High-Performance RuCl3 Catalyst Systems for Hydro-Esterification of Methyl Formate and Ethylene
High-Performance RuCl3 Catalyst Systems for Hydro-Esterification of Methyl Formate and Ethylene
复制标题
用于甲酸甲酯和乙烯加氢酯化的高性能 RuCl3 催化剂体系
DOI：
10.1002/cjoc.201900084
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发表时间：
2019
影响因子：
5.4
通讯作者：
Guo-Cong Guo
中科院分区：
文献类型：
--
作者：
Yan-Ru Li;Zhong-Ning Xu;Bing Bai;Zhi-Qiao Wang;Guo-Cong Guo
RuCl3催化体系对甲酸甲酯和乙烯氢酯化合成丙酸甲酯具有许多优点。然而，不尽如人意的性能制约了这条路线的发展。本文首次报道了用于该反应的高性能RuCl3催化剂体系(RuCl3-[PPn]Cl-Et4NI和RuCl3-NaI)。在RuCl3-[PPN]Cl-Et4Ni催化体系中，在温和的反应条件下(165℃，2.5 Mpa)，甲酸甲酯的转化率为93.9%，丙酸甲酯的选择性为90.9%。值得注意的是，一个简单的无机RuCl3-NaI催化剂体系在相同的条件下，甲酸甲酯的转化率为88.8%，丙酸甲酯的选择性为97.6%(产率为86.7%)。NaI作为促进剂，可抑制甲酸甲酯的分解，有利于丙酸甲酯的生成。详细考察了溶剂和促进剂的影响。此外，还对反应机理进行了分析。希望为进一步的工业应用奠定一定的基础。
Summary of main observation and conclusionRuCl3catalyst 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 RuCl3catalyst 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.