Studies On Zirconium-containing Catalysts For Baeyer-Villiger Reaction

The thesis consists of four parts as follows:Chapter I: ReviewsThis chapter reviewed the development of Baeyer-Villiger(BV) reaction from four sections: Firstly, it is introduced the invention of the BV reaction , described its developmental history and applications in organic synthesis; Secondly, the development of oxidant from the traditional peracid to green oxidant (hydrogen peroxide ,oxygen); Thridly, we expatiated on the mechanism of BV oxidation, which was general accepted; Lastly, the common catalyst of BV reaction were listed as follows: homogeneous catalysis, enzyme catalysis and heterogeneous catalysis. this section mostly concerned on the applications of heterogeneous catalyst in BV reaction.Chapterâ…¡: Baeyer-Villiger reaction catalyzed by ZrCl4 at room temperatureWith hydrogen peroxide(30wt%) as oxidant, ZrCl4 as catalyst, we tested the catalytic effect of ketones in the BV reaction. With cyclohexanone as substrate, we investigated the best system of catalytic oxidation procedure. In this system, it is shows that some cyclic and acyclic ketones are converted into the corresponding lactone or ester with high conversion and selectivity, especially, the conversion of 2-adamantanone and cyclohexanone were over 90%, lactone's selectivity forereached 99%. This catalytic system includes some advantages: firstly, the catalyst can be obtained by commercial sources and avoided the cockamamie fussy procedure of tradition; secondly, the safe reaction conditions with the hydrogen peroxide (30%) ; lastly, environmental friendly with the byproduct of water.Chapterâ…¢: Baeyer-Villiger reaction catalyzed by montmorillonite(MMT) supported Zirconium compounds catalystMMT is considered as silicate of TOT shape, the structural unit is mainly made up of two-dimensional array of the Si-O tetrahedron and embedded with the one-dimensional array of the Al (or Mg)-O-OH octahedra through shared oxygen atoms, finally, its formed a highly ordered quasi-one dimensional chips. According to the unique structure of the MMT, we prepared MMT supported Zirconium compounds catalyst through ion exchanged technology. With hydrogen peroxide as green oxidant, we found that the MMT supported Zirconium compounds catalyst has high catalytic activity on some cyclic and acyclic ketones in the BV reaction. In particular, the preparation process of catalyst is simple, inexpensive, security, environment friendly and the catalyst can be recycled. With these advantages, this catalyst has potential applications in the BV reaction of ketones.Chapterâ…£: Baeyer-Villiger reaction catalyzed by SO42-/ZrO2 solid acid catalystFor the first time, SO42-/ZrO2 solid acid as catalyst was used in BV reaction. The catalyst was characterized by XRD,EDS and SEM. 2-adamantanone as substrate, we investigated the best system of catalytic oxidation. With this system, the catalyst has high catalytic activity on some cyclic ketones, such as 2-adamantanone, cyclohexanone and 4-methyl-cyclohexanone.However, it was limited to acyclic ketones, we should modified the catalyst on the futhure, additionally, the catalyst can be recycled several times and has a certain use value.