Studies On The Oxidation Of Cyclohexene,Alcohols And Indole Catalyzed By 8-quinolinolato Manganese And Molybdenum Complexes

Oxidation reaction is a main kind of organic reaction.Epoxide as the selective oxidation product for olefin,and aldehyde,ketone as the selective oxidation product for alcohol,are all very important fine chemical intermediates.This thesis focuses on the study about the selective oxidation of cyclohexene,alcohols and indole catalyzed by hexadentate binding 8-quinolinolato manganese(â…¢) complexes and 8-quinolinolato molybdenum complexes.A preferable effect is obtained.1) A series of hexadentate 8-quinolinolato manganese(â…¢) complexes are synthesized and proven to own a distorted octahedral geometry via elemental analysis,solid UV-vis spectroscopy and Hartree-Fock/3-21G+ calculation.The oxidation of cyclohexene with H₂O₂ catalyzed by 5,7-dichloro-8-Quinolinolato manganese(â…¢) complexes is studied in this thesis.We studied the reaction condition influence,including the type of catalysts,reaction solvent,reaction temperature,the amount of catalyst and the volume ratio for solvent.It turns out that PH of system plays a great role in oxidation reaction,and that when PH ranges from 6 to 8,the best effect can be obtained. Moreover,the catalyst is proved of great industrial value for its catalytic activity didn't get down apparently even after 4 times' recycling using.2) The oxidation of alcohols with hydrogen peroxide catalyzed by hexadentate 8-quinolinolato manganese(â…¢) complexes is studied. These Mn(â…¢) complexes are found to be more efficient than their corresponding tetradentate 8-quinolinolato manganese(â…¡) and salen-Mn^â…¢OAc for the oxidation of alcohols in acetone medium,being due to their special hexadentate binding structures that could open an axial bond to form the more active pentadentate structures in the presence of aqueous hydrogen peroxide,as supported by UV-Vis spectra.The halogen substituents in ligand's aryl ring could significantly enhance the catalytic activities and 5-chloro-7-iodo-8-quinolinolato manganese(â…¢) gave the highest turnover number(TON). A reasonable mechanism for the present catalytic system is proposed.3) The oxidation of indole with TBHP catalyzed by 8-quinolinolato molybdenum(â…¥) complexes is studied.A series of 8-quinolinolato molybdenum complexes is synthesized and its structure is characterized via elemental analysis,FIIR and UV-vis spectroscopy. It shows that this molybdenum complex contains not only Oxo Bridge but also Peroxo Bridge.The first step is oxidation of the 3-position of indole to 3-oxyindole.A molybdenum-peroxy complex is postulated to be an active species of the first step,and then indigo was obtained throught dimerization of 3-oxyindole.At last the reaction conditions for synthesizing indigo is optimized systematically.Under the optimizing condition the yield of indigo was as high as 66%.