摘要
研究了在乙酰丙酮钯催化体系中,一氧化碳和亚硝酸酯偶联合成草酸二酯的反应。其催化活性为8.3mol草酸二乙酯/mol Pd·h。反应前后催化体系的NMR和IR谱表明,该体系的活性催化组分含有钯苯基膦和烷氧羰基络合物。以金属-烯酮中间体[L_3Pd=C=O]为钯络合物催化剂上的基元反应模型,提出了一氧化碳偶联合成草酸酯的机理。
The catalytic reaction of the synthesis of diethyl oxalate (DEO) by the coupling of CO with C2H5ONO over Pd(acac)2 catalyst system was studied. The activity for DEO is 8.3 mol/mol Pd·h. The active complex PdL3 and the alkoxycarbonyl palladium are examined with NMR and IR spectra. By suggesting the metal-carbene-ketone (L3Pd = C = O) as intermediate, the mechanism of the formation of DEO via the coupling of CO with C2H5ONO is proposed.
基金
国家自然科学基金
