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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.

目前主要对环丙烯离子、环丙烯酮、环丙烯乙酮等最小成员环芳香体系的电子结构和物理性质等方面进行了理论研究。另一方面，本研究项目主要关注上述<pi>-电子化合物由于高应变三元环开口而产生的特殊反应，以及合成具有新物理性质和功能的新型<pi>-电子体系。在这个研究期间，发现了以下两个反应。(1)在三正丁基膦催化剂存在下，双（羟基苯基）环丙烯硫酮发生二聚化反应，得到具有氧化还原活性的四（羟基苯基）噻吩[3,2-b]噻吩，与二电子和四电子氧化伙伴构建了稳定而独特的三色有机电致变色体系。(2)极极化的二氨基-二硫代和-二苯基杯烯与二氨基呋喃反应生成了新型的（pi）电子体系，二氨基-二噻唑-呋喃和醌型戊二烯，其中前者在基态具有较大的极性结构，因此作为非线性光电子学的有前途的组分而备受期待。目前的研究在钙烯化学方面也取得了很大的进展。因此，我们合成了环状n-萼烯，并通过核磁共振、x射线结构分析和MO计算对其电子结构进行了鉴定。