催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (8): 1044-1048.DOI: 10.3724/SP.J.1088.2010.00456

• 研究论文 • 上一篇    下一篇

钯催化 1,3-丁二烯羧酯化合成 3-戊烯酸甲酯

王连弟 1, 吴小伟 1,2, 赫巍 1, 刘子双 1, 余正坤 1   

  1. 1中国科学院大连化学物理研究所, 辽宁大连 116023 2大连民族学院生命科学学院, 辽宁大连 116600
  • 收稿日期:2010-04-29 出版日期:2010-08-30 发布日期:2013-12-26
  • 通讯作者: 余正坤

Palladium Catalyzed Carboxylation of 1,3-Butadiene to Methyl 3-Pentenoate

WANG Liandi1, WU Xiaowei1,2, HE Wei1, LIU Zishuang1, YU Zhengkun1,*   

  1. 1Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China 2College of Life Science, Dalian Nationalities University, Dalian 116600, Liaoning, China
  • Received:2010-04-29 Online:2010-08-30 Published:2013-12-26

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摘要： 以 1,3-丁二烯、CO 和甲醇为原料, 进行羧酯化反应合成 3-戊烯酸甲酯是 Altam 路线生产己内酰胺绿色工艺的关键步骤. 将 Pd 与三齿 N-杂环配体或双膦配体组成的催化体系用于 1,3-丁二烯的羧酯化反应中, 其中乙酸钯/2,6-二 (3,5-二甲基吡唑基) 吡啶催化剂表现出中等的催化活性, 在 150 ºC, p(CO) = 6.0 MPa 的优化条件下反应 6 h, 1,3-丁二烯转化率为 78.8%, 3-戊烯酸甲酯选择性达 92.2% (TON = 226); 而乙酸钯/2,2?-二 (二苯基膦基) 苯醚催化体系的活性更高, 在优化反应条件下, 1,3-丁二烯转化率达 90.4%, 3-戊烯酸甲酯选择性为 91.6% (TON = 181). 在 200 ºC 及类似的羧酯化反应条件下, 1,3-丁二烯发生二聚反应, 其转化率为 99% 以上, 二聚产物 4-乙烯基-1-环己烯选择性高于 96%.

关键词: 1,3-丁二烯, 钯, 三齿 N-杂环配体, 羧酯化, 3-戊烯酸甲酯, 己内酰胺, 双膦配体

Abstract: Palladium salts with N-heterocyclic ligand or biphosphine ligand were used as the catalysts for the carboxylation of 1,3-butadiene with carbon monoxide in methanol to methyl 3-pentenoate, which is one of the key reactions in Altam process for production of ?-caprolactam. The combination of Pd(OAc)2 with 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine exhibited moderate catalytic activity under the optimized conditions (150 ºC, p(CO) = 6.0 MPa, 6 h), reaching 78.8% conversion of 1,3-butadiene and 92.2% selectivity for the target product (TON = 226). Using Pd(OAc)2/(oxydi-2,1-phenylene)bis(diphenylphosphine) as the catalyst remarkably increased the reaction efficiency, achieving 90.4% conversion of 1,3-butadiene and 91.6% selectivity for the product (TON = 181). At temperature above 200 ºC, 1,3-butadiene underwent dimerization to form 4-vinyl-1-cyclohexene in 96% yield.

Key words: 1,3-butadiene, palladium, N-heterocyclic ligand, carboxylation, methyl 3-pentenoate, ?-caprolactam, biphosphine ligand