Page 169 - 《精细化工》2021年第12期

第 38 卷第 12 期 精 细 化 工 Vol.38, No.12
2021 年 12 月 FINE CHEMICALS Dec. 2021

催化与分离提纯技术
Pd 催化剂上乙酰丙酸与腈还原胺化制

吡咯烷酮类化合物

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刘迎新 ，张 粮 ，张凯悦 ，成毓然 ，魏作君
（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）
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 xCeO 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/xCeO 2 -Al 2 O 3 催化剂。采用 XRD、N 2 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 H 2 ），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。
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
中图分类号：TQ251.3；TQ426 文献标识码：A 文章编号：1003-5214 (2021) 12-2531-08

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

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LIU Yingxin , ZHANG Liang , ZHANG Kaiyue , CHENG Yuran , WEI Zuojun
（1. College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China; 2. Key
Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering,
Zhejiang University, Hangzhou 310027, Zhejiang, China）
Abstract: A series of xCeO 2-Al 2O 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 2O 3, the same below) using citric acid complex method.
Then, 5% Pd/xCeO 2-Al 2O 3 catalysts (5% being Pd loading amount, on the basis of the mass of Al 2O 3, the
same below) were prepared by deposit-precipitation method. The physico-chemical properties of these
catalysts were characterized by XRD, N 2 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% CeO 2-Al 2O 3 catalyst under mild reaction conditions of 90 ℃ and 1.5
MPa H 2 for 5 h. Meanwhile, 5% Pd/10% CeO 2-Al 2O 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 2O 3 catalyst did not decrease significantly even if being recyled for 4 times.
Key words: biomass; levulinic acid; nitriles; catalysts; reductive amination; pyrrolidone compounds;
catalysis technology

收稿日期：2021-06-02; 定用日期：2021-07-12; DOI: 10.13550/j.jxhg.20210555
基金项目：国家自然科学基金（21878269，21476211）；浙江省自然科学基金（LY18B060016）
作者简介：刘迎新（1973—），女，教授，E-mail：yxliu@zjut.edu.cn。联系人：魏作君（1976—），男，副教授，E-mail：weizuojun@
zju.edu.cn。