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A Theoretical Study on the Reaction Mechanism of Epoxidation Reaction of the [4-(bromomethyl)bicyclo [4.4.1]undeca-1,3,5,7,9-pentaen-3-yl]methanol
Zhang Jingchang,Zhang Sen,Yang Zuoyin,Cao Weiliang*
Author NameAffiliationE-mail
Zhang Jingchang Research Institute of Modern Catalysis, the Key Laboratory of Science and Technology of Controllable Chemical Reactions Ministry of Education Beijing University of Chemical Technology, Beijing 100029  
Zhang Sen Research Institute of Modern Catalysis, the Key Laboratory of Science and Technology of Controllable Chemical Reactions Ministry of Education Beijing University of Chemical Technology, Beijing 100029  
Yang Zuoyin Research Institute of Modern Catalysis, the Key Laboratory of Science and Technology of Controllable Chemical Reactions Ministry of Education Beijing University of Chemical Technology, Beijing 100029  
Cao Weiliang* Research Institute of Modern Catalysis, the Key Laboratory of Science and Technology of Controllable Chemical Reactions Ministry of Education Beijing University of Chemical Technology, Beijing 100029 caowl@mail.buct.edu.cn  
Abstract:
A reaction mechanism of epoxidation reaction of the [4-(bromomethyl)bicyclo[4.4.1]undeca-1,3,5,7,9-pentaen-3-yl]methanol has been studied by using the density functional theory(DFT) method at B3LYP level with 6 31G* basis set. The geometric structures of reactant, product and transition state have been optimized. The transition state is found by the QST2 method and characterized by the vibration frequency analysis. The intrinsic reaction coordinate(IRC) for this reaction is traced and confirms the reaction mechanism. The changes and the nature of related chemical bonds along the IRC path have been analyzed by the theory of electronic charge density. The result shows that the elimination reaction and ring closing reaction are synergistic, and the hydrogen in the elimination reaction derives from hydroxyl. In addition, the activation energy of the reaction is 139.2 kJ/mol.
Key words:  [4-(bromomethyl)bicyclo[4.4.1]undeca-1,3,5,7,9-pentaen-3-yl]methanol, Epoxidation reaction, DFT, Reaction mechanism, Topological analysis of charge density
FundProject:
(4-溴甲基双环[4.4.1]-1,3,5,7,9-十一碳五烯基-3-)甲醇环氧化反应机理的理论研究
张敬畅,张森,杨作银,曹维良*
摘要:
采用量子化学的密度泛函理论(DFT),在B3LYP/6-31G*水平上研究了(4-溴甲基双环[4.4.1]-1,3,5,7,9-十一碳五烯基-3-)甲醇环氧化反应机理,在对反应物和产物几何结构优化的基础上,搜索优化了反应的过渡态结构,通过振动分析和内禀反应坐标(IRC)跟踪方法对过渡态及其所处的反应路径进行了确认,并用电荷密度拓扑分析方法考察了反应过程中旧键断裂和新键形成的细节.计算结果表明,该反应中的消除反应和成环反应是协同进行的,溴化氢消除反应中的氢来自与O(22)相连的羟基氢,反应的活化势垒为139.2 kJ/mol,反应放热25.1 kJ/mol.
关键词:  (4-溴甲基双环[4.4.1]-1,3,5,7,9-十一碳五烯基-3-)甲醇  密度泛函理论  环氧化反应  反应机理  电荷密度拓扑分析
DOI:10.1088/1674-0068/18/2/167-173
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