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研究了金属卟啉仿生催化环辛烷选择氧化的反应。结果表明,反应时间、反应温度、反应压力、催化剂浓度和类型对反应具有明显的影响,适宜的反应条件是反应温度135℃、压力2.5 MPa、时间4 h、金属卟啉浓度7×10-4mol%、搅拌速率800 rpm。金属卟啉的中心金属、环外取代基的类型和位置对于反应活性同样具有影响,不同中心金属的金属卟啉的催化活性顺序为Mn>Co>Fe;不同取代基位次的金属卟啉的催化活性顺序为o->p-;不同取代基的金属卟啉的催化活性顺序为—NO2>—Cl>—OCH3。其中,催化效果较好的为T(p-Cl)PPMn Cl,产物的总收率和总选择性最高,分别为25.5%和62.3%。
The biocatalytic cyclooctane selective oxidation of metalloporphyrin was studied. The results showed that the reaction time, reaction temperature, reaction pressure, catalyst concentration and type had a significant effect on the reaction. The optimum reaction conditions were reaction temperature 135 ℃, pressure 2.5 MPa, time 4 h, metal porphyrin concentration 7 × 10-4mol %, Stirring speed 800 rpm. The central metal of metalloporphyrin and the type and position of the substituents outside the ring also have an influence on the reactivity. The catalytic activity of the metal porphyrins with different central metals is Mn> Co> Fe. The metalloporphyrins with different substituent orders The order of catalytic activity is o-> p-. The order of catalytic activity of different substituted metalloporphyrins is -NO2> -Cl> -OCH3. Among them, T (p-Cl) PPMnCl with good catalytic performance was the best, with the highest total yield and total selectivity of 25.5% and 62.3%, respectively.