【作者】 赵玉龙；

【导师】 刘群；

【作者基本信息】 东北师范大学 ， 无机化学， 2005， 博士

【摘要】 由于共轭烯炔化合物含有炔烃和烯烃的基本结构以及双键和三键相互共轭的结构特征,使其不但具有孤立烯烃和炔烃的基本性质,同时又具有一些不同与它们的独特性质,是一类非常重要的有机合成中间体。虽然人们对共轭烯炔化合物已进行了相当深入和广泛的研究,但对含有供电子基团的共轭烯炔化合物各种性质及其应用的研究却相当有限。而此类化合物由于受供电子基团的影响,具有一些不同于一般共轭烯炔类化合物的独特性质,很可能是一类极其重要的有机合成中间体。因此,深入研究含有供电子基团的共轭烯炔化合物各种性质,扩展其在各领域上的应用都是非常必要和有意义的。 最近,在研究α-羰基二硫缩烯酮化合物的合成及其应用的基础上,我们研究小组获得了一系列在共轭烯炔的双键上连有强给电子基团（烷硫基）的共轭烯炔类化合物,对其各种性质的研究以及扩展其在有机化学和材料科学等领域中的应用成为我们近期的研究工作重点。本论文即以此为研究对象,着重讨论了这类共轭烯炔化合物和各种试剂的加成反应、和醛类化合物之间的碳碳偶联反应以及其自身的偶联反应,具体研究内容如下: 1.实现了烷硫基活化的共轭烯炔化合物和有机酸、硫醇以及芳胺类化合物的加成反应,获得了一系列重要的烯酯类、烯硫醚类和苯并1,4-氮杂卓类化合物。实验结果表明,上述加成反应具有很高的化学选择性和区域选择性,只得到相应的Markovnikov加成产物。 2.在TiCl₄催化下,成功实现了烷硫基活化的共轭烯炔化合物和各种芳香醛类化合物之间的偶联反应,立体选择性地制备了一系列（Z,E）-1,5-双氯-1,4-双烯类化合物。该偶联产物不仅是一类多官能团化合物,而且具有很强的反应活性,是一类非常重要的有机合成中间体。 3.通过烷硫基活化的共轭烯炔化合物自身偶联反应,成功地制备了一系列带有强供电子基团（烷硫基）、具有全碳骨架结构的共轭型有机分子。在所制备的一系列的共轭型有机分子中,尤为重要的是合成了迄今为止第一例在共轭全碳环的烯碳上连有杂原子取代基的扩展型舵轮烯化合物。同时,由于受烷硫基强给电子作用的影响,该扩展型舵轮烯化合物表现为很强的分子内电子推拉作用和加强的大环交叉共轭程度。这为以后这种烷硫基活化的共轭烯炔化合物在材料科学领域中的进一步应用展现了非常好的前景。 4.实现了α-羰基二硫缩烯酮α-位的官能（团）化反应:通过碘代脱羧反应、溴代/硝化脱乙酰基反应,获得了一系列α-碘代、α-溴代和α-硝基的二硫缩烯酮类化合物。该类反应不但具有反应条件温和以及产率高等优点,而且具有普遍性。这为利用α-羰基二硫缩烯酮化合物α-位的性质在有机合成中的进一步应用奠定了基础。更多还原

【Abstract】 Due to not only including the basic structures of olefins and alkynes but also possing unique conjugation property between carbon-carbon double bond and carbon-carbontriple bond, conjugated enynes are a kind of very important building blocks in organic synthesis, and have been applied in various fields. While conjugated enynes with electron-donating substitutes can have some special characters due to the effect of electron-donating groups, and are more important organic synthetic intermediate. In contrast to the extensive studies on the common conjugated enynes, the investigations on conjugated enynes with electron-donating substitutes remained poorly explored. So it is very necessary to study the characters and extend applications of this kind of conjugated enynes with electron-donating substitutes.In our recent research on the synthetic applications of a-acetyl ketene-S,S-acetals and their analogues, a series of conjugated enynes with electron-donating alkylthio groups were obtained in high yields. To get insight into the property and synthetic applications of this kind of alkylthio activated enynes, the addition reactions of alkylthio activated enynes with nucleophiles and electrophiles, the coupling reaction of alkylthio activated enynes with aryl aldehydes and the self-coupling reaction of alkylthio activated enynes were invesigated and the main results are listed as follows.The addition reactions of alkylthio activated conjugated enynes compounds with carboxylic acids, thiols and aromatic amines were carried out, respectively, and the corresponding enol esters, vinyl sulfides and benzo[b][l,4]diazepines were obtained in good yield. The above experimental results revealed that the addition reactions proceeded in a highly chemo- and regioselective manner, and afford the corresponding Markovnikov addition products.In the presence of TiCl4, the coupling reaction of alkylthio activated conjugated enynes with aryl aldehydes were performed and regioselectively generated the corresponding (E/Z)-l,5-dihalo-l,4-dienes compounds. These dihalodiene compounds can are potentially useful intermediates in organic synthesis due to the multifunctionality in the molecules.By the oxidative self-coupling reaction of alkylthio activated conjugated enynes, several series of π-conjugated nonaromatic all-carbon backbones organic moleculars with the electron-donating alkylthio substitutes on the conjugated chain were prepared, and especially synthesized the first heteroatom-substituted expanded radialene molecule with dithiolanylidene groups as strongly donor termini. More importantly, owing to the introduction of the strong electron-donating alkylthio groups, per(alkylthiolated) expandedradialene shows an extremely strong intramolecular push-pull interaction and enhanced macrocyclic cross-conjugation. These results indicated that the conjugated enynes with electron-donating alkylthio groups could be new kinds of important organic synthetic intermediates in materials chemistry.The a-functionalized ketenedithioacetals, α-Iodo/bromo/nitro ketenedithioacetals, were prepared in high yields under mild reaction conditions by the iododecarboxylation reaction of a-carboxylate ketenedithioacetals and the bromo/nitrodeacetylation reactions of a-oxo ketene dithioacetals. These results further confirmed the electrophilic nature of the a-carbon atom on a-oxo ketene dithioacetals. These a-functionalized ketenedithioacetals have the potential to be used as important new intermediates in organic synthesis.The intramolecular [2+2] photocyclizations of bis(alkenoyl)ketenedithioacetals were achieved by the irradiating with high-pressure mercury lamp, and obtained three isomeric compounds of substituted bicyclo[3.2.0]heptane-2,4-diones. The experimental results provided a sufficient proof that the above intramolecular [2+2] photocyclizations reaction may be mainly completed via a radical reaction process.更多还原