苯萘体系普朔尔环化反应中桥原子与取代基对芳香自由基诱导分子内1,5-氢转移的影响  

Effect of the bridging atoms and substituent groups on the aromatic radical-induced intramolecular 1,5-hydrogen transfer in Pschorr cyclization of phenyl naphthyl system

作　　者：王静[1] 程耀邦[1] 边悦玲[1] 徐兆超[2] 崔京南[1] 

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116024 [2]中国科学院大连化学物理研究所,辽宁大连116023

出　　处：《中国科技论文》2012年第6期454-461,468,共9页China Sciencepaper

基　　金：高等学校博士学科点专项科研基金资助项目(20100041110021)

摘　　要：以1,8-萘酐为母体,合成了多种萘酐和萘酰亚胺重氮盐,在相同条件下进行普朔尔环化反应,证实了该体系中存在芳香自由基诱导的分子内1,5-氢转移。通过分析萘苯醚、硫醚和胺体系普朔尔环化产物中五元环化合物与六元环化合物的比率,探讨了桥原子和取代基对芳香自由基诱导的分子内1,5-氢转移的影响。研究发现,取代基能显著影响萘苯醚和萘苯胺体系的1,5-氢转移速率,但对萘苯硫醚体系影响不明显。同时推测,由于桥原子不同,环化反应速率差别较大,使得其环化产率和异构体比例差异明显。Diazonium salts of naphthalic anhydride and naphthalimide derivatives have been synthesized from 1,8-naphthalic anhydride and underwent Pschorr cyclization under the same condition, which confirms that there are aromatic radical-induced intrarnolecular 1,5-hydrogen transfers. Analysis of their oxa-, thio-and amin-cyclic fused five-and six-membered isomers of Pschorr cyclization shows that substituent groups of phenyl naphthyl ether and phenyl naphthyl amine have considerable effects on the ratios of the isomers, but there is no obvious variation for phenyl naphthyl thioether. It can be speculated that the variation ofcyclization yields and ratios of isomers result from the different bridging groups.

关 键 词：普朔尔环化 分子内1 5-氢转移 取代基 桥原子 

分 类 号：O621.2[理学—有机化学]