Institut für Chemie

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Influence of microwave irradiation and ionic liquids on multi component reactions
(2013) Mert-Balci, Fadime; Beifuss, Uwe
The present thesis focuses on the influence of microwave irradiation and ionic liquids on the outcome of two well-known three component reactions, the Groebke reaction and the Povarov reaction. The first part of the thesis deals with the influence of microwaves and ionic liquids on the Groebke reaction. The reaction of 2-aminopyridines with aldehydes and isocyanides using montmorillonite as a catalyst in toluene under microwave conditions at 160°C delivers the corresponding imidazo[1,2-a]pyridines within only seven minutes with yields ranging from 16 to 98%. The organic solvent can be replaced by ionic liquids like imidazolium and guanidinium salts. With guanidinium salts, it is possible to perform the Groebke reaction in the absence of any other catalyst and solvent under microwave conditions. The second part of this work is about the extension of the scope of typical Groebke reactions by replacing the aldehyde component with a bifunctional 2-carboxybenzaldehyde. The reaction of 2-aminopyridines with isocyanides and 2-carboxybenzaldehydes with 20 mol% methanesulfonic acid as a catalyst in toluene under microwave conditions at 160°C affords the corresponding pyrido[2?,1?:2,3]imidazo[4,5-c]isoquinolin-5(6H)-ones with yields ranging between 35 and 68%. The new method can easily be performed, is robust, and highly efficient. The third part of the thesis is focused on the intermolecular Povarov reaction. Using the reaction between aniline, benzaldehyde, and 2,3-dihydrofuran as a model reaction, the influence of ionic liquids, such as imidazolium and guanidinium salts, and microwaves on the outcome of the Povarov reaction was evaluated. It was established that the model reaction can be promoted by imidazolium salts like [bmim]BF4 under thermal as well as under microwave conditions. The reaction temperature has a strong impact on the chemical yield and the diastereoselectivity of the model reaction. At lower temperatures the formation of the endo-isomer is favored. However, the influence of microwave irradiation on yield and selectivity is not very pronounced. The Povarov reaction can also be promoted by a great number of guanidinium salts. Reactions that were performed under thermal conditions in a sealed vial demonstrated that both the chemical yield and the diastereoselectivity of the reaction are strongly influenced by a) the structure of the guanidinium ion and the nature of the anion of the guanidinium salt, and b) the concentration of the guanidinium salt. Remarkably, the Povarov can also be performed successfully in the presence of only catalytic amounts of a guanidinium salt. Finally, it was demonstrated that the guanidinium salts can be recycled and reused several times without loss of reactivity.

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