Meso-四(3,4-二甲苯基)卟啉金属配合物的合成

Synthesis of meso-tetra(3,4-dimethylphenyl) porphyrin complexes

为筛选催化环己烷氧化合成己二酸用仿生催化剂,研究了以吡咯、3,4-二甲基苯甲醛和金属盐为原料,合成一种带多个疏水性短碳链对称卟啉化合物meso-四(3,4-二甲苯基)卟啉(简称TDMPP)金属钴(Ⅱ)、铜(Ⅱ)配合物的方法,探讨了溶剂配比、反应时间、反应物的物质量浓度等对产率的影响;并利用UV-Vis和IR对合成的物质结构进行了表征.结果表明合成TDMPPCo的适宜工艺参数为:v(丙酸)∶v(冰乙酸)等于2∶1;n(吡咯)∶n(3,4-甲基苯甲醛)∶n(醋酸钴)等于1.00∶1.04∶0.29;吡咯的物质量浓度为0.25mol/L;反应时间为50min;反应温度为125～130℃;产率达32%.合成TDMPPCu的适宜工艺参数为:v(丙酸)∶v(冰乙酸)等于3∶1,n(吡咯)∶n(3,4-甲基苯甲醛)∶n(醋酸铜)等于1.00∶1.04∶0.27;吡咯的物质量浓度为0.25mol/L,反应时间为50min,反应温度为130～135℃,产率达38%.

To select the bionic catalyst for synthesizing adipic acid with catalytic cyclohexane oxidation,the synthetic method of symmetrical metalloporphyrin complexes with multiple hydrophobic short carbon chain,i. e.,meso-tetra （3,4-dimethylphenyl） porphyrin （TDMPP） complexes with Co2＋（TDMPPCo） and Cu2＋（TDMPPCu）,was investigated,where 3,4-dimethyl-benzaldehyde,pyrrole and metal salt were taken as raw materials. The effect of the mixed solvent volume ratio,reactive time and reactant concentration on the reaction yield was discussed. The obtained complexes were characterized by UV-Vis and IR. The experimental results show that the yield of TDMPPCo is 32%,when the mixed solvent volume ratio of propionic acid to acetic acid is 2∶1,the molar ratio of pyrrole to 3,4-dimethylbenzaldehyde to acetate cobalt is 1.00∶1.04∶0.29,the concentration of pyrrole is 0.25mol/L,the reactive time is 50min,and the reaction temperature is 125 to 130℃.The yield of TDMPPCu is 38%,when the mixed solvent volume ratio of propionic acid to acetic acid is 3∶1,the molar ratio of pyrrole to 3,4-dimethylbenzaldehyde to acetate manganese is 1.00∶1.04∶0.27,the concentration of pyrrole is 0.25mol/L,the reactive time is 50min,and the reaction temperature is 130 to 135℃.