Beckmann Rearrangement Reactions Catalyzed By Novel Catalysts And Deoximation Reactions In Environmentally Benign Media

The thesis consist of two parts as follows section:Part I Study on the reaction of Beckmann rearrangementFirst chapter: The developments of Beckmann rearrangement reaction companiedwith new catalyst and innovative methodology were reviewed in detail. After a briefintroduction of the history and significance of Beckmann rearrangement reaction, thedevelopments of the research domain were reviewed from two different division: thedevelopment in the vapour phase; the development in the liquid phase. Consideringour experimental content, the latter was paid more attention.Second Chapter: Silica supported sulfonic catalyzed Beckmann rearrangement under microwave irradiation. The different affects of varies factors (including amount of catalyst, solvent and irradiation power) on the reactions were studied to optimize the reaction condition. The catalyst afforded high efficiency and could be recycled for several times.Third Chapter: CeCl₃·7H₂O-NaI/SiO₂ system catalyzed Beckmann rearrangement reaction under solvent-free condition and microwave irradiation. The different affects of varies factors (including amount of catalyst, irradiation power and different ingredient of catalyst) on the reactions were studied to afford the optimized reaction condition. The catalyst provided high efficiency and could be recycled for several times.Fourth Chapter: TiO₂ nanoparticulates catalyzed Beckmann rearrangement under ultraviolet irradiation in H₂O₂. We studied the different affects of varies factors (including the disposal temperature of catalyst and the concentration of catalyst) on the reaction to optimized the reaction condition. The catalyst provided moderate efficiency and the reaction was environmental benign without additional organic solvent.Fifth Chapter: According to the reaction in second chapter, we took silica supported Phosphorus oxychloride as catalyst to catalyze Beckmann rearrangement. The different affects of varies factors (including amount of catalyst, solvent and irradiation power ) were studied to optimized the reaction condition. The catalyst afforded high efficiency and could be recycled for several times.Part II Study on the reaction of deoximationFirst Chapter: In organic chemistry, protection and deprotection of carbonyl compounds is a common and essential process in multiple organic syntheses and purification of carbonyl compounds. The developments in recent years on the deoximation were reviewed in detail, consisting of the reaction mechanism, superiority and foreground.Second Chapter: Deoximation using HIO4 under grinding in solvent-free condition, which had wonderful efficiency and easy work-up. The affect of ratios on the yield were studied to optimized the reaction condition and applied to more than 20 kinds of oximes. The reagent afforded high efficiency with a simple progress and easy work-up and the reaction was environmentally benign because of solvent-free condition.Third Chapter: Deoximation using KIO3 in aqueous medium under traditional reflux condition. We studied the different affects of varies factors (including ratios and the reaction temperature and microwave irradiation) on the reaction to optimized the reaction condition. The reaction was a alternative way for deoximation which was environmentally benign.Fourth Chapter: According to the reaction in second chapter, we selected Fe(NO₃)₃ as oxidative reagent for deoximation using similar condition. Compared to HIO₄, the reagent afford higher efficiency with a simple progress and easy work-up and the reaction was still environmentally benign, however, not compatible with aliphatic oximes.