The Selective Oxidation Of Arenes And Heterocyclic Arenes Catalyzed By Metalloporphyrins

The oxidation of hydrocarbons is one of the most important components of human's livelihood industry in china.The oxidation of hydrocarbons is mainly concerned with the oxidative activation of C-H bonds.Cytochrome P-450?CYP450?,a heme containing monooxygenase,ia an iron porphyrin heme protein existed in biology class and it can activate molecular oxygen under mild conditions to achieve hydroxylation of C-H bond activation.The CYP450 enzyme has a complex multistep and single electron transfer process due to the hydroxylation of the C-H bond,and the oxidation resistance is poor and easy to inactivate.The catalytic oxidation of metalloporphyrins,which is mainly reported in the oxidation of sp3,such as toluene,cyclohexane and cyclic C-H,has little effect on the activation of sp2 hybrid bonds on the aromatic hydrocarbons.Therefore,design and synthesis of some porphyrins and metalloporphyrins with specific structure mimic enzyme catalysts in structure and function,and its application in macrocyclic aromatic hydrocarbons sp2 try hybrid orbital C-H activation,will promote the modern pharmaceutical industry,chemical industry,especially the development of green chemical industry.The first part of this paper focuses on the synthesis of a series of porphyrins by Lindsey method:under the protection of nitrogen from pyrrole and benzaldehyde as raw materials in dichloromethane system,with three boron trifluoride ether complex as catalyst,under room temperature condition of 4hours to get porphyrinogens and then use two chloro two nitrile further oxidation of benzoquinone porphyrin.It will be applied to the biomimetic oxidation of naphthalene ring.The optimum reaction conditions were obtained through the screening of the conditions,and the yield reached 64%.The naphthalene oxidation reaction was used to produce naphthalene quinone.The TPPF₂₀ Fe Cl/Oxone catalytic oxidation system for the oxidation of macrocyclic Aromatic Hydrocarbons Catalyzed by metalloporphyrins was determined.67 kinds of substrates have been developed,among which the 9products are new compounds.It is proved that the substrate of TPPF₂₀ Fe Cl/Oxone catalytic oxidation system has wide application range.TPPF₂₀ Fe Cl/Oxone catalytic oxidation system has a good application prospect because of its small amount of catalyst and green cleaning.The second part of this paper focuses on the application of TPPF₂₀ Fe Cl/Oxone catalytic oxidation system on oxidation of N substituted indole formation of isatin.Isatin is important raw material for the synthesis of analgesic two diclofenac,has good medicinal value.Through the literature known to occur in N,indole substitution reaction,generate N methylindole indole or benzyl N,use the TPPF₂₀ Fe Cl/Oxone catalytic oxidation system of N substituted indole,the success will be oxidized into isatin.And 35 kinds of substrates were extended,the yield was from 18% to 69%.In the third part of this paper,we mainly study on the oxidation of N to produce 2-indole ketone by TPPF₂₀ Fe Cl/Oxone catalytic oxidation system.2-indole ketone has anti-inflammatory,antibacterial,anti-tumor activity.By means of the above methods,the acyl 2-reaction of indole N was obtained,and the N indole was synthesized by catalytic oxidation.The 23 kinds of substrates have been extended,and the N group of different substituents on the benzene ring can be certified and oxidized,the yield of which is from 28% to 65%,of which the new product is the new compound.Through the introduction of different substituents on indole N,the controllable oxidation of indole ring was realized,and the target product was obtained.