【作者】 刘武军；

【导师】 尹炳柱；

【作者基本信息】 延边大学 ， 有机化学， 2004， 硕士

【摘要】 本文首先介绍了四硫富瓦烯（TTF）的部分研究进展。然后，在改进的高度稀释条件下，首次，以4，5-二溴甲基-1，3-二硫杂环戊烯-2-硫酮60，多缩乙二醇的1，ω-二巯基衍生物63a-d为原料进行缩合反应，方便地合成了4，5-位带二硫杂冠醚残基的2-硫代-1，3-二硫杂环戊烯的衍生物65a-d，后者在亚磷酸三乙酯存在下，与相应的氧代产物交叉偶联或自偶联得到两个系列新型不对称或哑铃形的四硫富瓦烯（TTF）硫杂冠醚衍生物67a-d和73a-d。讨论了合成单臂硫杂冠醚65a-d的“模板效应”和两系列偶联四硫富瓦烯（TTF）硫杂冠醚衍生物的产率，并用IR、¹H-NMR、¹³C-NMR、LC-MS对它们进行了表征。用循环伏安法、紫外光谱法和核磁共振氢谱探讨了67a-d和73a-d与碱金属离子、铵根离子和部分过渡金属离子的络合性能，同时尝试了以上化合物与TCNQ合成电子转移复合物的实验并用红外光谱进行表征。化合物67c-d是优于文献报道的较好的离子传感分子。 另外，还进行了4，5-位带全氧冠醚残基的2-硫代-1，3-二硫杂环戊烯的衍生物及一些含氮杂薁环的偶氮类液晶化合物的合成尝试。更多还原

【Abstract】 In this paper, first, we introduce some main research branches about tetrathiafulvalene (TTF). Then, under improved high dilution condition, we synthesized a series of 4,5-dithiacrown ether annulated l,3-dithiole-2-thiones 65a-d from readily available 4,5-bis(bromomethyl)-1,3-dithiole-2-thione 60 and 1, w -dimercapto glycol 63a-d. The target derivetives of tetrathiafluvalene(TTF) incoporating crown ether, including novel asymmeric 73a-d and dumbbel-shaped 67a-d, were prepared in fairly good yields via the standard coupling reaction generating TTF from 4,5-dithiacrown ether annulated l,3-dithiole-2-thiones with corresponding transchalogenated product in net triethyl phosphite. "Template effect" in the synthesis couse of 65a-d and yields of the two series of TTF thia-crown ethers were discussed. All the compounds were typed by IR, 1H-NMR, 13C-NMR, LC-MS. Via cyclic voltammograms, UV and ’H-NMR, respectively, with alkali metal ions, ammonium ion and some transation metal ions, we studied the complexing ability of 67a-d and 73a-d. We also synthesized CT complexes, which were typed by IR spectrum using above compounds with TCNQ. Compounds 67c-d were better cation sensor molecules that were superior to those of reported.We also attempted to synthesize 4,5-all-oxygen crown ether annulated 1,3-dithiole-2-thiones derivatives and some azo-liquid crystal compounds coupling 1,3-diazaazulene.更多还原