Study On Conjugate Hydrocyanation Of α,β-unsaturated Esters Using Potassium Hexacy-anoferrate(Ⅱ) As A Green Cyanide Source

The cyanating agent is a kind of very useful reagent in organic synthesis. The signifi-cant organic intermediates such as nitriles, cyanohydrins,-aminonitriles, amino acids andso on, could be synthetized by cyanating reactions. Therefore, it has been very extensivelyused in industry, pesticides, medicine, dyestuff, pigments, crystal materials and polymermaterials. At present, many cyanting agents are widely used in organic reaction, for exam-ple, HCN, TMSCN, KCN, NaCN, CuCN, Ni(CN)2and so on. Howerer, these cyanideshave strongly toxic, corrosive and unstable features. Using these chemicals are so danger-ous that it makes great threat for the environment. With the uninterrupted growth of theprinciple of green organic synthesis, the development of eco-friendly and sustained organicsynthetic methods become more and more important. Consequently, exploring a kind ofsafe and green cyanide source instead of traditional harmful reagents is very meaningful.Potassium hexacyanofferrate(II) is a by-product of the coal chemical industry andprice is very low. It is mainly used as carburizing agent in the iron and steel industry. Andit has extensively applied for dyeing and printing industry, medical industry and dyestuffindustry. Because of non-poisonous，it is even used in the food industry as an antagglu-tinating auxiliary for table salt. In addition, recently, chemical researchers has found thatpotassium hexacyanoferrate(II) is a kind of very important and environmentally friendlycyanide source, which is used in organic cyanating reaction.Therefore, in this thesis, an efficient and environmentally friendly method for conju-gate hydrocyanation of, β-unsaturated esters and nitriles by one-pot, two-step procedureusing potassium hexacyanoferrate(II) as an original eco-friendly cyanide source is investi-gated.The paper includes three sections.In section1The section mainly introduced the applications of the different cyanating rea-gents in organic reactions, the progress in organic cyanating reactions using potassiumhexacyanoferrate(II) as an original eco-friendly cyanide source and the progress in conju-gate hydrocyanation of, β-unsaturated carbonyl compounds.In section2The method of conjugate hydrocyanation of diethyl2-benzylidenemalonate by one-pot, two-step procedure using potassium hexacyanoferrate(II) as an eco-friendly cya-nide source, benzoyl chloride as a promoter, potassium carbonate as a catalyst, and etha-nol as a solvent has investigated. This protocol has the advantages of use of green cyanidesource, efficient yield, widely application and simple work-up procedure.In section3An efficient method of conjugate hydrocyanation of-cyano-β-substituentacrylic esters by one-pot, two-step procedure using potassium hexacyanoferrate(II) as anovel eco-friendly cyanide source, benzoyl chloride as a promoter, potassium carbonate asa catalyst, and ethanol as a solvent has described. This protocol has the advantages of useof eco-friendly cyanide source, high yield, mild condition and large scope.