The Application Of Organic Selenium In The Synthesis Of Pharmaceutical Intermediates Such As Organic Nitriles And Carbonyl Compounds

In this paper,the methods of synthesis organic nitrile and carbonyl compounds catalyzed by organic selenium as well as alcohol dehydration to synthesis of olefins were studied.The main achievements include the following three aspects:1.The reaction of aldehyde oxime dehydration catalyzed by organic selenium was studied.The process conditions of the reaction were investigated,such as:solvent,catalyst,catalyst dosage,etc.The optimum preparation process of synthesis of organic nitrile compounds with catalytic amount of benzeneseleninic acid was selected as catalyst and no solvent involved.The reaction products were separated by simple distillation apparatus.In the optimum conditions,seven organic nitrile compounds were prepared and all compounds were characterized by IR,1H NMR,and 13C NMR methods.Compared with existing methods,this method does not require the use of solvent,and mild reaction conditions,simple operation,not using any ligand,low dosage of catalyst,recyclable catalysts,for the production of organic nitriles compounds provides a green and efficient synthetic process.In addition,the method has succeeded in amplifying the reaction of aldehyde oxime dehydration to a kilogram scale,which is likely to be applied to large-scale industrial production in the future.2.The reaction of organic selenium catalyzed olefin cracking was studied.The method used the catalytic amount of organic selenium reagent as catalyst,the clean hydrogen peroxide as oxidant,and the non-toxic and harmless ethanol as the solvent.The reaction conditions of the substrate was investigated,such as:catalyst,reaction temperature,reaction time,etc.21 kinds of carbonyl compounds were prepared and all compounds were characterized by IR,1H NMR,and 13C NMR methods.Through a series of confirmatory experiments,the possible reaction mechanism was proposed.Compared with existing methods,the reaction process of this method is clean,no waste,the widely application range of the substrate,and according with the concept of green chemistry,for clean oxiding the two or three substituted olefin C=C double bond cracking to synthesis of corresponding carbonyl compounds provides a new way.3.The reaction of alcohol dehydration catalyzed by sodium bisulfate monohydrate was studied.The reaction conditions were investigated,such as:solvent,catalyst,etc.The optimum preparation method was using the clean and environmental water as solvent and the catalytic amount of sodium bisulfate monohydrate as catalyst.In the optimum reaction conditions,16 kinds of olefins were prepared and all compounds were characterized by IR,1H NMR,and 13C NMR methods.In the optimum reaction conditions,the effect of catalyst recycling of the 20 mmol scale of 1,1-diphenyl ethanol dehydration reaction was studied.Compared with existing methods,this method was environmental friendly,low cost,the widely application range of the substrate,recyclable catalyst,and according with the spirit of green chemistry,opened up a kind of high efficient,clean and practical method for synthesis of olefins compounds.