Oxidation Of Alcohols Utilizing Oxone As Oxidant Catalyzed By Metal-catalysts

The thesis consists of five chapters as followings:Chapterâ… :ReviewsThe catalytic oxidation of alcohols with both non-metal-catalysts and metal catalysts has been reviewed in this chapter.In the first section,the applications of TEMPO and its derivatives in homogeneous as well as in heterogeneous conditions in the catalytic oxidation of alcohols were well discussed.As for the metal-catalyzed oxidation,the author reviewed the research progress from the following three subsections,such as:ruthenium,manganese,and other transition metal catalyzed system(palladium,gold,iron and copper).Chapterâ…¡:The oxidation of alcohols utilizing Oxone^? as oxidant catalyzed by Ru(â…¢) complexA catalyst Ru complex Quin-Ru-Quin was synthesized and its structures were characterized by IR,ICP,XPS and elemental analysis.The results show that this Ru complex is excellent catalyst for the oxidation of alcohols.In the presence of the Ru-complex catalyst and phase transfer agent n-Bu₄NBr,a series of benzylalcohol and benzhydrol derivatives were oxidized to the corresponding aldehydes and ketones with high conversion and selectivity using Oxone^?(2KHSO₅·KHSO₄·K₂SO₄) as oxidant.It is interesting to find that this oxidation system is also efficient for the oxidation of aliphatic alcohols.Chapterâ…¢:The oxidation of alcohols utilizing Oxone^? as oxidant catalyzed by Mn(â…¢) complexIn this study we found that Oxone^? is active towards the oxidation of alcohols to their corresponding aldehydes and ketones catalyzed by manganese-containing complex Mn-(quin)₃ under biphasic conditions(CHCl₃/H₂O) at room temperature.A series of alcohols were treated with this catalyst system.Benzyl alcohol was transformed to benzaldehyde with the conversion of 100%and the selectivity of 98%. Benzyl alcohol derivatives were oxidized to give the corresponding aldehyde completely.The results obtained from this study also indicated that the system oxidizes benzhydrol,substituted benzhydrol to the corresponding ketones efficiently in good-to-excellent yields and purities.Chapterâ…£:The oxidation of alcohols utilizing Oxone^? as oxidant catalyzed by FeCl₃·6H₂O.The catalytic activities of the FeCl₃·6H₂O for the oxidation of alcohols was investigated.The results showed that 1.0 equiv,of Oxone^? and 0.005 mmol of FeCl₃·6H₂O are needed for the benzyl alcohol to be completely transferred in 16 hours at 50℃.Most of benzylalcohol and benzhydrol derivatives can be oxidized to the corresponding carbonyl compounds with high conversion by the utilization of FeCl₃·6H₂O.Chapterâ…¤:The chlorination of alcohols into their corresponding chlorides with AlCl₃The transformation of alcohols into the corresponding alkyl halides is one of the most studied reactions in organic synthesis,and many reagents can be usually used. Often the conversion requires elaborate reagents and quite drastic reaction conditions. In this chapter,we reported a more economically,efficiently,and simply procedure for the quantitative conversion of alcohols into the corresponding alkyl chlorides.The procedure is operationally simple and allows a rapid and high-yielding conversion of alcohols to the corresponding chlorides Using AlCl₃ as halogenating agent under mild conditions.The method seems to be more convenient with respect to other reports and can be used as a valid alternative to other methods,so avoiding the use of more toxic reagents.