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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (04): 490-496. 上一篇    下一篇

研究论文

N-(ω-三甲基硅烷基醚)马来酰亚胺的光诱导单电子转移反应

黄益慧，张晓媛，谭广慧，刘岩，魏树权，曲凤玉，岳群峰，金英学*   

  1. (哈尔滨师范大学化学化工学院 哈尔滨 150025)
  • 收稿日期:2010-05-04 修回日期:2010-09-06 发布日期:2010-11-23
  • 通讯作者: 金英学 E-mail:yenghak@hrbnu.edu.cn
  • 基金资助:

    多供电子体-酰亚胺体系电子转移光反应效率及大话化合物的合成与荧光感应性能研究;光诱导电子转移反应大环化合物的合成与其荧光感应性能研究;光催化大环分子化合物的合成及超分子纳米材料的研究

Photoinduced Single Electron Transfer Reactions of N-(ω-Trimethylsilylether)maleimides

HUANG Yi-Hui, ZHANG Xiao-Yuan, TAN Guang-Hui, LIU Yan, WEI Shu-Quan, QU Feng-Yu, YUE Qun-Feng, JIN Ying-Xue   

  1. (College of Chemistry & Engineering, Harbin Normal University, Harbin 150025)
  • Received:2010-05-04 Revised:2010-09-06 Published:2010-11-23

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合成了两个N-(ω-三甲基硅烷基醚)马来酰亚胺衍生物(2a, 2b), 并以2a, 2b为光反应底物在HCN, MeOH, 30% H2O-HCN, 丙酮等溶剂中进行了光反应. 结果显示, 化合物2a在强的亲硅性溶剂MeOH, 30% H2O-MeOH, 30% H2O-HCN中经单电子转移反应以很高的产率和区域选择性生成环胺醇产物3, 在HCN、丙酮等弱的亲硅性溶剂中发生[2＋2]环加成副反应生成双分子偶合产物5|2b无论是在强的亲硅性溶剂, 还是在弱的亲硅性溶剂HCN、丙酮中, 都发生分子内单电子转移反应, 生成分子内双离子自由基中间体8. 一部分8发生脱三甲基硅烷基反应生成环化物4的前体分子内双自由基9, 多数8发生特殊的分子间偶合反应得到不对称双分子偶合产物6. 所有新化合物均经NMR和质谱验证.

关键词: 马来酰亚胺, 光反应, 单电子转移, 氢提取反应, 双分子化

Two N-(ω-trimethylsilylether)maleimides (2a, 2b) were synthesized and their photoreaction procedures in different solvents, such as HCN, MeOH, 30% H2O-MeOH, 30% H2O-HCN and acetone, were investigated respectively. The results showed that, 2a occurred intramolecular SET to provide cyclic amidol 3 with highly yield and highly regioselectivity in silophiles such as MeOH, 30% H2O-MeOH, 30% H2O-MeCN, and occurred side reaction to produce [2＋2] dimerization product 5 in the weak silophiles HCN and acetone. 2b occurred intramolecular SET to provide intermediate zwitterionic radicals 8 in all the highly and weak silophiles. A few of 8 occurred desilylation to produce intramolecular biradicals 9 which is the precursor of the cyclic amidol 4. Most of 8 occurred intermolecular radicals coupling to produce cyclic asymmetric dimerization compound 6. Structure of all compounds were characterized by MS (EI), NMR data.

Key words: >maleimide, photoreaction, single electron transfer, H-atom abstraction, dimerization