Synthesis And Catalysis Of Guanidinato-metal Compounds

Organometallic chemistry is the bridge of organic chemistry and inorganic chemistry. It is one of the most active chemical subjects. Organometallic compounds have played a very important role in catalytic, medical, material chemistry and agriculture. Especially, as the catalyst, organometallic compounds can reach the requirements of green chemistry to achieve high selectivity, low pollution and 100% the atom economy.In the view of the above research background, a series of aluminum guanidinate compounds were synthesized, and applied to catalyze the Tishchenko reaction and Mannich reaction.Chapter 1. To introduce in detail development of the research topics of the thesis:(1) carbodiimide insertion into amino aluminum compounds and the synthesis of alkoxy aluminum compounds; (2) the research progress of the Tishchenko reaction; (3) the research progress of Mannich reaction.Chapter 2. The starting materials which are a series of secondary amine reacted with AlMe3 to synthesize the amino aluminum compounds, then the aluminum guanidinate compounds were synthesized by the carbodiimide insertion into amino aluminum compounds. The structures were characterized by NMR and X-ray single crystal diffraction analysis. In addition, a special alkoxy aluminum compound also was synthesized.Chapter 3. The aluminum and zinc guanidinate compounds were used to catalyze the Tishchenko reaction. As a conclusion, we confirmed that the aluminum and zinc guanidinate compounds were active catalysts and have good catalytic effect for the dimerization reaction of aromatic aldehydes and aliphatic aldehydes. Especially, the reaction condition was mild and can achieve the high yield with aliphatic aldehydes.Chapter 4. The aluminum guanidinate compounds were applied to catalyze the Mannich reaction. The one-pot Mannich-type reaction of aromatic aldehyde, aromatic amine, and acetophenone was discussed and studied under solvent-free condition and at room temperature. Some β-amino carbonyl compounds were synthesized with high yield.