有机化学 ›› 2012, Vol. 32 ›› Issue (07): 1247-1254.DOI: 10.6023/cjoc201203013 上一篇    下一篇

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   

  1. 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 出版日期:2012-07-25 发布日期:2012-05-11
  • 通讯作者: 王家喜 E-mail:jwang252004@126.com
  • 基金资助:
    河北省自然科学基金(No. B2011202087 )资助项目.

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

Duan Kai, Li Xiaona, Li Yunqing, Wang Jiaxi   

  1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130
  • Received:2012-03-30 Revised:2012-05-07 Online:2012-07-25 Published:2012-05-11
  • Supported by:
    Project supported by the Natural Science Foundation of Hebei province of China (No. B2011202087)

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

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