Study On The Synthesis Of Hydrazine Derivates And Application To Amination Reaction

At present, organic chemistry workers are paying their attention to study on C-H bond activation. Howeer, little information has been reported obtaining direct amination production by radical mothod about some substrates. The synthesis of hydrazine derivates and application to amination reaction were investigated in details. Meanwhile, we also gave a study on the reaction of bromcyclopropane with amide under Ullmann condition.Firstly, a series of hydrazine derivates were synthesized by reference. The synthetic method was simple, shortcut and high efficient.Secondly, our attention was focused on the hydrazine derivates applying to amination. We made the hydrazine derivates reacting with various substrates under the condition of metal catalyst or initiate radical agent, and had some results. When tetramethylhydrazine reacted with 2-naphthol under the condition of TEMPO, we had a result that tetramethylhydrazine formed radical ortho-coupling with the double molecules of 2-naphthol, and this result could extend to phenols. Meanwhile, the possible reaction mechanism was discussed. We also corrected the reaction mechanism of 2-naphthol reacting with N-methyl-N-phenylhydrazine, which could involve a bimolecular nucleophilic substitution with participation of radical induced by electron transfer. When we put the 8-Fluo-2-naphthol into the system of p-cresol reacting with N-methyl-N-phenyl hydrazine, we could obtain trace production of the direct ortho-amination of p-cresol.Through changing the reaction condition, the quantity production of the direct ortho-amination of p-cresol was as before. But, the result of reaction could make a bright future about the amination of phenols with hydrazine.Finally, we researched the reaction of the 1-Bromo-2-phenylcyclopropane under the condition of Ullmann reaction. From the result of study, the structure of cyclopropane was opened and the substance-opened was occured coupling between the double molecules. When added the nucleophilic substances to the reaction, the substance-opened was able to occur coupling reaction with the nucleophilic substances, and had a medium reaction efficiency.