铜催化含氮杂环化合物的n-芳基化分析-analysis of n - arylation of nitrogen-containing heterocyclic compounds catalyzed by copper.docx

chemistry. This catalyst is stable in air and can be reused for several times. 12 Betti bases were prepared and their spectrum identification were confirmed. Their promotion abilities in N-arylation reaction were investigated and 1-[(dimethylamino)-(pyridin-2-yl)methyl]naphthalen-2-ol (L7) was found to be the optimal ligand. N-arylation reaction of heterocycles with both aryl -iodides and -bromides proceeded smoothly under lower temperature with good to excellent yields. The monocrystal structure of Cu(OAc)2·L7 prepared in mixed solvent of ethyl acetate and ethanol was confirmed by X-ray single crystal diffraction. Keywards: Ullmann condensation, N-heterocycle, arylhalide, aqueous phase reaction, copper I I 目 录 第一章 前 言···································································································································1 1.1 铜催化 Ullmann 反应研究进展························································································1 1.1.1 N-芳基化合物的主要合成路线 1 1.1.2 Ullmann 反应的进展 2 1.2 无配体、铜催化含氮杂环的 N-芳基化反应 5 1.3 配体促进的 C?N 偶合反应 10 1.3.1 N,N 配体促进的铜催化 N-芳基化反应 10 1.3.2 N,O 多齿配体促进的铜催化的 N-芳基化反应 16 1.3.3 含 O,O 配体促进的含氮杂环的 N-芳基化反应 23 1.3.4 含 P/S 配体促进的铜催化 N-芳基化反应 26 1.4 文献中的反应机理··········································································································29 1.5 本课题存在的问题和拟解决方案··················································································32 第二章 CuI/NaH/DMSO 催化体系中 N-芳基化反应·································································33 2.1 试剂与仪器·······················································································································33 2.2 CuI/NaH 催化的 N-芳基化反应 34 2.2.1 实验条件的优化（溶剂、铜盐、温度的筛选） ···············································34 2.2.2 通用合成方法·······································································································34 2.2.3 实验结果···············································