高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (9): 1604.

• 论文 • 上一篇    下一篇

12-(酰氧亚氨基)-1,15-十五内酯的合成及结构表征

张建军, 董燕红, 梁晓梅, 王道全   

  1. 中国农业大学应用化学学院, 农药化学及农药使用技术农业部重点开放实验室, 北京 100094
  • 收稿日期:2002-08-28 出版日期:2003-09-24 发布日期:2003-09-24
  • 通讯作者: 王道全(1944年出生),男,博士,教授,博士生导师,主要从事大环化合物化学及新农药创制研究.E-mail:wangdq@cau.edu.cn E-mail:wangdq@cau.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20272079)

Synthesis and Characterization of 12-Acyloxyimino-1,15-pentadecanolides

ZHANG Jian-Jun, DONG Yan-Hong, LIANG Xiao-Mei, WANG Dao-Quan   

  1. Key Lab of Pesticide Chemistry and Application Technology, College of Applied Chemistry, China Agricultural University, Beijing 100094, China
  • Received:2002-08-28 Online:2003-09-24 Published:2003-09-24

PDF (PC)

被引次数

3

摘要： 以α-硝基环十二酮为原料,与丙烯醛加成、扩环并经Nef反应合成了12-氧代-1,15-十五内酯,再经成肟和酰化及硅胶柱层析分离分别得到12-(酰氧亚氨基)-1,15-十五内酯的顺式及反式异构体.结构经IR,1HNMR及元素分析确证.通过对个别化合物的单晶X射线分析,结合1HNMR数据,分别确定了它们的Z,E构型.结果表明,12-氧代-1,15-十五内酯成肟时对顺、反异构体的形成缺少明显的选择性,而目标化合物环骨架的优势构象为[23434],羰基和肟基位于两个不同的角碳位置.

关键词: 12-肟基-1, 15-十五内酯, 12-(酰氧亚氨基)-1, 15-十五内酯, 合成

Abstract: By the addition with acraldehyde, ring-enlargement and Nef reaction, 12-acyloximino-1, 15-pentadecanolides were synthesized from α-nitro-cyclododecanone. cis- and trans-isomers of 12-acyloxyimi-no-l,15-pentadecanolides were obtained by oximation, O-acylation and silica gel column chromatography separation, respectively. The structure of all the title compounds were confirmed by IR, 1HNMR and elementary analysis. Their configurations and conformations were determined by the crystal X-ray analysis of a representative compound and 1HNMR. The results show that the oximation of 12-oxo-l,15-pentade-canolide displays low selectivity for cis- and trans- isomers and the preferred conformation of the ring skeleton is[23434], with the carbonyl group and oximido group present in the two different corner-carbon positions, respectively.

Key words: 12-Oximido-1,15-pentadecanolide, 12-Acyloxyimino-1,15-pentadecanolide, Synthesis

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