摘要
开发了一种高效、绿色的苯乙烯环氧化催化体系,以碘化钾(KI)为催化剂、叔丁基过氧化氢(TBHP)为氧化剂、邻二氯苯(o-DCB)为溶剂。通过系统优化,确定最佳反应条件为10 mol%KI、2 eq.TBHP、1 mL o-DCB、100℃反应12 h,在此条件下可获得90.2%的苯乙烯转化率和86.0%的氧化苯乙烯产率,环氧化选择性高达95.3%。机理研究表明,KI与o-DCB的协同作用促进了TBHP均裂生成叔丁基过氧自由基(t-BuOO·),进而通过自由基加成-氧迁移路径实现环氧化。该体系对多种芳香烯烃表现出良好的底物适应性,且无需昂贵过渡金属或复杂配体,为工业环氧化合成提供了更为经济的替代方案。
An efficient and green catalytic system for styrene epoxidation was developed using potassium iodide(KI)as the catalyst,tert-butyl hydroperoxide(TBHP)as the oxidant,and o-dichlorobenzene(o-DCB)as the solvent.Systematic optimization established the optimal reaction conditions as 10 mol%KI,2 equivalents of TBHP,1 mL o-DCB at 100℃for 12 h.Under these conditions,90.2%styrene conversion and 86.0%styrene oxide yield were achieved,with an epoxidation selectivity as high as 95.3%.Mechanistic investigations revealed that the synergistic interaction between KI and o-DCB facilitated the homolytic cleavage of TBHP to generate tert-butylperoxy radicals(t-BuOO·),which subsequently achieved epoxidation through a radical addition-oxygen migration pathway.The system demonstrated excellent substrate compatibility with various aromatic alkenes while eliminating the need for expensive transition metals or complex ligands,offering a cost-effective alternative for industrial epoxide synthesis.
作者
刘远昊
李跃辉
杨维冉
LIU Yuanhao;LI Yuehui;YANG Weiran(School of Chemistry and Chemical Engineering,Nanchang University,Nanchang 330031,China;School of Smart Energy,Shanghai Jiao Tong University,Shanghai 200240,China)
出处
《南昌大学学报(理科版)》
2025年第6期599-606,共8页
Journal of Nanchang University(Natural Science)
基金
国家自然科学基金资助项目(22169011)。
关键词
烯烃环氧化
碘化钾
邻二氯苯
环境友好
olefin epoxidation
potassium iodide
o-dichlorobenzene
environmentally friendly
