2,3,4-三甲氧基苯基-苯基-烯酮与乙氧基乙炔的加成重排反应  

Reaction of 2-Phenyl-2-( 2,3,4-trimethoxyphenyl) ketene with Ethoxyethyne

作　　者：王泽东[1] 岳晓东[1] 陈莉[1] 

机构地区：[1]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《高等学校化学学报》2014年第8期1681-1685,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21072103);天津市自然科学基金(批准号:10JCYBJC04200)资助~~

摘　　要：研究了2,3,4-三甲氧基苯基-苯基-烯酮(9)与乙氧基乙炔的加成-重排反应,得到2种薁酮异构体产物(11和12),其结构经核磁共振波谱和X射线单晶衍射分析进行了确证.该研究结果为Woodward所提出的分步反应机理提供了实验依据.Nieuwenhuis and Arens discovered the reaction of diarylketenes with alkynyl ethers leads to substi-tuted azulenones in 1958 . This reaction involved the construction of four C-C bonds in a single operation and provided facile access to a functionalized bicyclo [ 5.3.0 ] decane skeleton. Although the mechanism of this transformation was rationalized later by Woodward and Barton, respectively, the synthetic value of this reaction has not been demonstrated so far. In this work, 2-phenyl-2-（2,3,4-trimethoxyphenyl）ketene（9） as a new ke-tene was first synthesized from 1,2,3-trimethoxybenzene and ethyl 2-chloro-2-oxoacetate through 5 steps. The reaction of compound 9 with ethoxyethyne（2） produced two novel angular aryl-substituted azulenone products 11 and 12, whose isomeric structures were characterized by NMR and X-ray crystallographic analysis. Treat-ment of azulenone 11 with Lewis acid afforded azulenone 12 . These results provided an additional experimental supported for a stepwise pathway rationalized by Woodward earlier on.

关 键 词：薁酮 二芳基烯酮 重排 降蒈二烯 

分 类 号：O621.3[理学—有机化学]