| Project/Area Number |
11440186
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | FOUNDATION FOR ADVANCEMENT OF INTERNATIONAL SCIENCE (2000-2001)
University of Tsukuba (1999) |
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Principal Investigator |
FURUKAWA Naomichi FOUNDATION FOR ADVANCEMENT OF INTERNATIONAL SCIENCE, CHIEF RESEARCHER, 主席研究員 (80015966)
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| Co-Investigator(Kenkyū-buntansha) |
ERNST Horn 立教大学, 理学部・化学科, 教授
SATO Soichi DEPARTMENT OF CHEMISTRY UNIVERSITY OF TSUKUBA, LECTURER, 化学系, 講師 (90280908)
KOBAYASHI Kenji DEPARTMENT OF CHEMISTRY UNIVERSITY OF TSUKUBA, LECTURER, 化学系, 講師 (40225503)
HORN Ernst DEPARTMENT OF CHEMISTRY RIKKYO UNIVERSITY, PROFESSOR
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥15,100,000 (Direct Cost: ¥15,100,000)
Fiscal Year 2000: ¥4,800,000 (Direct Cost: ¥4,800,000)
Fiscal Year 1999: ¥10,300,000 (Direct Cost: ¥10,300,000)
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| Keywords | Dication / Chalcogen Element / Interaction / Active Species / Accumulation Effect / Remote Reaction / Hypervalency / Benzothiete / カルコゲヌラン / テルラン / カルコゲニド / カルコゲナジカチオン / 情報伝達 / 渡環相互作用 / 分子内分子間相互作用 / 分子間相互作用 / ジカルコゲジカチオン / Pummerer反応 / テトラカチオン / 高配位テルル / 刺激の伝達 |
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| Research Abstract |
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
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