3-卤-2(5H)-呋喃酮的无钯催化脱卤反应  

Dehalogenation of 3-Halo-2(5H)-Furanones in the Absence of Pd Catalyst

作　　者：汪朝阳[1] 薛福玲[1] 霍景沛[1] 熊金锋[1] 彭湃[1] 莫广珍[1] 陈任宏[2] 

机构地区：[1]华南师范大学化学与环境学院,教育部环境理论化学重点实验室,广东广州510006 [2]广东食品药品职业学院,广东广州510520

出　　处：《华南师范大学学报（自然科学版）》2013年第6期113-123,共11页Journal of South China Normal University(Natural Science Edition)

基　　金：国家自然科学基金项目(20772035);广东省高等学校人才引进专项资金项目(粤财教[2011]431号);广东省自然科学基金项目(S2011010001556)

摘　　要：在研究钯催化的脱卤反应时,发现3-卤-2(5H)-呋喃酮在无钯催化的情况下可以发生脱卤反应.在碱为12当量的Et3N、反应溶剂为CH3CN、反应温度150℃、反应时间21 h的优化条件下,产率可达到52%.当底物中存在芳环卤结构时,该无钯催化的脱卤反应只脱去呋喃酮3-位上的卤素.这种反应的唯一性与钯催化脱卤反应组合,可以为多官能团(特别是多卤情况下)非芳基卤底物的选择性脱卤提供更多的控制方法.通过重水实验等研究发现反应体系中的有机碱三乙胺可能是脱卤反应的氢源,但不能完全排除水作为氢源的可能性.During the studies on the Pd-catalyzed dehalogenation reaction , it was accidentally found that the deha-logenation reaction of 3-halo-2（5H）-furanone could occur without Pd catalysts .Under the optimized reaction condi-tions, such as base 12 equiv.Et3N, solvent CH3CN, and reaction temperature 150 ℃, the best yield can be 52%.For the substrates simultaneously containing aryl halide structure , this Pd-catalyst-free dehalogenation reac-tion has good selectivity .The combination of this unique selectivity with the Pd-catalyzed dehalogenation reaction can provide many control choices for the selective dehalogenation of the non-aromatic halide substrates with many different functional groups , especially varied halogen atoms .The studies on the reaction mechanism by D 2 O experi-ments show that triethylamine is used as not only organic base , but also the hydrogen source of dehalogenation reac-tion.However, it is difficult to completely remove the possibility of water as a hydrogen source in this reaction .

关 键 词：2(5H)-呋喃酮 脱卤反应 反应机理 氢源 选择性 

分 类 号：O622.4[理学—有机化学]