高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (8): 1681.doi: 10.7503/cjcu20140053

• 有机化学 • 上一篇    下一篇

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

王泽东, 岳晓东, 陈莉()   

  1. 南开大学元素有机化学国家重点实验室, 天津 300071
  • 收稿日期:2014-01-16 出版日期:2014-08-10 发布日期:2019-08-01
  • 作者简介:联系人简介: 陈 莉, 女, 博士, 副教授, 主要从事有机合成方法学及天然产物全合成研究.E-mail: chenliyss@nankai.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21072103)和天津市自然科学基金(批准号: 10JCYBJC04200)资助

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

WANG Zedong, YUE Xiaodong, CHEN Li*()   

  1. State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China
  • Received:2014-01-16 Online:2014-08-10 Published:2019-08-01
  • Contact: CHEN Li E-mail:chenliyss@nankai.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21072103) and the Natural Science Foundation of Tianjin, China(No.10JCYBJC04200)

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.

关键词: 薁酮, 二芳基烯酮, 重排, 降蒈二烯

Abstract:

Nieuwenhuis and Arens discovered the reaction of diarylketenes with alkynyl ethers leads to substituted 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 ketene 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. Treatment 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.

Key words: Azulenone, Diarylketene, Rearrangement, Norcaradiene(Ed.: P, H, N, K)

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