Amination Based On The System Of Ammonium Formate-Pd/C

The application of Ammonium formate in organic synthesis was started from Leucart who transformed carbonyl compounds into amine using ammonium formate, and later successfully expanded this approach into1,5-dione and unsaturated ketones. Pd/C, which is of industrial importance, has been used widely, such as hydrogenation of unsaturated Olefin, Nitro and Nitroso as well as catalytic hydrogenation of carbonyl. The system of Ammonium formate-Pd/C combining the function of Ammonium formate and Pd/C, discussed in this thesis, could be used for the amination reactions of Carbonyl compounds.The amination based on system of ammonium formate-Pd/C is an example of the Catalytic Transfer Hydrogenation (CTH) reactions. In the reaction, Ammonium formate was the the source of hydrogen and nitrogen, and Pd/C as catalyst was used to catalyze the decomposing of Ammonium formate and the hydrogenation. The system had overcome lots of shortcomings of common methods, such as harsh reaction conditions, tedious operations, poor selectivity and so on. The amination took place under mild conditions in one-pot with high yield. The process was carried out by using ketones as substrates, such as3-quininone hydrochloride,2-admantone,1,3-diphenylacetone, acetophenone, tropinone,5-hydroxyl-2-admantone and so on. The amination product of2-admantone was2-admantadine which is used to produce flu drugs, for treatment of Parkinson’s disease, and that of the home-made5-hydroxyl-2-admanton from2-admantone was4-aminoadmantane-l-ol, which is the important raw material for the preparation of admantadine derivatives.3-aminequinine, the amination product of3-quininone, is the intermediate for the synthesis of digestive system drugs. However, only S-3-aminequinine is the effective component, thus, resolution of3-aminequinine racemate is greatly important. This thesis used a chemical resolution method to resolve3-aminequine, and obtained good results.During the experiments, reaction parameters, including Pd/C amount, recycling times of Pd/C, Ammonium formate amount, temperature, and solvent were carefully studied. The optimal reaction conditions were as follows:Solvent:CH3OH:H2O=9:1(volume ratio), HCOONH4:ketone:Pd/C=100:10:1(molar ratio), room temperature. Amination based on the system of ammonium formate-Pd/C is suitable for industrial production with the advantages of mild reaction conditions, easy availability, excellent reducibility and selectivity as well as low cost. The main products were confirmed by1H-NMR, GC-MS or MS, some of them were confirmed by IR and HPLC.