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Methyl ketones from carboxylic acids as valuable target molecules in the biorefinery
Catalysis Today ( IF 5.2 ) Pub Date : 2020-03-27 , DOI: 10.1016/j.cattod.2020.03.042
Olivier Marie , Alexey V. Ignatchenko , Michael Renz

For the preparation of methyl ketones, cross Ketonic Decarboxylation, i.e., the formation of a ketone from two different carboxylic acids, and the reketonization, i.e., the transformation of a carboxylic acid into a ketone employing a ketone as alkyl transfer agent, may be interesting alternatives to classical pathways involving metal-organic reagents.

The fine chemical 2-undecanone was chosen as model compound and ketonic decarboxylation and reketonization evaluated by Green Chemistry matrices, namely the carbon atom efficiency and the e-factor. The e-factor of the reaction of decanoic acid with acetic acid was less than five and, therewith, in the acceptable range for bulk chemicals, when valorizing acetone (e.g., as a solvent) and considering a 90% solvent recycling. The reketonization of decanoic acid with acetone provided a different main product, namely 10-nonadecanone, with a detrimental effect on atom efficiency.

By means of labeling experiments it was shown that ketonic decarboxylation is significantly faster than the reketonization reaction. The transformation of acetic acid into acetone was studied by in-situ and operando IR spectroscopy. Thereby it was found that the surface was covered by acetic acid. The lack of adsorption of acetone is a clear drawback for the reketonization of carboxylic acids. To improve the reaction outcome, and therewith, its sustainability a possibility has to be found to stabilize the ketone molecules on the surface in the presence of carboxylic acids.



中文翻译:

来自羧酸的甲基酮作为生物精炼厂中有价值的目标分子

对于制备甲基酮,交叉酮脱羧,即由两种不同的羧酸形成酮,再酮化,即用酮作为烷基转移剂将羧酸转化成酮,可能是有趣的。涉及金属有机试剂的经典途径的替代方法。

选择精细的2-十一烷酮作为模型化合物,通过Green Chemistry矩阵评估酮的脱羧和酮化反应,即碳原子效率和e-因子。癸酸与乙酸反应的e因子小于5,因此,在对丙酮(例如,作为溶剂)进行增价并考虑90%的溶剂回收利用时,在散装化学品可接受的范围内。癸酸与丙酮的再酮化反应提供了另一种主要产物,即10-十八碳酮,对原子效率有不利影响。

通过标记实验表明,酮的脱羧作用明显快于再酮化反应。通过原位操作红外光谱研究了乙酸向丙酮的转化。从而发现表面被乙酸覆盖。丙酮缺乏吸附是羧酸再酮化的明显缺点。为了改善反应结果,并由此改善其可持续性,必须找到在羧酸存在下稳定表面上的酮分子的可能性。

更新日期:2020-04-20
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