SYNTHESES OF NEW ORGANIC ELECTRON DONORS,ACCEPTORS,AND THEIR CHARGE-TRANSFER COMPLEXES,AND STUDIES ON THEIR PROPERTIES

本研究项目的目标分子是新型有机电子给体(1)和受体(2，3，4)，它们有望作为有效组分形成具有高电导率的电荷转移络合物。分子1携带两个7pi的电子环，在其两个近邻位置与一个Naplithalenen融合在一起，有望在两个阶段的氧化还原过程中作为良好的电子供体。1，2，4，6-三甲基-1，4，4-三甲基-4，4，4，4，6-三甲基-4，4，4，4-三甲基-4，4，4，4，5-三甲基-4，4，4-三甲基-4，4，4，4，4，5-三甲基-4，4，4-三甲基-4，4，4，4，5，5，6-三甲基-4，4，4，4，4，5-三甲基-4，4，4-三甲基-4，4，4，4，4，4，4，5，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4，4将酸酐经LAH还原得到的二元醇转化为1，8-二(二溴甲基)-4，5-二氯萘。二溴与由双[频那多]二硼和4-辛炔合成的顺式-4，5-双(硼基)辛烯反应，得到多茂烯。正在努力获得1(R=n-Pr)。Tellurophene-TCNQ(2)是杂环TCNQ中仅存的未知化合物。…的合成以1，4-双(TMS)-1，3-丁二炔和Na2Te为原料，经6步反应制得2，5-二元酸。羧基转化为二氰亚甲基得到2(XL，R=H)目前正在活跃地起泡。Crysene-TCNQ(3)具有独特的扩展共轭pi-体系，预计非常稳定，在其氧化态具有非常低的库仑排斥力。它们的合成计划通过Suzuki-Miyaura方法将2-溴-6-甲氧基萘和2-溴-5-甲氧基苯甲醛偶联，生成关键中间体2，8-二甲氧基丙烯。现在对偶联反应进行了仔细研究。菲-TCNQ(4)是唯一的，被认为是一个很强的受体，因为它具有喹啉部分结构。它的合成计划通过2-溴-5-甲氧基甲苯和N，N-二乙基-4-甲氧基苯甲酰胺通过Suzuki-Miyaura和Snieckus偶联方法得到的联苯衍生物来进行。联苯衍生物经过金属化、分子内缩合、脱羟基消除等反应，得到关键的菲衍生物3，6-二甲氧基菲。目前，我们正在积极研究偶联反应的条件和步骤，以获得联苯类化合物。虽然我们还没有目标分子在我们手中，但我们正在接近我们的目标，非常肯定能够在不久的将来获得它们。较少

The target molecules of this research projects are novel organic electron donors (1) and acceptors (2, 3, 4), which are expected to act as effective components to form charge-transfer complexes exhibiting high electric conductivities. The molecule, 1, carries two 7pi electron rings fused to a naplithalenene at its two peri-positions and is expected to behave as a good electron donor in the two stage redox processes. Synthesis of 1 is started from acenaphthene and are first dichiorinated its peri-positins then transformed its 5-membered ring to a cyclic anhydride via bromination with NBS and the following oxidation. The diol obtained by LAH reduction of the anhydride was transformed to 1, 8-Bis(dibromomethyl)4, 5-dichioronaphthalene. The dibromide was reacted with cis-4, 5-bis(boryl)octene, prepared from bis[pinacolato]diboron and 4-octyne, to yield a pleiadene. Efforts to obtain 1 (R=n-Pr) in progress. Tellurophene-TCNQs (2) are only ones left unknown amoung Hetero-TCNQs. Synthesis of … More 2 is started from tellurophene, which is prepared by 1,4-bis(TMS)-1, 3-butadiyne and Na_2Te and then converted to 2, 5-dicarboxylic acid via 6 steps. Transformation of carboxyl group to dicyanomethylene group to obtain 2 (xl, R=H) is now actively sudying. Crysene-TCNQ (3) has a unique extended conjugated pi-system and expected to be very stable and have very low coulombic repulsion in their oxidation states. Their synthesis are planned to couple a 2-bromo-6-methoxynaphthalene and 2-bromo-5-methoxybenzaldehyde by Suzuki-Miyaura method to yield a key intermediate to lead 2, 8-dimethoxyclirysene. The coupling reaction is now scrutinized. Phenanthrene-TCNQ (4) is unique and assumed to be a strong acceptor, because it has a oquinoid partial structure. Its synthesis is planned to execute via a biphenyl derivative, which is obtained from 2-bromo-5-methoxytoluene and N,N-diethy1-4-methoxybenzamide by a combination of Suzuki-Miyaura and Snieckus coupling methods. The biphenyl derivative is subjected to metalatation, intramnoleculari condensation followed dehydroxylic elimination to afford a key phenanthrene derivative, 3, 6-dimethoxyphenanthrene. Now we are actively investigating coupling reaction conditions and procedures to obtain the biphenyl derivatives. Although we do not yet have the target molecules in our hands, we are closely approaching our targets and very sure to be able to get them in near future. Less