XJIPC OpenIR  > 资源化学研究室
Thesis Advisor高 林 ; 赵文军
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline有机化学
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
Porphyrin-Salen-Porphyrin (PSP),并应用于仿生催化氧化环己烷制备环己醇、环己酮和己二酸的实验,取得了较好的催化效果。设计了一条反应路线并优化了各步的反应条件。①以苯甲醛,吡咯为起始原料合成四苯基卟啉,尝试了未见文献报道的几种溶剂和催化剂,确定以二甲苯为溶剂,有机弱酸为催化剂,反应收率均在25%以上;②在氮气保护下,以19mol 当量的发烟硝酸在-5-0℃下反应合成5-对硝基苯基-10,15,20-三苯基卟啉,反应产物单一,收率为75%;③用氯化亚锡作还原剂,浓盐酸作溶剂还原5-对硝基苯基-10,15,20-三苯基卟啉合成5-对氨基苯基-10,15,20-三苯基卟啉,采用先固液分离然后再中和的后处理方法,节省了浓氨水的用量;④分别选用四氢呋喃、甲苯、无水乙醇、三氯甲烷以及三氯甲烷与无水乙醇的混合溶液作为反应溶剂,Al2O3 作脱水剂合成水杨醛缩氨基四苯基卟啉,收率最高达到95%;⑤以二氯甲烷为溶剂,水杨醛缩氨基四苯基卟啉与不同的过渡金属盐化合物配合,首次合成了Porphyrin-Salen-Porphyrin(PSP)配合物。各化合物均通过UV-Vis,IR,1H NMR 进行了表征。将配合物应用于环己烷的催化氧化,催化活性与文献报道的单取代卟啉及μ-O 双卟啉相比有了不同程度的提高。此类催化剂应用于饱和碳氢键的催化氧化反应具有很好的应用前景。

Other Abstract

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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