Pd催化剂上乙酰丙酸与腈还原胺化制吡咯烷酮类化合物  

Synthesis of pyrrolidone compounds via reductive amination of levulinic acid with nitriles over Pd catalysts

作　　者：刘迎新[1] 张粮 张凯悦 成毓然 魏作君[2] LIU Yingxin;ZHANG Liang;ZHANG Kaiyue;CHENG Yuran;WEI Zuojun(College of Pharmaceutical Science,Zhejiang University of Technology,Hangzhou 310014,Zhejiang,China;Key Laboratory of Biomass Chemical Engineering of Ministry of Education,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,Zhejiang,China)

机构地区：[1]浙江工业大学药学院,浙江杭州310014 [2]浙江大学化学工程与生物工程学院生物质化工教育部重点实验室,浙江杭州310027

出　　处：《精细化工》2021年第12期2531-2538,共8页Fine Chemicals

基　　金：国家自然科学基金(21878269,21476211);浙江省自然科学基金(LY18B060016)。

摘　　要：采用柠檬酸络合法,通过调整CeO_(2)含量(x=5%、10%、20%、30%)(以Al_(2)O_(3)的质量计,下同)制备出一系列x CeO_(2)-Al_(2)O_(3)复合氧化物,以此为载体用沉积-沉淀法制备了Pd负载量(以Al_(2)O_(3)的质量计,下同)为5%的5%Pd/x CeO_(2)-Al_(2)O_(3)催化剂。采用XRD、N2吸附-脱附、TEM、XPS对催化剂的物化性质进行了表征,探讨了催化剂对生物质基乙酰丙酸与腈类化合物"一锅法"还原胺化合成N-取代基-5-甲基-2-吡咯烷酮类化合物的催化性能。结果表明,在温和的反应条件下(90℃、1.5 MPa H2),催化剂5%Pd/10%CeO_(2)-Al_(2)O_(3)上乙酰丙酸与苯甲腈反应5 h,N-苄基-5-甲基-2-吡咯烷酮收率高达87.5%。在该催化剂上,乙酰丙酸(酯)与其他多种腈类化合物反应同样获得了较高的吡咯烷酮类化合物收率(76.3%~87.4%)。催化剂5%Pd/10%CeO_(2)-Al_(2)O_(3)循环4次后,活性无明显下降。A series of x Ce O2-Al_(2)O_(3) composite oxides were prepared by adjusting the content of CeO_(2)(x=5%,10%,20%,30%)(on the basis of the mass of Al_(2)O_(3),the same below)using citric acid complex method.Then,5%Pd/x Ce O2-Al_(2)O_(3) catalysts(5%being Pd loading amount,on the basis of the mass of Al_(2)O_(3),the same below)were prepared by deposit-precipitation method.The physico-chemical properties of these catalysts were characterized by XRD,N2 adsorption-desorption,TEM and XPS.Moreover,the catalytic performances of the catalysts for the one-pot reductive amination of biomass levulinic acid with nitriles towards N-substituted-5-methyl-2-pyrrolidone compounds were investigated.The results showed an 87.5%yield of N-benzyl-5-methyl-2-pyrrolidone was achieved through the reductive amination of levulinic acid with benzonitrile over 5%Pd/10%Ce O2-Al_(2)O_(3) catalyst under mild reaction conditions of 90℃and 1.5MPa H2 for 5 h.Meanwhile,5%Pd/10%CeO_(2)-Al_(2)O_(3) catalyst was efficient for the reductive amination of levulinic acid/ester with various nitriles to give high yields(76.3%~87.4%)of pyrrolidone compounds.The activity of 5%Pd/10%CeO_(2)-Al_(2)O_(3) catalyst did not decrease significantly even if being recyled for 4 times.

关 键 词：生物质 乙酰丙酸 腈 催化剂 还原胺化 吡咯烷酮类化合物 催化技术 

分 类 号：TQ251.3[化学工程—有机化工] TQ426