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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个碳元素之间起作用。一般来说，排斥力主要作用于不配位的碳元素。另一方面，当分子中的一个碳原子通过氧化作用生成阳离子时，其他的二配位碳元素就会在引力作用下与阳离子中心反应，在这两个元素之间形成稳定的阳离子。此外，该化合物与其他的硫元素发生累积反应，在分子的中心硫元素处形成具有高价结构的新化学键。我们发现该化合物具有很强的吸电子性，并激活了附着在该化合物的碳元素上的碳原子。在本研究中，我们报告了以下结果：1)利用上述方法，我们成功地生成了新的活性化学物质，即碳正离子，多s，烯酮和碳。我们还成功地生成了第一个有机配位的硫和硒阳离子（R-S^+, R-Se^+）。此外，我们还可以用2-苄基噻吩苄基亚砜与Tf_2O反应生成苯二甲酸盐。2) 2,6 -双苯基硫基甲基苯基（或2,6 -双二甲氨基甲基）苯基碲化物与NOBF_4反应生成在中心碲原子上具有高价碲烷结构的化合物。利用这一氧化反应，我们发现了一种以多邻苯二甲酸乙酯为间隔基团的类似分子的远端氧化反应。这个反应产生的氧化产物位于与初始反应位点分离的位置上的硫原子上。我们建议将这种新型氧化反应称为远程氧化反应，是一种新型的化学反应。3)用CF_3CO_2H处理1,4 -甲基硫甲基亚砜时，通过1^H-NMR谱图确定了该反应的形成，作为该反应的延伸，我们可以制备各种活性多硫阳离子，从中制备环状聚苯聚硫化物。少