氧化腈与丙炔1,3-偶极环加成反应中区域选择性的理论研究  

Theoretical Study on the Regioselectivity of Nitrile Oxide 1,3-Dipolar Cycloaddition to Propyne

作　　者：张月梅 王若曦[1] 徐为人[2] 刘成卜[1] 

机构地区：[1]山东大学理论化学研究所,济南250100 [2]天津药物研究院天津药代动力学与药效动力学省部共建国家重点实验,室天津300193

出　　处：《化学学报》2005年第7期567-571,F005,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20133020)资助项目

摘　　要：用密度泛函(DFT)B3LYP/6-311++G**方法研究了氧化腈(RCNO,R=F,NO2,OCH3,OH,COOCH3,CHO,CONH2,H,CH3)与丙炔的1,3-偶极环加成反应,并且计算了不同温度下的反应速率常数,讨论了氧化腈上不同取代基R的取代效应和温度对反应区域选择性的影响.结果显示,氧化腈与富电子亲偶极体——炔烃反应,5-取代反应占优势;氧化腈上取代基R为强吸电子基团时或在较高温度下,有利于4-取代反应的进行.In order to discuss the regioselectivity of nitrile oxide 1,3-dipolar cycloaddition to propyne, 1,3-dipolar cycloaddition reaction of substituted nitrile oxide (RCNO, R=F, NO2, OCH3, OH, COOCH3, CHO, CONH2, H, CH3) with propyne was studied using density functional theory at the 6-311++G** level, and the reaction rates were calculated at different temperature from 200 to 400 K. The conclusions are that 5-substituted reaction of nitrile oxide with electron-deficient dipolarophile-propyne is dominant, while 4-substituted reaction of electron-deficient nitrile oxide with propyne is favored at relatively high temperature.

关 键 词：偶极环加成反应 区域选择性 氧化 理论研究 丙炔 腈 反应速率常数 取代反应 吸电子基团 密度泛函 取代效应 取代基 NO2 CHO 高温度 炔烃 

分 类 号：O621.255[理学—有机化学]