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

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的硫族元素。另一方面，当一个人通过氧化在分子中的一个硫族原子上产生阳离子时，其他二配位硫族元素在引力的作用下与阳离子中心反应，形成两个元素之间的稳定配位。此外，这一配位与其他硫族元素累积反应，创建了一种新的化学键，在分子中的中心硫族元素具有超价结构。在本研究中，我们报道了以下结果：1)利用前面的步骤，我们成功地生成了新的活性化学物种，即碳正离子…更多的S、烯酮和卡宾。我们还成功地合成了第一个有机二配位的硫和硒离子(R-S^+，R-Se^+)。此外，由2-苯硫基苯基苯基亚砜与Tf_2O反应生成苯二硫醚。2)2，6-二苯基硫代甲基苯基(或2，6-二二甲氨基甲基)苯基碲化物与NOBF_4反应，在碲原子中心形成高价碲烷结构。利用这个氧化反应，我们发现了分子中含有多个苯硫基作为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置分离的硫族原子上生成氧化产物。我们提出，这种新型的氧化反应应称为远程氧化和新型化学反应。3)用CF_3CO_2H处理1，4-甲硫基亚磺基苯，通过1H-核磁共振波谱确定了四化反应的形成，并作为该反应的延伸，我们可以制备各种活性的多硫杂阳离子，从这些阳离子中可以制备出环状聚苯硫醚。较少

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