Study On Some Organocyanation Using Potassium Hexacyanoferrate(Ⅱ) As A Green Cyanide Source

The organic cyanating reaction is a very significant organic reaction, it can introduces cyano into organic molecules. Many important organic intermediates can be synthesed by cyanating reaction, such as:nitriles, cyanhydrins, α-aminonitriles, α-amino acids, α-hydroxy acids, α-keto acids, acyl nitriles and so on. These substances are the very important organic intermediates, they have the considerable applications in the organic synthesis. Simultaneously it is also the important way to synthesize chiral organic compounds. Therefore, cyanation has a considerable applications in organic chemicals, medicines, pesticides, dyestuff, pigments, crystal materials and polymer materials. The reported cyanating reactions usually use hydrocyanic acid, metal cyanides, trimethylsilyl cyanide, cyanoformate,(R2N)2BCN, acetone cyanohydrin, acetyl cyanide as cyaniding reagents. However, these cyanating are strongly toxic, unsafe and not friendly to the environment. Therefore, based on this, we seek and explore an efficient green cyanide agent to replace traditional toxic cyanide agents. Potassium hexacyanoferrate(II) is the byproduct of the coal chemical industry, price is very cheap, even is cheaper than the KCN. The most important is that it is nontoxic and harmless. If it can be used as a cyanide agent, it will be very friendly to the environment.In this thesis, potassium hexacyanoferrate(II) was used as an environmentally friendly cyanide agent to react with sulfonyl chlorides and aroyl chlorides respectively to synthesize a series of sulfonyl cyanides and2,3-diaryloxirane-2,3-dicarbonitriles. The thesis is divided into three sections.Section1This section mainly summarizes application of some traditional toxic cyanide agents in organic cyanations. The latest research progress of using potassium hexacyanoferrate(Ⅱ) as an eco-friendly cyanide source and our laboratory some achievements using potassium hexacyanoferrate(Ⅱ) as an eco-friendly cyanide source are reviewed. The main points are focused on the types of organocyanation using potassium hexacyanoferrate(Ⅱ) as cyanide source. Section2In the conditions of without solvent, potassium hexacyanoferrate(II) as an environmentally friendly cyanide agent reacts with sulfonyl chlorides to synthesize a series of sulfonyl cyanides. This method avoids the use of traditional toxic agents and also has the features of cheap raw material and simple process.Section3Potassium hexacyanoferrate(Ⅱ) and aroyl chlorides react to give aroyl cyanides, first which then further converts into2,3-diaryloxirane-2,3-dicarbonitriles under triphenylphosphin and triethylamine as catalyst. This protocol has the features of use of eco-friendly cyanide source, high yield, and simple work-up procedure.