摘要
【目的】研究交叉脱氢偶联(cross-dehydrogenative-coupling,CDC)反应机理及条件,寻求一种新的合成方法,最终实现酰胺与N-甲基吡咯烷酮sp3 C-N官能化反应.【方法】根据酰胺与N-甲基吡咯烷酮sp^3C-N官能化反应的反应机理和反应路径,对该反应可能的催化剂AgNO_3,FeCl_3,CuCl_2,CuCl,NiSO_4·6H_2O,Fe_2(SO_4)_3·xH_2O,SnCl_2·2H_2O,CuI,BiCl_3,CoCl_2·6H_2O及氧化剂TBHP,Ca(ClO)_2,K2S_2O_8等化合物进行了筛选,同时优化了反应条件.【结果】最佳催化剂为AgNO_3,氧化剂为K_2S_2O_8,最佳反应条件为温度75℃,反应时间4h,溶剂为体积分数50%的乙腈水溶液.合成了6种不同的酰胺衍生物,它们的产率在64%~75%之间.用核磁1 H谱和红外光谱鉴定合成新化合物的结构,表明这些化合物都是酰胺与N-甲基吡咯烷酮反应的主产物.【结论】该方法是一种实现交叉脱氢偶联(cross-dehydrogenative-coupling,CDC)反应的高效绿色的合成方法.
[Objectivel The reaction mechanism and conditions were studied of cross-dehydrogenative coupling （CDC） reaction in order to find a new synthetic method of functionalized sp3C-N reaction of amide and N-methylpyrrolidone. [Method] According to the reaction mechanism and reaction route of the func- tionalized sp C-N reaction of amide and N-methylpyrrolidone, the possible catalysts include AgNO3, FeCl3, CuCl2, CuCl, NiSO4· 6H2O, Fe2（SO4）3· xH2O, SnCl2· 2H2O, CuI, BiCl3, COCl2 · 6H2O and oxidants include TBHP, Ca（C10）2 and K2 S2O8 ect were screened. The reaction conditions were optimized. [Result] The catalytic effect of silver nitrate and the works of potassium persulfate oxidation were opti- mum, the optimum reaction temperature and time were 75℃ and 4 h respective. The solvent of acetonitrile and water （v/v = 1：1）. Six different amide derivatives which yield between 64%-75% were synthesized by the method. The structures of six different amide derivatives were identified by 1H NMR spectra and infrared spectra, which shows that these compounds were the main products of amide and N-methylpyrroli- done. [Conclusion] The method was an effective and green synthesis channel for achieved cross-dehydro-genative coupling reaction.
出处
《甘肃农业大学学报》
CAS
CSCD
北大核心
2016年第6期155-160,共6页
Journal of Gansu Agricultural University
基金
2012年中医药部门公共卫生专项子课题
甘肃农业大学校创新基金(GAU-CX1110)
关键词
C-N键
交叉偶联反应
胺化反应
银催化
C-N bond
cross-coupling reaction
amination reaction
silver catalyzed
