料,通过氮气等温吸脱附、固体核磁等表征手段对所合成的有机微孔材料进行了表征,并初步研究了这些有机微孔聚合物材料在多相催化中的应用。本论文的第一章主要介绍了微孔材料的发展过程,着重介绍了有机微孔聚合物材料的发展过程以及近年来新型的有机微孔材料在多相催化、气体储存和分离等方面的应用。本论文的第二章与第三章旨在对共轭微孔聚合物材料进行骨架改性和结构修饰。第二章分别采用对碘三苯胺和对溴三苯硼作为前体合成了骨架中含有氮原子和硼原子的共轭微孔聚合物,并且通过氮气等温吸脱附、固体核磁等表征手段对这些材料进行了表征。第三章采用含有硝基(-NO2)和甲氧基(-OCH3)的前体合成了含有这两种官能团的共轭微孔聚合物材料并且对其进行了表征。在本论文的第四章中,我们首先合成了含有有机小分子催化剂L-脯氨酸、(R)-BINOL和(R)-BINOL磷酸的三种有机分子前体,然后通过Sonogashira-Hagihara偶联反应合成了一系列含有有机小分子催化剂的共轭微孔聚合物,并且对其进行了表征和催化反应性能的初步研究。在本论文的第五章中,我们通过Sonogashira-Hagihara偶联反应将特格勒碱引入有机微孔聚合物材料的骨架当中,通过各种表征手段表征了其结构和微孔性质,并且研究了其储存氢气的能力以及作为多相催化剂在二乙基锌对苯甲醛的加成反应中的催化效果。更多还原

【Abstract】 In the past decade, organocatalysis has been flourished by many research groups including those of List and MacMillan, and gradually becomes one of the emerging fields in asymmetric catalysis. However, utilization of organocatalysts suffers, still, from high catalyst-loading, expensive cost, and difficulty for recycle use. With respect to this important issue, heterogenization of organocatalysts may offer an effective solution instead. Current strategies for this purpose are mainly focused on the immobilization of organocatalysts onto magnetic nano-materials, inorganic mesoporous materials and polymer resins. On the other hand, polymers of intrinsic microposity (PIMs) and conjugated microporous polymers (CMPs) being developed recently may possess attractive prospects due to their excellent microporous characters, thermal stability, and chemical stability. To the best of our knowledge, however, there have been no reports on the combination of organocatalysts and microporous organic materials. Embedding of organocatalysts into the frameworks of organic microporous materials via covalent bonds may help mass transfer in heterogeneous catalysis, improve the efficiency of catalytic reactions, and avoid the loss of catalytic active centers.Accordingly, the main task of this PhD thesis is to design and synthesize several microporous polymers which are functionalized by hetero-atoms, functional groups, or organocatalysts. Characterization of these functional microporous materials was realized by nitrogen adsorption/desorption isotherms and soild-state NMR techniques. Applications of these organic microporous polymers as heterogeneous catalysts were also exploited.In ChapterⅠ, was introduced the research background on microporous materials, and highlighted the development of microporous organic polymers (MOPs). Applications of these organic microporous materials in heterogeneous catalysis, gas storage and separation were, accordingly, reviewed.ChapterⅡand ChapterⅢdescribe our attempts in the modification of CMPs by hetero-atoms and functional groups, respectively. In Chapter II, tris-(4-iodo-phenyl)-amine and tris-(4-bromo-phenyl)-borane were applied as precursors to synthesize the functional CMPs containing N or B heteroatoms. Characterization of these CMPs was performed by nitrogen adsorption/desorption isotherms and soild-state NMR techniques. In Chapter III, organic precursors containing-NO2 or-OCH3 groups were utilized to synthesize nitro- and methoxy-functionalized CMPs, respectively.In Chapter IV, asymmetric organic precursors containing the frameworks of organocatalysts, such as L-proline, BINOL, and BINOL-phosphoric acid, were succefully synthesized and further applied in constructing a series of organocatalyst-functionalized CMPs via Sonogashira-Hagihara cross-coupling reactions. The characterization and catalytic applications of these CMPs were conducted accordingly.In Chapter V, an organic nanoporous polymer containing bicovalently-bonded Troger’s base in the network constructed by the Sonogashira-Hagihara cross-coupling reaction was synthesized. The structure and microporous properties of the synthesized polymer were further characterized. Moreover, its catalytic activity in the addition reaction of diethylzinc to 4-chlorobenzaldehyde and its ability for hydrogen storage were examined.更多还原