Studies On Synthesis And Catalytic Properties Of Aluminum Compounds And Boron Compounds For Baeyer-Villiger Oxidation Of Ketones

The thesis consists of five chapters as follows:ChapterⅠ: ReviewsThe chapter reviewed the recent progress of Baeyer-villiger oxidation from the three sections(1) The author present a review of history, the characterization and the applications of Baeyer-villiger oxidation.(2)The author expatiated on the mechanism of Baeyer-villiger oxidation, which was first elucidated by Criegee and accepted abroad today.(3)The progress of Baeyer-villiger oxidation reaction, meanwhile progress of both oxidants and catalysts were introduced separately. As far as catalysts applications are concerned, we mainly introduced the applications of heterogeneous catalyst in Baeyer-villiger oxidation reaction. The inorganic supporters (such as zeolite, silica, clay and et al.) as well as the organic polymer supporters (such as cellous, chitosan, resins et al.) and other heterogeneous materials (metal oxide, metal complexes et al.) supported catalysts were well introduced.ChapterⅡ: Catalytic Baeyer-Villiger oxidation of ketones with boron trifluoride and its silica supportedBoron trifluoride etherate (BF3·OEt2) and silica supported BF3 are used as catalysts for Baeyer-Villiger oxidation of ketones with 30% hydrogen peroxide as oxidant. Serious of ketones are effectively oxidized to the corresponding esters or lactones under mild reaction conditions. 2-andamantanone, cyclopentanone, 2-methyl- cyclohexanone are efficiently oxidized to the corresponding lactones by boron trifluoride etherate (BF3·OEt2) with selectivity of 99%, 99% and 74%, respectively. The catalyst also shows catalytic activity for the oxidation of 4-methyl-2-heptanone with 25% conversion, 99% selectivity. The silica supported BF3, affords high lactone's selectivity in Baeyer-Villiger oxidation of ketones. It can be easily prepared and recycled.ChapterⅢ: Baeyer-Villiger oxidation of ketones using H2O2 as oxidant with aluminum chloride supported on palygorskitePalygorskite clays, a widely used species of hydrated magnesium aluminum silicate nonmetallic mineral, are characterized by a porous crystalline structure containing tetrahedral layers, joined together by longitudinal sideline chains. It possesses a large specific surface area, considerable porosity, the possibility for ion exchange, and thermal stability. According the structure of the Palygorskite, we prepared Palygorskite supported AlCl3 as catalyst and investigated the catalytic activity in Baeyer-Villiger oxidation. Fourier transform infrared (FT/IR), inductively coupled plasma (ICP) and X-ray photoelectron spectroscopy (XPS) analyses show that AlCl3 particles are successfully supported on the palygorskite clays. It is found that the catalyst shows high catalytic activity for 2-andamantanone, cyclohexanone, 4-methylcyclohexanone and 4-tertbutylcyclohexanone in Baeyer-Villiger oxidation. The catalysts can be easily prepared and recycled for several times without significant decline in catalytic activity.ChapterⅣ: Baeyer-Villiger oxidation catalyzed by montmorillonite supported aluminum chlorideMontmorillonite has a 2:1 layered structure with a single layer of aluminum octahedral between two layers of silicon tetrahedral. The Al3+ or Si4+ locations can be replaced by lower valent cations, which cause the montmorillonite structure to have an excess of electrons and high adsorption capacity. Here, we made use of its structure and property to synthesize MMT supported AlCl3 and then investigates its catalytic ability for the Baeyer-Villiger oxidation of some ketones. Fourier transform infrared (FT/IR), inductively coupled plasma (ICP) and scanning electron microscope (SEM) analyses shows that AlCl3 particles are successfully supported on the montmorillonite clays. It is found that the catalyst shows high catalytic activity for 2-andamantanone, cyclohexanone, 4-methylcyclohexanone and 4-tertbutylcyclohexanone in Baeyer-Villiger oxidation. The catalysts can be easily prepared and recycled for several times without significant decline in catalytic activity.ChapterⅤ: Oxidation of Ketones with 30% H2O2 catalyzed By Aluminium BromideAlBr3 is used as catalyst in Baeyer-Villiger oxidation of ketones with 30% aqueous hydrogen peroxide as oxidant. The influence of the solvents, reaction temperature, the amount of catalyst and the reaction time on the catalytic activity and product selectivity were investigated. In summary, AlBr3 was found to be an excellent homogeneous catalyst for the Baeyer-Villiger oxidation of ketones, with the oxidant of 30% hydrogen peroxide. The biggest advantage of this catalytic system includes of (1) the easily purification of the product; (2) the safe reaction conditions with the use of 30% H2O2 and (3) environmental friendly with the by product of water.