Syntheis Of ?-benzylated Amides Via Electrocatalytic Favorskii Rearrangement Of Benzy Letones

The theme of the world today is peace and development.The rapid change of science and technology at the sanme time,we are faced with the environmental problems is also growing.Now more and more countries and people have realized the seriousness of the environmental damage and the urgency of setting up environmental awareness and undertaking environmental protection.Electroorganic synthesis,as a relatively new technology,accords with the requirements of green chemistry,and is therefore increasingly valued by chemists.In the past decade,electroorganic synthesis that employs electrons as reagents,has been developed to be a versatile and environment-friendly synthetic tool and become increasingly attractive.The thesis altogether includes two parts,the first part is a brief introduction of organic electrochemistry and Favorskii rearrangement reactions are summarized.The second part details the synthesis of a-benzylated amides via electrocatalytic Favorskii rearrangement of Benzyl ketones.We found that in the process of filter response 1,3-diphenyl-2-acetone in four of the presence of hydrogen pyrrole,tetrabutyl ammonium iodide as a supporting electrolyte,acetonitrile as the solvent of Favorskii got in the process of constant current electrolysis method after rearrangement of a-benzylated saturated amide.To the best of our knowledge,a direct one-pot transformation of ketones into saturated amides via electrochemically induced Favorskii rearrangement has not been reported.This means that we provide a new synthetic pathway for the direct conversion of ketone to saturated amide.Compared with the classical method of Favorskii rearrangement reaction,the substrate ketone of this experiment not need been a-halogenated in beforehand,direct one-pot method get rearrangement product omitted a-halogenated ketone complex reaction steps and harsh reaction conditions.This thesis in 1,3-diphenyl-2-acetone as the model compound,adopt the method of constant current electrolysis,through to the electrode material,solvent,the type of supporting electrolyte,current density,power,such as electrolytic conditions are optimized,we find out the relative optimal reaction conditions.On the basis of this,we synthesize a series of amide products that have been rearranged by Favorskii.The electrocatalytic Favorskii rearrangement of 1,3-diarylacetones including electron-withdrawing substituents was favored and gave a good yield of a-benzylated amides,but the strong electron-donating group not get the desired product,and the benzyl is necessary in the substrate.When several unsymmetrical ketones were employed as substrates,this rearrangement with moderate regioselectivity was observed and the electron-withdrawing substituted benzyl group is relatively easy to migrate.We conducted extensive research on the substrate amine,the results suggest that aliphatic amines obtained better results but arylamines were unreactive due to poor nucleophilicity.In summary,we provide an efficient protocol for a direct one-pot transformation of ketones into saturated amides via electrochemically induced Favorskii rearrangement,and this chemistry also provides an efficient approach to construct a chiral center at a-position of amides.The whole reaction is done directly by one-pot,the route is simple and efficient,easy to operate and handle,and the use of the electron as a clean reagent meets the requirements of green development.