Guzmán Barrera Nydia I, Peydecastaing Jérôme, Esvan Jérôme, Albet Joël, Vaca-Garcia Carlos, Behra Philippe, Vedrenne Emeline, Thiébaud-Roux Sophie
Laboratoire de Chimie Agro-Industrielle (LCA), Université de Toulouse, INRAE, Toulouse INP, 31030 Toulouse, France.
CIRIMAT, Université de Toulouse, Toulouse INP, CNRS, 31030 Toulouse, France.
Molecules. 2024 Oct 11;29(20):4822. doi: 10.3390/molecules29204822.
Methyl ethyl ketone (MEK) is among the most extensively utilized solvents in various industrial applications. In this study, we present a highly efficient synthesis route for MEK via the decarboxylation of biomass-derived levulinic acid, using potassium persulfate (KSO) and silver nitrate (AgNO) as key reagents. The specific roles of AgNO and KSO were thoroughly investigated. Additional silver species, such as AgO and AgO, were also detected during the reaction. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses provided evidence of the evolution of solid phases throughout the reaction. Based on these findings, we propose a radical decarboxylation mechanism initiated by the generation of sulfate radicals (SO•⁻) through the catalytic breakdown of KSO by AgNO. This mechanistic understanding, combined with a parametric study, enabled us to achieve an unprecedented level of levulinic acid conversion (97.9%) and MEK yield (86.6%) with this system, surpassing all previously reported results in the literature.
甲乙酮（MEK）是各种工业应用中使用最广泛的溶剂之一。在本研究中，我们提出了一种通过生物质衍生的乙酰丙酸脱羧高效合成MEK的路线，使用过硫酸钾（KSO）和硝酸银（AgNO）作为关键试剂。对AgNO和KSO的具体作用进行了深入研究。反应过程中还检测到了其他银物种，如AgO和AgO。X射线光电子能谱（XPS）和X射线衍射（XRD）分析提供了整个反应过程中固相演变的证据。基于这些发现，我们提出了一种自由基脱羧机制，该机制由AgNO催化分解KSO产生硫酸根自由基（SO•⁻）引发。这种机理认识与参数研究相结合，使我们能够在该体系中实现前所未有的乙酰丙酸转化率（97.9%）和MEK产率（86.6%），超过了文献中先前报道的所有结果。
