Studies On The Synthesis Of Hydrazine Derivatives And Carboxylic Anhydrides Induced By Metal Amides

The dissertation covers the studies on the reaction activities of metal amides M[N(SiMe₃)₂]X (M = Lanthanide, Y, Li, X = 1, 3) in the synthesis of hydrazine derivatives through a novel N-N bond radical coupling reaction and in the synthesis of symmetrical carboxylic anhydrides from acid chlorides. There are mainly two parts in the dissertation.Firstly, a novel method of fast synthesis of hydrazine derivatives was investigated by reaction of secondary amine with rare amides [(Me₃Si)₂N]3RE(μ-Cl)Li(THF)₃ (M = Ln, Y) through the N-N bond coupling reaction. The electronic and steric effects on the reaction have also been examined. Compared with the limited traditional approaches, the new methodology has the advantages of good to high yields, a very short time and mild reaction conditions. And the proposed mechanism concerned about the N-N radical coupling reaction through the oxidation of rare-earth metal-nitrogen (RE-N) bonds.Secondly, an easy and straightforward preparation of various symmetrical carboxylic anhydrides through the reaction of acid chlorides in the presence of LiN(SiMe₃)₂ was studied. The electronic effects on the reaction have been examined. Through the reactions, the symmetrical carboxylic anhydrides could be obtained in good to high yields with the features of economical catalysts and simple reaction conditions.In conclusion, a new and novel methodology of synthesis of hydrazine derivatives could be obtained through the N-N bond radical coupling reaction. And good to high yields of various symmetrical carboxylic anhydrides by reaction of acid chlorides in the presence of LiN(SiMe₃)₂ could be prepared .