Synthesis of Organic Functionality Materials by Use of Trithio-Cyclopropenium Ion

三硫代环丙烯离子合成有机功能材料

基本信息

批准号：
60550610
负责人：
SUGIMOTO Toyonari
金额：
$ 1.41万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1987
项目状态：
已结题

项目摘要

Main interest has so far been directed toward theoretical investigation of electronic structures and physical properties etc. of cyclopropenium ion, cyclopropenone, and cyclopropenethione, samllest membered-ring aromatic systems. On theother hand, this research project was largely concerned in developing upique reactions due to a highly-strained three-membered ring opening of the above <pi>-electron compounds and furthermore in synthesizing new types of <pi>-electron systems with novel physicla properties and functions. During this research period the following two reactions were found out. (1) In the presenceof a tri-n-butylphosphine catalyst, bis(hydroxyphenyl) cyclopropenethione was subjected to dimerization, and a redox-active tetrakis(hydroxyphenyl)thieno[3,2-b]thiophene was obtained, which constructs a stable and distinct three-color organic electrochromic system with its two- and four-electron oxidized partner. (2)Very polarized dicyano-dithio- and -diphenyl calicenes reacted with diaminofulvene to afford new types of (pi)-electron systems, diaminoazulenofulvene and quinoid-type pentalene, of which the former compound has a large contributionof the polar structure in the ground state, thus giving much expectation as a promising component for non-linear optoelectronics.The present research also made a large progress in calicene chemistry. Thus,cyclic n-calicenes were synthesized, and their electronic structures were elucidated by the results of NMR, X-ray structural analysis, and MO calculations.

迄今为止，主要的兴趣已针对环丙基离子，环丙酮和环丙诺酮，Samllest Membered-Ring芳族系统的电子结构和物理性质等的理论研究。在其他方面，由于上述<pi> - 电子化合物的高度损坏的三元环开口，因此在很大程度上关注了发育反应，并在合成具有新型的<pi> - 电子系统具有新型物理和功能的新型类型中。在此研究期间，发现以下两个反应。 (1) In the presenceof a tri-n-butylphosphine catalyst, bis(hydroxyphenyl) cyclopropenethione was subjected to dimerization, and a redox-active tetrakis(hydroxyphenyl)thieno[3,2-b]thiophene was obtained, which constructs a stable and distinct three-color organic electrochromic system with its two- and four-electron氧化伴侣。（2）与二二苯基甲基烯烯与二二硫化反应的非常两极化的二苯基和二苯基烯基烯，提供新型类型的（PI） - 电子系统，二氨基二硫苯并二氟硫烯和喹啉型果仁烯，前者对基地的构成很大的构成，因此具有很大的贡献。在钙髓化学方面也取得了很大进展。因此，合成了环状N-核烯，并通过NMR，X射线结构分析和MO计算的结果阐明了它们的电子结构。