Study On The Newly Catalytic Baeyer-Villiger Oxidation

With the deepen recognition and the findings of a series of new results, Baeyer-Villiger oxidation has become a major research field in the chemistry.The oxidation reaction employed more and more application in the synthesis of variety of other chemicals,such as agriculture chemistry,pharmaceutical intermediate,natural products, biologic medicaments.In earlier studies,the primary limitations of Baeyer-Villiger were:(1)lots of per-acid were used in the reaction and it was needed to be separated,but the process was very difficult.Especially,the waste of the reaction pollutes environment badly.(2)The unsaturated bonds were oxidized firstly when unsaturated ketones were oxidized.On the other hand,when optical rotation ketones were oxidized,it obtained only racemic oxidation products.For many years the research of the Baeyer-Villiger oxidation was mainly focus on three points:(1)new mild oxidation systems,(2)the use of the environment friendly oxidants,and(3)asymmetric oxidation ofketones under catalysis.The thesis consists of three parts as follows:Partâ… :ReviewsThe thesis reviews the recent progress of Baeyer-Villiger oxidation from the five sections:(1)organic or inorganic polymer supported metal ions catalyzed system,(2)acid catalytic oxidation system,(3)transition metal complexes catalytic oxidation system,(4) metal compounds catalytic oxidation system,(5)enzyme catalytic oxidation system.We have introduced organic or inorganic supported metal compounds as very important catalytic oxidation system.Partâ…¡Baeyer-Villiger oxidation catalyzed by montmorillpnite(MMT)supported SnCl₂As an inorganic silicate support,MMT are constructed of a single octahedral sheet sandwiched between two tetrahedral sheets,with the octahedral sheet sharing the apical oxygen of the tetrahedral sheets.According the structure of the MMT,we prepared MMT supported SnCl₂(Sn-MMT(HCl))as catalyst through ion exchanged firstly and investigated the catalytic activity in Baeyer-Villiger oxidation.Through optimized the process of the oxidation,we obtained the prime condition in the reaction.The oxidations were carried out using Sn-MMT(HC1)as catalyst,environmentally friendly hydrogen peroxide as oxidant.The result indicates that the Sn-MMT(HCl)has high catalytic activity on some cyclic and acyclic ketones in the Baeyer-Villiger oxidation.In particular, 2-adamantanone and 4-methyl-2- pentanone were converted into the corresponding lactone or ester almost quantitatively.MMT is a biocompatible and environmentally friendly natural Clay mineral abundant in deposits all over the world.Partâ…¢Baeyer-Villiger oxidation catalyzed by AICI₃We used Lewis acid AlCl₃ as catalyst,ethanol as solution to investigate the catalytic activity on some cyclic and acyclic ketones and obtained the prime condition in the Baeyer-Villiger oxidation.It indicates that some cyclic and acyclic ketones are converted into the corresponding lactone or ester with high conversion and selectivity.In this catalytic oxidation system the catalyst is cheap and the solution is innocuity so the whole system is mild and innocuity.It also can be amplified easily and applied in chemistry.