双链(或单链)极性共轭多烯化合物的合成及其多环化反应

Poly-acetylene and carotenoids are well-known polyene-like compounds, but few research was done on the polar conjugated polyenes especially on the molecules with duplex polyenes[ X(CH=CH)mY(CH=CH)nX'(m,n=2,3,4,5…)] structure units attached to the polar substituted groups (X,X' : C=O, CO2R, NO2, O, S, NR, halogen atoms and others,Y: R or similar groups).Due to the influence of the polar functional groups' different electrical properties, the nature of the double bonds in the polyene is significantly different from the simple olefins, or conversely the polyene's conjugation also affects the functional group's reactivity. The preliminary study showed that a series of polycyclic compounds having a specific structure can be obtained from the single or double-stranded polar polyenes by intermolecular or intramolecular cycloaddition, the performance is solid dependent on the length of the conjugated polyene strand plus the properties of the polar substituted groups, and the related materials will exhibit unique physical and chemical properties. Recently isolated natural products containing unique polyene structure by other chemists have specific biological activities, also demonstrates the potential value of the study. The purpose of this project is to synthesize a series of novel conjugated polyene in double or single chain system with polar substitute group connected, and the unique polycyclic compounds will be synthesized from the above special polyene compounds by selecting the different catalysts and additives, adjusting the temperature or pressure and other conditions, so some useful precursors potentially for the exploration of the new drugs and optoelectronic materials will be suggested.

聚乙炔和胡萝卜素类多烯研究比较多，但给或吸电子官能团（如羰基、酯基、硝基、杂原子及卤素等）与多烯(CH=CH)m(m≥2)连接而成的极性共轭多烯特别是双链（极性多烯）化合物的研究则很少。与独立的简单烯烃或供(吸)电子官能相比，因极性官能团不同电性因素的影响，双键会有明显不同的性质或反过来多烯的共轭也会影响官能团的反应活性。前期研究表明,单或双链极性烯烃可以通过分子间或分子内环加成形成系列具有特殊结构的环状化合物,且共轭烯链越长或极性越不相同其性能和反应就越丰富,相关物质会表现出更独特的物理化学性质。国内外学者近期分离出的含独特多烯结构的天然产物有特殊的生物活性,也表明了该研究的潜在价值。 本课题旨在合成一系列有极性取代基连接的新型共轭多烯双(或单)链体系，通过调控选择不同催化剂及助剂、温度、压力等反应条件,合成一系列有独特环状结构的化合物,为新的药物及光电材料的探索打下基础。

共轭体系长度及取代基的特征(给电子或供电子能力) 会影响相关物质的合成难易程度、 物理化学性质如稳定性、 化学反应特征等。数个单链或双链的极性(含酯基、 芳酮体系、 烷基酮体系)共轭三烯或四烯体系可以通过醛与不同类型和长度的Wittig试剂进行反应而合成得到。 实验发现Wittig反应中双醛体系与单醛有明显不同的活性和反应特征, 且Wittig试剂P=CHR(Ar)中的C-负离子不仅可以与C=O羰基作用, 同时还可以与不饱和烯或炔键(C=C, C≡C)作用, 合成得到支链型化合物(新Wittig试剂)； 此外,分子内双链共轭体系增大了同样极性的不饱和体系的成环趋势, 可以形成比较复杂的多芳基或多环化合物,个别还有明显的荧光特征。调控单链共轭体系两端的官能团的给或吸电子能力可以诱导不饱和键参与明显不同的化学反应。此为单或双链共轭体系的独特反应的更系统更深入研究打下了很好的基础。

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