Application Of Hydroxyl Ammoniumionic Liquids In C-C And C-X Bond Constructed Reactions

Green chemistry has received great attention these years due to the serious environmental problems. Ionic liquids which was believed as green medium and functional materials has been widely used in organic synthesis, catalysis, material sciences, extraction and separation, mainly because of their low volatility, good thermal and chemical stability, strong solubility, designability and reusability. Hydroxyl ammonium ionic liquids are a new kind of functional ionic liquids and have high biocompatibility, which have shown great advantages in catalysis.As a part of the National Natural Science Foundation of China(NO. 21373079), in this work, we focused on the design and synthesis hydroxyl ammonium ionic liquids and their applications in chemical reactions, the details are as follows:1. A series of ionic liquids were synthesized using N,N-dimethyl ethanolamine(DMEA) and choline as cation through the acid-base neutralization reactions, and the application of these ionic liquids on the reductive amination reactions were investigated. It was found that when [DMEA][Lac] was used as a catalyst and solvent, the reactions had good conversion and the target compounds had high selectivity. Aslo, these reactions could proceed smoothly at ambient conditions, a wide scope of substrates including amino acids could be converted to the target functional amine.2. The catalytic performances of a series of hydroxyl ammonium ionic liquids on the reaction between benzaldehyde and 4-hydroxylcoumarin were investigated. The results showed that the increase of the basicity of ionic liquids benefit to their catalytic activity and the aqueous solution of choline hydroxide(40%) was found to be the favorite catalyst. The effect of the amount of catalyst and reaction temperature was also studied. The results showed that a wide range of aldehyde could be converted to biscoumarins under mild conditions and acidic sensitive groups could be well kept in this catalytic system. In addition, the catalyst can be easily recovered and recycled with high efficiency. The scale-up experiment showed this catalytic system could be conducted with multigrams, suggesting the potential application of this method in industrial.3. A series of hydroxyl ammonium ionic liquids based on acetate anions were designed and synthesized, and the influences of the length of carbon chain and the number of hydroxyl groups on cations on the PdCl2 catalyzed Suzuki reactions were investigated. The effect of substrate ratio, reaction temperature and the amount of catalyst on the reactions were also studied. The results showed that the increase of the length of carbon chain and the number of hydroxyl groups benefit to the catalysis. When the catalyst was 0.1% mol of substrate, the reactions could proceed smoothly without the need of ligand and base. This catalytic system was applicable for a wide range of substrates and aryl halides containing electron-withdrawing group and organoboronic acids containing electron-donating group benefit to the proceeding of the reaction.4. A series of hydroxyl ammonium ionic liquids composed of phenol-type anions were designed and synthesized, and their application in the synthesis of quinazoline-2,4(1H, 3H)-diones was investigated. It was found that hydroxyl ammonium ionic liquids can promote the reaction effectively and [Choline][2,4-Cl-PhO] was the best one. The reaction temperature and the amount of catalyst were also optimized. The results showed that this catalytic system can promote the CO2 convertion at mild conditions with high efficiency and the catalyst is feasible to synthesize, recover and reutilize, which provide an efficient and green method for the conversion of CO2.