| Isocoumarin was widely found in natural products and an important medical intermediates.As a kind of common nature coumarin lactone,Isocoumarin display a wide range of biological activities,such as antibacterial,sterilization,pheromones,plant toxins physical and biological activity.Therefore the research of synthesis Isocoumarin were widely carried out,and a large number of work were reported especially the synthesis of 3,4-substituted isocoumarins.The traditional methods to obtain isocoumarins were mainly include electrophilic cyclization and transition metal catalyzed reactions.In which,the electrophilic cyclization of o-(1-alkynyl)benzoic acid and their corresponding esters was regard as the most effectient methed to synthesis isocoumarins.Different isocoumarin derivatives can be obtained thing this simple,mild and high selective condition.Transition catalyzed synthesis of isocoumarins mainly contained pallsdium,silver,mercury and copper catalysts.Although,the synthesis of isocoumarins derivatives were wildly reported,palladium caralyzed o-(1-alkynyl)benzoic esters to get 3-substituted-4-sulfurisocoumarins were rare reported.This thesis mainly to research 4-sulfurisocoumarin derivatives synthesis method.4-sulfurisocompounds is important of synthetic intermediates,exist widely in many of natural medicine,and also is many biologically active compounds of basic structure.In diminish inflammation,antibacterial,antivirus and treatment of both use the contains the skeleton of 4-sulfurisocoumarins derivatives and different compounds.In addition,4-sulfurisocoumarins is also an important kind of heterocyclic compounds,has the unique physical activity,pesticide and a wide range of applications in pharmaceutical products.Therefore,synthesis 4-sulfurisocoumarins by different method have arouse the'people wide attention,the great significance is exploration and study their synthetic route and method.But,as the preparation 4-sulfurisocoumarins general way usually catalyst by Louis acid or alkali,with nitrogen or phosphorus ligands,heating for long time,direct to get 4-sulfur isocoumarins.Louis acid or alkali as catalyst thar catalytic activity is high,but it also exists many disadvantages:selective is poor,many by-products,production yield is low,environment pollution and equipment loss seriously.But with o-iodine benzoic acid as the starting material first preparation it to o-iodine benzoic acid ester,and then after cross coupling,the last cyclization get product.These methods have many advantage it not only good selectivity and production yield are higher and reaction time is short.In addition,the reaction has mild conditions,simple operation etc,thus it has the important academic significance and application value.C-H activation reaction since it been discover,it get organic chemist's extensive concern,and become the typical representative of organic reactions,and widely used in organic to synthetic complex structure of compounds,even it can be used for synthesis of saturated,unsaturated compounds and some of the natural products.In recent years,C-H activation reaction research gradually development and become hot spot,this kind of reaction main features is the oxidation of C-H bond to activate and constitute the C-C bond.This paper mainly studies the oxidation and activation of DMF and synthesis unsaturated armour amides.In addition,unsaturated amide also is a kind of new type resistant high temperature thermosetting polymers.1.Established a kind of high yield,room temperature and the wide range of substrate by Pd/Ag cyclization catalytic system.In the existence of palladium and silver,a series of o-(1-alkynyl)benzoic acid ester can be very smoothly react to cyclization,and the synthesis of the corresponding 3-substituted 4-sulfurisocoumarin product to compare in high yield,and reaction at room temperature belong to green chemical concept.2.Developed a novel,efficient use of styrene and DMF for the substrate to synthesis unsaturated amides compounds by the new method.FeCl3 as catalyst,DABCO as ligands and DTBP as oxidant,in argon,styrene and the DMF successfully to happen C-H activation reaction with good yeild to synthesis of the corresponding(E)-N,N-dimethyl-3-p-toluene alkenyl unsaturated amides. |
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