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High‐Performance RuCl3 Catalyst Systems for Hydro‐Esterification of Methyl Formate and Ethylene
Chinese Journal of Chemistry ( IF 5.5 ) Pub Date : 2019-06-13 , DOI: 10.1002/cjoc.201900084
Yan‐Ru Li 1, 2, 3, 4 , Zhong‐Ning Xu 1 , Bing Bai 1 , Zhi‐Qiao Wang 1 , Guo‐Cong Guo 1
Affiliation  

RuCl3 catalyst system has many advantages for the hydro‐esterification of methyl formate and ethylene to methyl propionate. However, the unsatisfied performance restricts the development of this route. In this work, high‐performance RuCl3 catalyst systems (RuCl3‐[PPN]Cl‐Et4NI and RuCl3‐NaI) are firstly reported for this reaction. In RuCl3‐[PPN]Cl‐Et4NI catalyst system, the conversion of methyl formate and the selectivity to methyl propionate are 93.9% and 90.9% at mild reaction conditions (165°C, 2.5 MPa), respectively. Noticeably, a simple inorganic RuCl3‐NaI catalyst system achieves 88.8% conversion of methyl formate and 97.6% selectivity to methyl propionate (86.7% yield) at same conditions. NaI, as a promoter, may inhibit the decomposition of methyl formate and be conducive to the formation of methyl propionate. The effects of solvents and promoters are investigated in detail. In addition, the reaction mechanism has been also analyzed. It is hoped to lay a certain foundation for further industrial application.

中文翻译:

用于甲基甲酸酯和乙烯加氢酯化反应的高性能RuCl3催化剂体系

RuCl 3催化剂体系对于甲酸甲酯和乙烯加氢酯化成丙酸甲酯具有许多优势。但是,不满意的性能限制了这条路线的发展。在这项工作中,首次报道了用于该反应的高性能RuCl 3催化剂体系(RuCl 3- [PPN] Cl-Et 4 NI和RuCl 3 -NaI)。在RuCl 3- [PPN] Cl-Et 4 NI催化剂体系中,在温和的反应条件下(165°C,2.5 MPa),甲酸甲酯的转化率和对丙酸甲酯的选择性分别为93.9%和90.9%。值得注意的是,简单的无机RuCl 3‐NaI催化剂体系在相同条件下实现了甲酸甲酯的88.8%转化率和丙酸甲酯的97.6%选择性(产率86.7%)。NaI作为促进剂,可以抑制甲酸甲酯的分解,并有利于丙酸甲酯的形成。详细研究了溶剂和促进剂的作用。另外,还分析了反应机理。希望为进一步的工业应用打下一定的基础。
更新日期:2019-06-13
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