Monohydrocyanation Of P-phenylenedimethanimines Using Potassium Hexacyanoferrate(?) As Green Cyanide Source And Monocondensations Of 1, 2-diketones With Ethy1 Cyanoacetate

The organic cyanating reaction is a class of very important organic reaction, because it can be used to synthesize many organic intermediates such as nitriles, aminonitriles, cyanhydrins, acylnitriles and so on. Meanwhile, the organic cyanation reactions have widespread applications in organic chemical industry, medicine, pesticides, dyes, pigments, liquid crystal materials, and polymer materials.Nowadays, the reported cyanating reactions usually use hydrocyanic acid, metal cyanides(for example sodium cyanide, potassium cyanide, cuprous cyanide, nickel cyanide, zinc cyanide), and organic cyanating agents(trimethylsilyl cyanide, ethyl cyanoacetate, ethyl cyanoformate, cyanoimidazole, acetone cyanohydrin, acetyl cyanide, manolonitrile and so on), and mixed cyanide sources(eg. DMF and NH3, DMSO and NH4HCO3), and potassium hexacyanoferrate(II) and so on. Among them, they are poisonous except potassium hexacyanoferrate(II) and mixed cyanide sources. Potassium hexacyanoferrate(II) is non-toxic and harmless, even it can be used as an additives of food salt. Simultaneously, it is byproduct of coal chemical industry, and is very cheap.This paper is focused on the monohydrocyanation of p-phenylenedimethanimines using potassium hexacyanoferrate(II) as an environmentally-friendly cyanating agent. In addition, the monocondensations of 1,2-diketones with ethyl cyanoacetate is also investigated.The paper is divided into three sections: Sections 1In this section, the applications of different cyanating agents in organic cyanation reactions, and the progress using potassium hexacyanoferrate(II) as an original eco-friendly cyanide source in organic cyanation reactions were reviewed. In addition, synthesis of ?-aminonitriles via Strecker reaction was also introduced. Sections 2An environmentally friendly method has been explored for monohydrocyanation of p-phenylenedimethanimines using potassium hexacyanoferrate(II) as an original eco-friendly cyanide source, benzoyl chloride as a promoter, chloroform as a solvent, triethylamine as a catalyst. The features of these reactions are use of environmentally friendly cyanide source, mild condition and simple work-up procedure. Section 3A method has been explored for monocondensations of 1, 2-diketones with ethyl cyanoacetate using piperidine as a catalyst and DMF as a solvent. The features of these reactions are mild condition, high selectivities and simple work-up procedure.