Mechanistic Studies On Electrochemical Carboxylation Of Benzalacetone

In recent years, the research of organic electrochemical synthesis developed rapidly, mainly due to the reaction process of electrochemical synthesis compared to traditional organic synthesis is more efficient, much less reaction steps and avoided the tough reaction steps..Mechanistic studies on electrochemical carboxylation of benzalacetone is the mainly studied content of this thesis. This study can not only make a research on the reaction mechanistic of the structure with Michael receptor in electrochemistry, but also is very meaningful because the electrocarboxylation of benzalacetone is totally accord with green chemistry. In the research process of electrocarboxylation of benzalacetone, we discussed some factors, such as electrode materials, electricity quantity, solvent, electrolytic potential and so on, which may affect the yield. Through the systematic research, we hope to improve the yield of 2-phenyllevulinic acid and have a preliminary understanding of this reaction.In the field of electrochemistry, cyclic voltammetric behavior is a routine means from which we can get related information of the reaction. But the information got through such metod is very limited. In recent years, with the rapid development of computer and theory models in chemical field, chemical related softwares were wildly accepted. In the process of research, we investigated the cyclic voltammetric behavior of benzalacetone under N2 and CO2 at first. Secondly, with the help of Digisim software and the proposed mechanism, we can get the kinetic data such as standard reduction potential Eo, rate constant ks of heterogeneous reaction, equilibrium constant Keq of homogeneous raction, etc.In addition to the simulation software like Digisim, some classical theory can also get the kinetic data from the reaction. But the reports about applied these classical theories, including the Koutecky-Levich equation, the semi-empirical Tafel equation in kinetic research of organic electrochemical synthesis are rare. In this thesis we applied these classical theories in kinetic research of organic electrochemical synthesis with the help of rotating disk electrode device. And got a series of kinetic data including limiting current density jiy exchange current density jo, Tafel slop b and heterogeneous reaction rate ks on different electrode. Through the kinetic data we can well explaine the experimental results and guide the new experiments.By means of the DFT calculation, we can study the energy of intermediate state, transition state and the reaction path. Therefore, DFT calculation is an effective way to study the reaction mechanism. To explain the experimental results more prisely, we can also research the reaction mechanisim through DFT calculation with proper solvent model. Finally, we proved that electrochemical carboxylation of benzalacetone can get the only acid product 2-phenyllevulinic acids through DFT calculation and got the related reaction path.