氨基取代苯并咪唑衍生物的合成及在酮的氢转移反应中的应用  

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

作　　者：段凯[1] 李小娜[1] 李云庆[1] 王家喜[1] 

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《有机化学》2012年第7期1247-1254,共8页Chinese Journal of Organic Chemistry

基　　金：河北省自然科学基金(No.B2011202087)资助项目~~

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(Turnover frequency)可达到40200 h-1.A series of a-amino-benzimidazole derivatives 1-5 were synthesized by reaction of a-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 la^ld; and the N-alkylated derivatives 1i-1g were syn thesized 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 ketones using iso-PrOH as hydrogen donor and solvent. The results revealed that catalyst generated in situ from RUC1E（PPh3）3 and ligands had moderate to high activity. The catalyst system with a-amino-benzimidazole derivative containing NH2 group is the most active and the highest TOF （turnover frequency） was up to 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 

分 类 号：O626.23[理学—有机化学]