Co(Ⅲ)席夫碱配合物的合成及其在硫醚催化上的研究

Synthesis of Co(Ⅲ) Schiff Base Complexes and Application in Sulfide Catalysis

利用2′,4′-二羟基苯乙酮和乙二胺在高温下合成了Co(Ⅲ)配合物(CoL)。通过MS、元素分析以及单晶衍射分析方法对该配合物进行了详细表征。在试验中为了尽可能减少化学污染,选择了成本较低、无毒无污染的过氧化氢作为氧化剂,反应溶剂选择水溶液,金属配合物作为催化剂,牛血清白蛋白作为手性助剂,探究了CoL对苯基甲基硫醚氧化的催化活性和对映体选择性。在环境友好的条件下,考察了不同氧化剂、反应溶液的pH、各物质的浓度、氧化剂用量和温度等反应条件对催化活性的影响。通过单因素试验并筛选出最优反应条件,试验结果表明,最优的反应条件为:pH为8,氧化剂用量28.7μL,催化剂用量37.31μL,反应温度0℃、底物浓度22.16μmol/L,在最优反应条件下获得了较高的转化率(98%)和化学选择性(100%),但对映体选择性较差(6.3%)。

Co( Ⅲ) complex(CoL) was synthesized by 2′, 4′-dihydroxyacetophenone and ethylenediamine at high temperature. The complex was characterized by MS, elemental analysis and single crystal diffraction. In the experiment, in order to reduce chemical pollution as much as possible, hydrogen peroxide with low cost, non-toxic and pollution-free was selected as the oxidant, the reaction solvent was aqueous solution, the metal complex was used as the catalyst, and bovine serum albumin was used as the chiral assistant to explore the catalytic activity and enantioselectivity of col for the oxidation of phenylmethyl sulfide. Under environmentally friendly conditions, the effects of different oxidants, pH of reaction solution, concentration of various substances, amount of oxidant and temperature on catalytic activity were investigated. The results showed that the optimal reaction conditions, pH was 8, dosage of oxidant was 28.7 μL, dosage of catalyst was 37.31 μL, reaction temperature was 0 ℃,substrate concentration was 22.16 μmol/L, high conversion(98%) and chemical selectivity(100%) were obtained, but the enantioselectivity was poor(6.3%).