The Study Of Oxidation Of Gem-disubstituted Aromatic Alkenes To Ketones

This paper reports gem-disubstituted aromatic alkenes as raw materials, copper(I) or transition metal-free as catalyst, oxidized alkenes to the corresponding ketones. In chapter 1, we used 1,1-diphenylethylene as raw material, the sorts of copper (I) salt, many kinds of nitrogen ligands, temperature, solvents, oxidants and other factors were explored in the reaction. Finally, We achieved the optimum conditions of the reaction, pyridine as solvent, CuBr as catalyst, TBHP as oxidant, catalytic the oxidation of gem-disubstituted olefins to ketones. During the expansion of the substrates, we found that the electron effect has little effect, and the structure of the olefins has a decisive effects on the reaction. The 1,2-disubstituted olefins, mono-substituted olefins and the alkyl substituted olefins can not react.In chapter 2,1,1-diphenylethylene was used as raw material,1,2-di-tert-butyldi-aziridinone as ligand, different catalysts, solvents, oxidants and other factors were studied in the reaction. Ultimately, the optimum conditions were determined and oxidized the gem-disubstituted olefins to ketons successfully. In the investigation of substrates, we found that the substituent group on the benzene ring reduced the oxidation yield, while the steric hindrance has no effects on the reaction. In addition, the structure of the olefins determines the reaction.1,2-disubstituted olefins or mono-substituted olefins could not be oxidized. Finally, we obtained the corresponding carbonyl compounds with higher oxidation yields and expanded the application range of 1.2-di-tert-butyldiaziridinone, which opened up a new direction of research.In chapter 3, through selecting appropriate solvent and using metal-free catalyst, we oxidized the gem-disubstituted aromatic alkenes to ketones directly. After the optimization of the reaction conditions, we obtained the final reaction conditions, acetonitrile as solvent, and TBHP as oxidant. In the substrate scope part, We found that the benzene ring played a great role in the reaction, when one of the benzene ring was replaced with methyl, the reaction effect decreased and the substituents on benzene further reduced the oxidation yield, we obtained the corresponding carbonyl compounds in medium yields.