Eco-friendly Conjugate Hydrocyanation Of α,β-unsaturated Ketones And α,β-unsaturated Dinitriles

Organic cyanation is a kind of very important organic reaction, because it can synthesize a lot of important organic intermediates, such as α-amino nitriles, cyanohydrins and α-amino acids, α-amino ketones and so on. At the same time, it is also an important method to synthesize chiral compounds. Hence, organic cyanation has very extensive applications in industry, agriculture, medicine, dyestuff, pigment, polymer materials and other industries. But organic cyanation mainly uses highly poisonous hydrocyanic acid and metal cyanide(KCN, NaCN, Zn(CN)2, CuCN, etc.), as well as TMSCN, which is unstable and easy hydrolysis to lose poisonous hydrocyanic acid. These cyanide agents is also not safe for operation process, and cause serious harm to the environment. This dosen’t conform to the national energy saving and emission-reduction policy, is not accord with the advocating green global concept.Therefore, exploring the safe and eco-friendly cyanide agents to replace the traditional toxic cyanide agents has the very vital significance. This paper chooses K4[Fe(CN)6] and 2-cyano acetamide as eco-friendly new cyanating agents, respectively, to realize green conjugate hydrocyanation reaction of α,β-unsaturated ketones, α,β-unsaturated ketones and α,β-dinitriles. This thesis is divided into four parts: Part 1The applications of different cyanide agents in organic reactions and conjugate hydrocyanation reactions of α,β-unsaturated carbonyl compounds are reviewed.Part 2The conjugate hydrocyanation of α,β-unsaturated diketones using potassium hexacyanoferrate(II) as a cyanide source by one-pot two-step procedure was described. The advantages of this protocol are no use of strong toxic cyanating agents, the high yield of the products and a simple work-up procedure. Part 3The conjugate hydrocyanation of α,β-unsaturated dinitriles using potassium hexacyanoferrate(II) as a cyanide source by one-pot two-step procedure was described. This method uses benzoyl chloride as the promoter, potassium carbonate as catalyst and ethanol as solvent. Part 4The conjugate hydrocyanation of chalcones using cyanoacetamide as a cyanide source, DMF as solvent, sodium tert-butoxide as a catalyst was described. The advantages of the reactions are metal-free catalyst, high yield, mild conditions, and simple work-up procedure.