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，主要兴趣集中在环丙烯鎓离子、环丙烯酮和环丙烯硫酮等最小元环芳族体系的电子结构和物理性质等方面的理论研究。另一方面，该研究项目主要致力于开发由于上述<pi>-电子化合物的高应变三元环开环而产生的upique反应，以及合成具有新颖物理性质的新型<pi>-电子系统。属性和功能。在本研究期间发现了以下两种反应。 (1) 在三正丁基膦催化剂存在下，双(羟苯基)环丙烯硫酮发生二聚反应，得到具有氧化还原活性的四(羟苯基)噻吩并[3,2-b]噻吩，构建了稳定且稳定的结构。独特的三色有机电致变色系统及其二电子和四电子氧化伙伴。 (2)高度极化的二氰基二硫代和二苯基卡芘烯与二氨基富烯反应生成新型(π)-电子体系，二氨基薁富烯和醌型五烯，其中前一种化合物对地下极性结构的贡献较大态，因此作为一种有前景的非线性光电子器件被寄予厚望。目前的研究在杯烯化学方面也取得了很大进展。由此合成了环状正二烯，并通过NMR、X射线结构分析和MO计算结果阐明了其电子结构。