Researchers at the State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences (CAS), have developed a method for synthesizing α,β unsaturated acetyenic ketone compounds by carbonylation. They received a Chinese invention patent for the technique on July 4.
In this method, iodo arene, a terminal acetylene compound and carbon monoxide are used as reactants and activated carbon loaded palladium as a catalyst. The products are obtained through 1 to 4 hours’ reaction of reactants with the reaction temperature controlled between 80 and 140 ℃ and the pressure of the carbon monoxide between 0.5 and 3.0 MPa in the presence of a catalyst accelerator and a reaction solvent.
The method can realize separation of the catalyst and the products right after the reaction is over, and can reuse the catalyst and maintain the activity of the catalyst unchanged. And the selectivity is more than 99% and the conversion rate is more than 90%.
α,β unsaturated acetyenic ketone is a kind of important organic intermediate. It is widely used in the synthesis of heterocyclic compounds, biomacromolecules, natural products, medicine, etc. Traditional synthetic methods of α,β unsaturated acetyenic ketone have certain shortcomings, such as harsh reaction condition, difficulty in obtaining substrates and low product yield. Carbonylative Sonogashira Coupling of iodo arene, a terminal acetylene compound and carbon monoxide is another way to synthesize α-β unsaturated acetyenic ketone. However, the existing Carbonylative Sonogashira Coupling reactions all use homogeneous palladium catalysts containing phosphine. The use of homogeneous palladium catalysts containing phosphine has the disadvantages of the toxicity of phosphine and difficulty in separation products from catalysts . |