|Thesis Advisor||高 林 ; 赵文军|
|Place of Conferral||北京|
|Keyword||卟啉 席夫碱 多活性中心配合物 环己烷|
由于卟啉配合物与Salen 配合物均具有携氧功能，可以模拟生物体内的催化过程，因此两者都可以称作仿生催化剂。本文为结合这两类配合物的优点，设计并合成了一系列尚未见文献报道的同时具有卟啉结构和Salen 结构的多活性中心的金属配合物
Both of metalloporphyrin and salen-M complexes have the function of carrying oxygen and simulation of catalysis oxidation process in biological bodies, therefore both of them are called bionic catalysts. In this work, a series of new complexes Porphyrin-Salen-Porphyrin (PSP) were designed and synthesized, which had more catalytic active centers and were used in the reaction of catalytic oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid and better results have been obtained. In this dissertation, a novel reaction route was designed and the optimum condition of synthesis of the Porphyrin-Salen-Porphyrin (PSP) was obtained. ①The better methods of synthesis tetraphenyl-porphyrin were obtained from benzaldehyde and pyrrole, the yield beyond 25% from xylene as the solvent and organic weak acids as the catalysts. Different methods in several solvents and using different catalysts which have not been reported also were tried. ②5-(4-nitrophenyl)-10,15,20-triphenyl-porphyrin was synthesized under the protection of nitrogen, at the temperature of -5-0℃ and the nitration of 19 equivalent fuming HNO3. ③5-(4-amidophenyl)-10,15,20-triphenyl-porphyrin was synthesized from the reduction of 5-(4-nitrophenyl)-10,15,20-triphenyl-porphyrin with the SnCl2 as the reducing agent and HCl as the solvent. The aftertreatment method of the product was improved and the dense ammonia was saved. ④The highest yeild of synthesis 5-(4- salicylidene amino phenyl)-10,15,20-triphenyl-porphyrin achived 95% from the 5-(4-amidophenyl)- 10,15,20- triphenyl-porphyrin and salicylaldehyde in the solution of tetrahydrofuran, toluene, anhydrous alcohol, chloroform and chloroform-alcohol mixed solvents as the solvents and Al2O3 as the dehydrating agent. ⑤The Salen-Porphyrin complexes(PSP) were obtained after complexing with transition metal salts in the dichlormethane solvent for the first time. The structure of these compounds were chacterized by the UV-Vis，IR and ′H-NMR. The complexes were applied to the reaction of catalytic oxidation of cyclohexane，catalytic activity was improved in varied degree compared to the metalloporphyrin and μ-Oxo-bismetalloporphyrin. The synthesized new catalysts have promising practical prospect on catalytic oxidation of saturated carbon.
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