Mn对Ru/SiO_(2)催化2,5-己二酮与伯胺合成N-取代-2,5-二甲基吡咯烷的促进作用  

Promotion effect of Mn on Ru/SiO_(2)catalyst for the synthesis of N-substituted 2,5-dimethylpyrrolidines from 2,5-hexadione and primary amines

作　　者：胡锦波 钟齐锋 陈诗怡 吴海梅 刘迎新[1] HU Jinbo;ZHONG Qifeng;CHEN Shiyi;WU Haimei;LIU Yingxin(College of Pharmaceutical Science,Zhejiang University of Technology,Hangzhou 310014,China)

机构地区：[1]浙江工业大学药学院,浙江杭州310014

出　　处：《石油化工》2024年第7期940-946,共7页Petrochemical Technology

基　　金：浙江省自然科学基金项目(LY23B060006)。

摘　　要：采用共浸渍法制备了Mn掺杂的Ru/SiO_(2)催化剂,将其用于2,5-己二酮与伯胺经Paal-Knorr/加氢级联反应合成N-取代-2,5-二甲基吡咯烷,利用XRD,TEM,NH3-TPD,XPS等方法探究了Mn对催化剂结构和性质的影响,并考察了催化剂的稳定性与适用性。实验结果表明,Mn掺杂可提高催化剂中Ru纳米粒子的分散度和催化剂的酸性位,进而提高催化剂的性能。当Ru/Mn摩尔比为1∶2时,催化剂的催化活性最高,在H2O溶剂中130℃、氢气压力3 MPa下反应90 min,2,5-己二酮转化率和N-丁基-2,5-二甲基吡咯烷的收率均达到100%。催化剂重复使用9次后仍保持高活性,且催化剂具有良好的普适性,为N-取代吡咯烷类化合物的绿色合成提供了一种新思路。Mn-doped Ru/SiO_(2)catalysts were prepared by a co-impregnation method and used for the synthesis of N-substituted 2,5-dimethylpyrrolidines through a Paal-Knorr/hydrogenation cascade reaction of 2,5-hexadione with primary amines.The effects of Mn on the structure and properties of the catalysts were investigated using XRD,TEM,NH3-TPD,and XPS techniques.The stability and applicability of the catalysts were also examined.The results show that Mn doping improves the dispersion of Ru nanoparticles and increases the acidic sites of the catalysts,thereby enhancing their catalytic performance.When the Ru/Mn molar ratio is 1∶2,the catalysts exhibit the highest catalytic activity,achieving 100%conversion of 2,5-hexadione and 100%yield of N-butyl-2,5-dimethylpyrrolidine in H2O solvent at 130℃and 3 MPa hydrogen pressure after 90 min.The catalyst maintains high activity after nine cycles of reuse and shows good universality.This work provides a new approach for the green synthesis of N-substituted pyrrolidines.

关 键 词：2 5-己二酮 N-取代吡咯烷 RuMn/SiO_(2)催化剂 级联反应 生物质 

分 类 号：TQ426.8[化学工程]