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Synthesis of Polycation-type Helicenes with Electron-accepting Properties for Stereoselective Molecular Recognition

具有电子接受特性的聚阳离子型螺旋烯的合成用于立体选择性分子识别

基本信息

批准号：
04650781
负责人：
ARAI Sadao
金额：
$ 1.28万
依托单位：
Tokyo Metropolitan 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：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04650781/
关键词：
Helicenes Aronia Aromatics Quinolizinium Salts Photocyclization

项目摘要

Two types of azonia-helicenes, in which a carbon atom of the middle and inner helix skeleton is replaced by a quaternary nitrogen atom, were synthesized by the use of three-types photocyclization : (A) photocyclization of 1-styrylpyridinium salts to benzo[a]quinolizinium derivatives, (B) photocyclization of styrylquinolizinium salts to fused azonia compounds, (C) photocyclization of 2-styrylpyridine derivatives to benzo[c]quinolizinium salts. Helicenes with azonia-nitrogen at the middle helix skeleton were synthesized by the use of types A and B.Irradiation (type A) of 4-methyl-1-[2-(2-naphthyl)vinyl]pyridinium salt in methanol led to 2-methylnaphto[1,2-a]quinolizinium salt(1). The condensation reaction of 1 with benzaldehyde derivatives in the presence of piperidine in acetonitrile gave the corresponding styryl derivatives (2). The styryl derivatives (2) were photocyclized in the presence of iodine by the irradiation with a Pyrex-filtered light to afford the desired azonia[6]helicenes with a quaternary nitrogen at the middle helix skeleton.The reaction of benzo[h]quinoline and 1,10-phenanthroline with methyl lithium in toluene gave the corresponding 2-methyl derivatives. The methyl derivatives reacted with 1-chloro-2-formyl-naphthalene in refluxing acetic anhydride to afford the corresponding olefins. New 16c-azonia[6]helicenes with a quaternary nitrogen at the inner helix skeleton were obtained by photoinduced intramolecular quternization of the olefins in acetonitrile.

通过使用三种类型的光环化合成了两种类型的氮鎓-螺旋烯，其中中间和内部螺旋骨架的碳原子被季氮原子取代：（A）将1-苯乙烯基吡啶鎓盐光环化成苯并[a]喹嗪鎓衍生物，（B）将苯乙烯基喹嗪鎓盐光环化成稠合氮鎓化合物，（C）将2-苯乙烯基吡啶衍生物光环化成苯并[c]喹嗪鎓盐。用A型和B型催化剂合成了中间螺旋骨架含氮的螺烯。A型催化剂在甲醇中辐照4-甲基-1-[2-（2-萘基）乙烯基]吡啶盐，得到2-甲基萘并[1，2-a]喹嗪盐（1）。1与苯甲醛衍生物在哌啶存在下在乙腈中缩合得到相应的苯乙烯基衍生物（2）。苯乙烯基衍生物（2）在碘的存在下，经Pyrex滤光光照射，得到中间螺旋骨架上含季氮的偶氮[6]螺烯，苯并[h]喹啉和1，10-菲咯啉与甲基锂在甲苯中反应，得到相应的2-甲基衍生物。甲基衍生物与1-氯-2-甲酰基萘在无水乙酸酐中反应生成相应的烯烃。以乙腈为溶剂，通过光诱导烯烃分子内季铵化反应，合成了一系列新的16碳氮[6]螺烯。