钯催化的乙炔双羰化——高效合成丁烯二酸二甲酯（英文）

Palladium-catalyzed Dicarbonylation of Acetylene:Efficient Synthesis of Dicarboxylic Acid Dimethyl Esters

报道了无酸和重金属盐的催化乙炔双羰化反应的钯催化体系(催化剂组成为Pd Cl2/KI).正交实验表明空气的初始分压和助剂KI的用量在乙炔双羰化反应中起着重要的作用.在相同的实验条件下,发现催化体系为Pd Cl2/HCl/Cu Cl2和Pd Cl2/H_2SO4/Fe Cl3时,顺、反丁烯二酸二甲酯的总收率分别为15.3%和21.8%,而用Pd Cl2/KI时总收率达到了81.9%.在最优反应条件下,即Pd Cl20.056 mmol,KI 0.677 mmol,总压5.3 MPa,70℃反应3 h,顺、反丁烯二酸二甲酯的总收率为91.0%.

In this work, we reported a palladium-catalyzed system （PdC12/KI） without acid （HC1, H2SO4 ） and heavy metal salts cocatalyst （ CuC12 and FeC13 ） for dicarhonylation of acetylene. The orthogonal experiments demonstrated that the partial pressure of air and the amounts of KI played the crucial roles in the reaction process. Moreover, comparison with other Pal- catalyzed systems （PdCl2/HCl/CuCl2, yield： 15.3% and PdCl2/H2SO4/FeCl3, yield： 21.8% ） under the same reaction conditions, the PdCl/KI catalytic system showed much higher activity （yield： 81.9% ）. The total yield of diesters can reach 91.0% under the total pressure of 5.3 MPa with the catalyst composition of O. 056 mmol PdC12 and 0. 677 mmol KI at 70 ℃ for three hours.