高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (5): 893.doi: 10.7503/cjcu20141144

• 有机化学 • 上一篇    下一篇

碘化1-甲基-2-异丙基(或丙基)-3-苯磺酰基咪唑啉的合成及基团转移反应

温雪山1,3, 霍明章2, 陈建新1()   

  1. 1. 山西师范大学化学与材料科学学院, 临汾 041004
    2. 山西大同大学医学院, 大同 037008
    3. 宁夏环境监测站宁东能源化工基地, 银川 750000
  • 收稿日期:2014-12-29 出版日期:2015-05-10 发布日期:2015-04-08
  • 作者简介:联系人简介: 陈建新, 男, 教授, 主要从事有机合成、 仿生有机合成和有机硅化学研究. E-mail: jjxxcc2002@yahoo.com
  • 基金资助:
    山西省留学回国人员基金(批准号: 0713)、 山西省自然科学基金(批准号: 2012011046-9)和山西师范大学基金(批准号: SD2014CXXM-53)资助

Synthesis and Group Transfer Reaction of 1-Methyl-2-isopropyl(or propyl)-3-benzenesulfonyl Imidazolidinium Iodide

WEN Xueshan1,3, HUO Mingzhang2, CHEN Jianxin1,*()   

  1. 1. College of Chemistry and Material Science, Shanxi Normal University, Linfen 041004, China
    2. Medical College of Shanxi Datong University, Datong 037008, China
    3. Ningdong Energy Chemical Base, Environmental Monitoring Site of Ningxia, Yinchuan 750000, China
  • Received:2014-12-29 Online:2015-05-10 Published:2015-04-08
  • Contact: CHEN Jianxin E-mail:jjxxcc2002@yahoo.com
  • Supported by:
    † Supported by the Foundation for Returness of Shanxi Province, China(No.0713), the Natural Science Foundation of Shanxi Province, China(No.2012011046-9) and the Foundation of Shanxi Normal University, China(No.SD2014CXXM-53)

摘要:

合成了新的四氢叶酸辅酶(THF)模型化合物碘化1-甲基-2-异丙基-3-苯磺酰基咪唑啉(5a)和碘化1-甲基-2-丙基-3-苯磺酰基咪唑啉(5b), 研究了其反应性能. 结果表明, 化合物5与双官能团亲核体邻苯二胺或邻氨基苯酚反应, 完全转移了4个碳的异丁基和正丁基单元, 基于此探索了合成2-取代苯并咪唑及2-取代苯并唑的新方法; 化合物5a与单官能团亲核体胺类反应部分转移了4个碳的异丁基单元, 生成不同基团取代的N,N,N'-三取代乙二胺盐; 化合物5a在NaBH4作用下可发生还原反应, 在NaOH水溶液中可发生水解反应, 也可与碳负离子基团(硝基甲基负离子或二腈基甲基负离子)发生亲核加成反应, 生成了3类不同基团取代的N,N,N'-三取代乙二胺衍生物, 探索了此类化合物的简易合成方法. 这些反应模拟了四氢叶酸辅酶在生物体内转移一碳单元的功能, 并将其扩展到4个碳原子单元, 获得了可应用于有机合成的新方法和新试剂.

关键词: 四氢叶酸, 咪唑啉盐, 转移反应, 模型, 加成反应

Abstract:

In the course of developing synthetic methods based upon mechanisms of biochemical processes, 1-methyl-2-isopropyl-3-benzenesulfonyl imidazolidinium iodide(5a) and 1-methyl-2-propyl-3-benzenesulfonyl imidazolidinium iodide(5b) were prepared as the tetrahydrofolate model compounds at the oxidation level of formate, which reacting with bifunctional nucleophiles o-phenylenediamine and 2-aminophenol. In the synthe-tic process, four carbon fragments were transferred completely and we found a way directly to benzimidazoles, benzoxazoles. The reaction of the model compound 5a with monofunctional nucleophiles(butylamine, aniline, benzylamine, p-methoxyaniline) afforded the products transferred part of four carbon fragments, containing three different groups of N,N,N'-trisubstituted ethylenediamine salt. Sodium borohydride reduction of 5a afforded compound 9. Treatment of compound 5a with NaOH caused hydrolysis and the corresponding carbonyl compound 10 was formed. The nucleophilic addition reaction of compound 5a with some carbanion(nitrome-thane carbanion and malononitrile carbanion) gave compounds 12 and 13, respectively. Compounds 9, 10, and 12 or 13 are three kinds of containing different groups of N,N,N'-trisubstituted ethylenediamine.

Key words: Tetrahydrofolate, Imidazolinium salt, Transfer reaction, Model, Addition action

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