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Synthesis of the novel fused pi-electronic systems by the intramolecular electrophilic attack of tropylium ion

通过鎓离子分子内亲电攻击合成新型熔融π电子系统

基本信息

批准号：
08640685
负责人：
YAMAMURA Kimiaki
金额：
$ 0.32万
依托单位：
KOBE UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

项目摘要

Fused full pi-conjugated systemss containing seven-membered ring are molecules of both theoretical and experimental interest due to their unique electronic structures, and various kinds of such compounds have been prepared. However the reported synthetic methods generally suffered from tedious multistep procedures and low yields at the stage of construction of the unsaturated seven-membered ring. We pay our attention to electrophilic nature of tropylium ion, and developed two facile synthetic methods of the compounds containing conjugated seven-membered ring. Our synthetic stratery was to use commercially available 1,3,5-cycloheptatriene as the seven-membered unit.1) The facile and novel synthesis of fused full conjugated cyclic compounds containing tropylium ion by an intramolecular Friedel-Crafts type reaction of o-aryl-, and o-heteroaryl-tropyliobenzenes. Cyclohepta [a] thienonaphthalenylium ions and cyclohepta [a] furonaphthalenylium ion which are the isoelectronic cations of triphenylene, and cyclohepta [a] benzofuro [c] naphthalenylium ions, cyclohepta [alpha] benzothieno [c] naphthalenylium ions and cyclohepta [a] indoro [c] naphthalenylium ion which are the isoelectronic carbocations of the potent carcinogenic benzo [g] chrysene, were obtained in reasonable yields.2) The facile and novel synthesis of heteroaromatic fused azurene derivatives.beta- (10-Benz [a] -azulenyl) -a, b-unsaturated ketone and beta- (9-azuleno [1,2-b] thienyl) -alpha, beta-unsaturated ketones were obtained from omicron- [2-furyl] tropyliobenzenes and 1-tropylio-2- [2-furyl] thiophenes, respectively, in reasonable yields. The mechanism involving a novel ring-cyclization by intramolecular attack of the tropylium ion to the 2-position of the furan ring is postulated. X-ray crystal structure of two of beta- (9-azuleno [1,2-b] thienyl) -alpha, beta-unsaturated ketones have been determined.

含七元环的稠合全π共轭体系由于其独特的电子结构而在理论和实验上都具有重要的意义，并且已经合成了各种各样的此类化合物。然而，报道的合成方法通常遭受繁琐的多步程序和低收率的不饱和七元环的建设阶段。我们注意到托吡酯离子的亲电性，发展了两种合成含共轭七元环化合物的简便方法。我们的合成策略是使用市售的1，3，5-环庚三烯作为七元单元。1）通过邻芳基和邻杂芳基托品基苯的分子内Friedel-Crafts型反应，简便新颖地合成了含托品基离子的稠合全共轭环状化合物。作为苯并菲的等电子阳离子的环庚并[a]噻吩并萘鎓离子和环庚并[a]呋喃并萘鎓离子，以及作为强致癌性苯并[g]芘的等电子碳阳离子的环庚并[a]苯并呋喃并[c]萘鎓离子、环庚并[a]苯并噻吩并[c]萘鎓离子和环庚并[a]吲哚并[c]萘鎓离子，2）杂芳稠合氮杂茂衍生物的简便新颖的合成方法。（10-苯并[a] -甘菊环基）-a，b-不饱和酮和β-以合理的产率分别从邻- [2-呋喃基]托品基苯和1-托品基-2- [2-呋喃基]噻吩得到（9-奥并[1，2-B]噻吩基）-α，β-不饱和酮。的机制，涉及一种新的环化的分子内攻击的tropypyramidion的2-位的呋喃环的假设。测定了两种β-（9-奥基[1，2-B]噻吩基）-α，β-不饱和酮的X-射线晶体结构。