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

The thesis consists of four chapters as follows:Chapter I: ReviewsThe chapter reviewed the recent progress of Baeyer-Villiger oxidation from the threesections: (1) The author presents a review of the history, the characterization and theapplications of Baeyer-Villiger oxidation. (2) The author expatiated on the mechanism ofBaeyer-Villiger oxidation, which was first elucidated by Criegee and accepted abroadtoday. (3) The progress of Baeyer-Villiger oxidation reaction, meanwhile progress of bothoxidants and catalysts were introduced separately. As far as catalysts applications areconcerned, we mainly introduced the applications of heterogeneous catalyst inBaeyer-Villiger oxidation reaction. According to the difference of catalyst carriers, fouraspects were reviewed, they are:β-zeolite, mesoporous material, clay and otherheterogeneous materials (metal oxide, resins, metal complexes and so on) as the carriers ofthe catalyst.ChapterⅡ: Baeyer-Villiger oxidation catalyzed by silica supported AlClB3 BThe silica, of which the formula is x SiOB2B·y HB2BO, is a kind of crystal and milk-whitesolid particles, has open porous structure and can strongly absorb many kinds ofsubstances. There are a number of hydroxyls which can be functionalized on its surface, ithas many different molecular internal pores, so it can simultaneously carry targetcompounds within and without. According to and making use of the structure of the silica,here, silica supported AlClB3B was synthesized by using silica as the carrier and AlClB3B as thecatalytic metal ion respectively. We then used silica supported AlClB3B as the catalyst,30%HB2BOB2B as the oxidant to investigate its catalytic activity in Baeyer-Villiger oxidation.The result indicates that the catalyst silica-AlClB3B has high catalytic activity on some cyclicand acyclic ketones in the Baeyer-Villiger oxidation. In particular, it is active and highlyselective for the Baeyer–Villiger oxidation of 2-adamantanone, cyclohexanone,4-methyl-cyclohexanone and 4-tert-butylcyclohexanone. The carrier silica is available andthe procedure of preparation of this catalyst is simple, so we think it is worthwhile to choose silica-AlClB3 Bas a kind of catalyst for Baeyer-Villiger oxidation reaction.ChapterⅢ: Baeyer-Villiger oxidation catalyzed by MCM-41 supported AlClB3 BSiOB2B is the main component of MCM-41, its structure is orderly honeycomb-like, itsone-dimensional pore is hexagonal close packing array, free–SiOH on the silica surface,which can graft many metal ions. Here, we made use of its structure and property tosynthesize MCM-41 carried AlClB3 Band then investigates its catalytic ability for theBaeyer-Villiger oxidation of some ketones. The results indicated that the structure ofMCM-41 carried AlClB3 Bis stable and it has good catalytic effect of Baeyer-Villigeroxidation reactions of 2-adamantanone, 4-methyl-cyclohexanone and4-tert-butylcyclohexanone.Chapter : the StudyⅣudy of Catalytic Baeyer-Villiger Oxidation of AlClB3B/OB2B/Benzaldehyde Reaction SystemWe used Lewis acid AlClB3B as catalyst, OB2B/ benzaldehyde as oxidant to investigatecatalytic activity of the catalyst on some cyclic and acyclic ketones and obtained the primereaction conditions of the Baeyer-Villiger oxidation. It indicates that 2-adamantanone andcyclopentanone are converted into the corresponding lactone with high conversion andselectivity when ethanol was used as the solvent. The catalyst AlClB3B of this reactionsystem is cheap and available, oxidant OB2B is also cheap and available, and what's more,oxidant OB2B is environmentally-friendly and safe to use, the whole process is accordingwith the up to date demands of green chemistry.