中国科学院新疆理化技术研究所机构知识库
Advanced  
XJIPC OpenIR  > 资源化学研究室  > 学位论文
题名: 仿生催化氧化环己烷催化剂的合成
作者: 苏建玲
答辩日期: 2007-06-20
导师: 高 林 ; 赵文军
专业: 有机化学
授予单位: 中国科学院研究生院
授予地点: 北京
学位: 硕士
关键词: 卟啉 ; 席夫碱 ; 多活性中心配合物 ; 环己烷
摘要: 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。
英文摘要: 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.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3497
Appears in Collections:资源化学研究室_学位论文

Files in This Item:
File Name/ File Size Content Type Version Access License
苏建玲硕士论文.pdf(1307KB)学位论文--暂不开放View 联系获取全文

作者单位: 中国科学院新疆理化技术研究所
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[苏建玲]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[苏建玲]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 苏建玲硕士论文.pdf
格式: Adobe PDF
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace