Functionalization Of α-carbon Atom Of Ketone Compounds Under The Electrochemical Condition

Organic electrochemistry is also called organic electrolytic synthesis, which is an edge discipline combination of organic synthesis and electrochemical technology. The reactions which carried by electrochemical method including the formation of carbon-carbon bonds and functional groups of addition, substitution, cracking, elimination, coupling, oxidation and reduction reactions and indirect electrosynthesisWith the rapid development of green organic synthesis, chemists always devote their efforts to make the reaction condition milder, the procedure of reaction simpler, more efficiency and environment friendly. Compared with the traditional oxidants and reductants, electrons are environment friendly, post processing simple and mild, which more meeting the requirement of sustainable development and low carbon economy.This thesis mainly studied the forming of carbon-carbon, carbon-nitrogen with the help of electrochemical methods. The thesis includes five parts; the first part summarizes the development direction of organic synthesis and the latest progress at home and abroad. The second part and the third part studies the organic synthesis of a-ketoamides and a-ketoesters; The fourth part and the fifth part studied the organic electrochemical synthesis of (3-enaminones and a-enaminones.First, on the basis of previous work of our laboratory, the method of combination electrochemical and iodine catalytic was developed. a-Ketoamides and a-ketoesters were synthesized by this method. In this series of reactions, iodine free radical which was generated in the anode can catalyze the functionalization of acetophenone, so as to realize esterification and amidation.of the alpha carbon of acetophenone. At the same time, during the reaction, oxygen was involved in the reaction.Then, on the basis of the above reaction, we added nitromethane to the reaction, P-enaminones were successfully synthesized. In the reaction, nitromethane ccould be used as the source of the carbon atoms. Compared to traditional methods, this method because of the use of acetophenone and nitromethane as substrate, the raw materials are relatively cheap and easy to obtain. At the same time, the reaction of no additional metal catalyst and additional oxidant, and the reaction also could be carried under room temperature, so this electrochemical method is of important value in industrial application.Finally, we studied the coupling reaction of aromatic amine and cyclopentanone under the electrochemical conditions. During the reaction, iodine was oxidated to the corresponding iodine free radical.2-Iodocyclopentanone was formed through the reaction between cyclopentanone and iodine free radical. Then2-(phenylamino)cyclopentanone was formed through nucleophilic substitution reaction between aniline and2-iodocyclopentanone. Finally,2-(phenylamino)cyclopentanone was oxidated to2-(phenylimino)cyclopentanone in the anode and was transfered further into a-enaminone through the rearrangement reaction. The method could direct synthesis a-enaminone using cyclopentanone as the starting materials, which did not need be oxidated to cyclopentane-1,2-dione. So this method could realize one pot synthesis of a-enaminone under the mild condition.In conclusion, a new method of forming carbon-carbon and carbon-nitrogen was developed with the combination of organic synthesis and electrochemistry. These methods were featured by mild conditions, simple procedure, broadening the scope of reaction substrates or catalysts and high industrial value, which provide new thoughts and direction for the development of green organic synthesis.