|Budget Amount *help
¥3,300,000 (Direct Cost : ¥3,300,000)
Fiscal Year 2000 : ¥500,000 (Direct Cost : ¥500,000)
Fiscal Year 1999 : ¥500,000 (Direct Cost : ¥500,000)
Fiscal Year 1998 : ¥2,300,000 (Direct Cost : ¥2,300,000)
|Keywords||Orthogonal π Conjugated Compounds / aldol reactions / elongation of pi conjugation / 9,10-diacetylanthracene / 1,4-diacetylbenzene / 1,5-diacetylnaphthalene / -ray crystalogrphy / Eglinton method / 直交型芳香族化合物 / アルドール反応 / 伸長反応 / 1,4-ジアセチルアントラセン / 9、10-ジアセチルベンゼン / 1,5-ジアセチルナフタレン / X線構造解析 / エグリントンのカップリング反応 / 9,10-ジアセチルベンゼン / 1、4ージアセチルアントラセン / 9、10ージアセチルベンゼン / 1、4-ジアセチルアントラセン / 9、10-ジホルミルアントラセン|
The synthesis and properties of the novel three types of the orthogonal π conjugated compounds (1a〜c) is described. Furthermore, the formation and properties of their ionic species such as corresponding dications and dianions.
The target compounds (2a〜c) are composed with benzenoid aromatic such as benzene, anthracene, and naphthalene, and the orthogonal peripheral π conjugation. The general synthetic method was as follows. The starting materials were chosen aromatics bearing diacetyl groups at proper positions, such as 9,10-diacetylanthracene, 1,4-diacetylbenzene, and 1,5-diacetylnaphthalene. The aldol reactions of (2a〜c) with 1-ethynyl-2-formylcyclohexene (3) under the basic conditions (LDA) gave condensed compounds (4a〜c) in proper yields respectively. For the elongation of pi conjugation, the coupling reaction of the bis terminal acetylene by Eglinton method (Cucl-Py) gave fully conjugated quinones (1a〜c) in 42-54% yields. The structures of these compounds were confirmed by the data of the spectral measurements.
Furthermore, the absolute structure of these tree compounds were determined by the X-ray crystalogrphy. It showed that the angles between anthracene moiety and periphry in (1a) is 83° and 90°, benzene and periphery in (1b) is 37.6°, and naphthalene and periphery in (1c) is 90°, respectively. The formation of dicationic species (5a〜c) were observed in strong acid media, and dianionic species (6a〜c) also observed by the cyclic voltammogram measurement.