摘要
在M06-2X/SMD/6-311+G(d,p)理论水平下,研究水液相1个大气压、 310.15 K温度下依达拉奉(Eda)酮式异构体与超氧化氢自由基(·HO_(2))的反应机理.结果表明:Eda酮式异构体与·HO_(2)的反应有抽H、加成和单电子转移3个过程;抽H反应主要通过·HO_(2)抽取杂环H和甲基H实现,反应的自由能垒为77.1~78.7 kJ/mol;加成反应可通过·HO_(2)加成不饱和C的过程实现,加成自由能垒为48.2~95.0 kJ/mol;加成到杂环上与甲基相连的C原子的放热反应最具优势,自由能垒为48.2 kJ/mol;单电子转移的自由能垒为141.1 kJ/mol,该过程不能实现.可见,水液相下Eda酮式异构体可通过抽H和加成反应消除·HO_(2).
At the theoretical level of M06-2X/SMD/6-311+G(d,p),we studied the reaction mechanism between Edaravone(Eda)keto isomers and superoxide hydrogen radical·HO_(2) in aqueous liquid phase at 1 atmospheric pressure and 310.15 K temperature.The results show that there are three processes in the reaction of Eda keto isomers with·HO_(2):H extraction,addition and single electron transfer.The H extraction reaction is mainly achieved through·HO_(2) extraction of heterocyclic H and methyl H,and the free energy barrier of the reaction is 77.1—78.7 kJ/mol.The addition reaction can be realized by the process of·HO_(2) addition to unsaturated C,and the free energy barrier of addition is 48.2—95.0 kJ/mol.The most advantageous exothermic reaction is the addition of C atoms connected to methyl groups on heterocycles,with a free energy barrier of 48.2 kJ/mol.The free energy barrier of single electron transfer is 141.1 kJ/mol,which is impossible.Therefore,the Eda keto isomer in aqueous liquid phase can eliminate·HO_(2) by H extraction and addition reactions.
作者
潘宇
姜春旭
王颢霖
杨应
董雷刚
王佐成
李冰
PAN Yu;JIANG Chunxu;WANG Haolin;YANG Ying;DONG Leigang;WANG Zuocheng;LI Bing(Theoretical Computing Center,Baicheng Normal University,Baicheng 137000,Jilin Province,China;College of Physics and Electronic Information,Baicheng Normal University,Baicheng 137000,Jilin Province,China;College of Forest,Beihua University,Jilin 132013,Jilin Province,China;College of Medicine,Hainan Vocational University of Science and Technology,Haikou 571126,China)
出处
《吉林大学学报（理学版）》
CAS
北大核心
2024年第5期1254-1266,共13页
Journal of Jilin University:Science Edition
基金
吉林省教育厅科研重点项目(批准号:JJKH20240033KJ)
吉林省自然科学基金(批准号:YDZJ202201ZYTS666)。
