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2012 , Vol. 32 >Issue 07: 1247 - 1254

DOI: https://doi.org/10.6023/cjoc201203013

研究论文

氨基取代的苯并咪唑衍生物的合成及在酮的氢转移反应中的应用

  • 段凯 ,
  • 李小娜 ,
  • 李云庆 ,
  • 王家喜
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  • 河北工业大学化工学院,天津 300130

收稿日期: 2012-03-30

  修回日期: 2012-05-07

  网络出版日期: 2012-05-11

基金资助

河北省自然科学基金(No. B2011202087 )资助项目.

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Syntheses and Application of Aminated Benzimidazole Derivatives in Transfer Hydrogenation Reaction of Ketones

  • Duan Kai ,
  • Li Xiaona ,
  • Li Yunqing ,
  • Wang Jiaxi
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  • School of Chemical Engineering, Hebei University of Technology, Tianjin 300130

Received date: 2012-03-30

  Revised date: 2012-05-07

  Online published: 2012-05-11

Supported by

Project supported by the Natural Science Foundation of Hebei province of China (No. B2011202087)

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摘要

以α-氨基酸与邻苯二胺在微波辐射下反应合成了α-氨基取代苯并咪唑(1~5),1-(1H-苯并[d]-咪唑-2-基)乙胺(1)与溴丁烷反应可形成单丁基、二丁基、三丁基取代产物(1a~1d), 1的氨基经Boc保护,N-烷基化后制备咪唑环上的N-烷基化产物(1i~1g)。制备的氨基取代咪唑与Ru(Ⅱ)化合物原位组成催化体系,考察了其在取代苯乙酮的氢转移反应中的催化活性。结果表明RuCl2(PPh3)3与各配体组成的催化剂均有较好的催化活性,含有NH2基团的α-氨基取代苯并咪唑化合物参与的催化体系催化活性最好,TOF可达到40200 h-1。

关键词： 氨基酸; 苯并咪唑; N-烷基化; 微波; 钌络合物; 酮; 氢转移反应

本文引用格式

段凯 , 李小娜 , 李云庆 , 王家喜 . 氨基取代的苯并咪唑衍生物的合成及在酮的氢转移反应中的应用[J]. 有机化学, 2012 , 32(07) : 1247 -1254 . DOI: 10.6023/cjoc201203013

Abstract

A series of α-amino-benzimidazole derivatives (1~5) were synthesized by reaction of α-amino acid with o-phenylenediamine under microwave irradiation. 1-(1H-benzo[d]imidazol-2-yl)ethanamine 1 reacted with bromobutane forming mono-butyl, dibutyl and tributyl substituted benzimidazole (1a~1d); and the N-alkylated derivatives (1i~1g) were synthesized by protection of amine group by Boc and then N-alkylation. The catalytic capability of the catalyst generated in situ from Ru (Ⅱ) compound and obtained benzimidazole derivatives were evaluated in the transfer hydrogenation of ketone using iso-PrOH as hydrogen donor and solvent. The results revealed that catalyst generated in situ from RuCl2(PPh3)3 and ligands had moderate to high activity. The catalyst system with α-amino-benzimidazole derivative containing NH2 group is the most active and the highest TOF was up to 40200 h-1.

Key words： amino acid; benzimidazole; N-alkylation; microwave; Ru(Ⅱ) complex; ketone; transfer hydrogenation

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