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Investigation for Strategy on Preparation of New Accumulated Molecules by the Interaction of Chalcogen Elements

硫族元素相互作用制备新聚集分子的策略研究

基本信息

批准号：
11440186
负责人：
FURUKAWA Naomichi
金额：
$ 9.66万
依托单位：
FOUNDATION FOR ADVANCEMENT OF INTERNATIONAL SCIENCE (2000-2001)University of Tsukuba (1999)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

Both electronic and steric interaction work among the multiple chalcogen elements arranged appropriately in the molecules. In general, the repulsive forces predominantly work in the dicoordinated chalcogen elements. On the other hand, when one generates a cation at one of the chalcogen atoms in the molecule by oxidation, other dicoordinate chalcogen elements react with the cationic center by the attractive forces to form the stable dications between the two elements. Furthermore, this dication reacts cumulatively with other chalcogen elements to create a new chemical bonds having a hypervalent structure at the central chalcogen elements in the molecule. We have found that the dication species become a strong electron withdrawing property and activate the carbon atoms attached at the chalcogen elements of the dication.In the present investigation, we report the following results : 1) by using the previous procedure, we succeeded to generate new active chemical species, i.e., carbocation … More s, ketenes, and carbens. We also succeeded to generate first organo-dicoordinated sulfur and selenium cations(R-S^+, R-Se^+). Furthermore, we could generate benzodithiete by the reaction of 2-benzylthiophenyl benzyl sulfoxide with Tf_2O. 2) 2, 6-Bisphenylchalcogenylmethylphenyl(or 2, 6-bisdimethylaminomethyl)phenyl telluride reacts with NOBF_4 to afford dication bearing a hypervalent tellurane structure at the central tellurium atom. By using this oxidation reaction we found a new remote oxidation reaction of the analogous molecules which have multi phenylenethio moiety as a spacer in the molecule. This reaction gave the oxidized product at the chalcogen atom at the separated position from that of the initial reaction site. We proposed that this new type of oxidation reaction should be called a remote oxidation and a new type of chemical reaction. 3) We identified the formation of the tetracation by following the 1^H-NMR spectorscopy on treatment of 1, 4-methylthiomethylsulfinylbenzene with CF_3CO_2H and as an extension of this reaction we could prepare various active polythiapoly cations from which cyclic polyphenylenepolysulfides were prepared. Less

电子和空间相互作用在分子中适当排列的多种硫族元素之间起作用。一般来说，排斥力主要作用于双配位硫族元素。另一方面，当分子中的一个硫族原子通过氧化产生阳离子时，其他双配位硫族元素通过吸引力与阳离子中心反应，在两种元素之间形成稳定的阳离子。此外，该双阳离子与其他硫属元素累积反应以在分子的中心硫属元素处产生具有超价结构的新化学键。我们发现双阳离子物质具有很强的吸电子特性，并激活了双阳离子硫族元素上附着的碳原子。在本研究中，我们报告了以下结果：1）通过使用之前的过程，我们成功地生成了新的活性化学物质，即碳阳离子、烯酮和碳。我们还成功生成了第一个有机双配位硫和硒阳离子（R-S^+，R-Se^+）。此外，2-苄基苯硫基苯甲基亚砜与Tf_2O反应可以生成苯并二硫醚。 2) 2, 6-双苯基硫属基甲基苯基(或2, 6-双二甲氨基甲基)苯基碲化物与NOBF_4反应，在中心碲原子处提供带有高价碲烷结构的双阳离子。通过使用这种氧化反应，我们发现了具有多苯硫基部分作为分子中间隔基的类似分子的一种新的远程氧化反应。该反应在与初始反应位点分开的位置处的硫族原子处产生氧化产物。我们提出这种新型氧化反应应称为远程氧化，是一种新型化学反应。 3）我们通过用CF_3CO_2H处理1, 4-甲硫基甲基亚磺酰基苯的1^H-NMR光谱确定了四阳离子的形成，并且作为该反应的延伸，我们可以制备各种活性多硫杂多阳离子，由此制备环状聚苯多硫醚。较少的