高价碘﹣过渡金属配合物双功能催化体系研究-有机化学专业论文.docxVIP

万方数据 万方数据 摘要 摘要 本学位论文的研究内容由以下二部分组成： 1. 含碘苯的四齿配体及其过渡金属(Mn2+，Co2+，Cu2+)配合物的合成表征与 催化性能的研究。 设计、合成了含 N 杂原子的四齿配体，L1(C30H32I2N4O2)和 L2(C30H32N4O2) 以及它们的过渡金属(Mn2+，Co2+，Cu2+)配合物[CuL1CH3CN](ClO4)2 (4)， [CoL1(CH3CN)2](ClO4)2 (5)，[MnL1Cl2] (6)，[MnL2Cl2] (7)，用 IR、UV-Vis、质 谱和元素分析等方法对有关化合物进行了表征，通过 X-射线单晶衍射测定了配 合物 4-7 的晶体结构。以配合物 4-7 为催化剂、过硫酸氢钾(Oxone)为氧化剂， 研究了这些金属配合物催化乙苯氧化的反应。研究结果表明在含有碘原子的配 合物 4-6 中，配合物 6 表现出最好的催化活性，其产率达到 87%；而不含碘原子 的配合物 7 的产率仅为 16%。 2. 空气氧化苄溴制备醛的研究 设计、合成了 7 个苄溴化合物，研究了空气氧化苄溴制备醛的反应。在光 照和碱的作用下，其中部分苄溴能被空气中的氧气在室温下氧化为苄醛。这个 氧化反应是一个自由基反应，在反应中苄溴在光照下产生苄基自由基。理论计 算表明，苄基自由基与芳环取代基的 π-π 重叠作用有利于自由基的稳定，从而促 进氧气氧化苄溴形成苄醛的反应。没有这种 π-π 重叠作用的苄溴则无法实现空气 氧化成苄醛的反应。 关键词：碘，高价碘，金属配合物，催化氧化，乙苯，苄溴，氧气，苄醛，π-π 重叠 III Abst Abstract ABSTRACT This dessertation is consisted of following two parts: Synthesizing tetradentate ligand of iodine benzene and its transition metal (Mn2+, Co2+, Cu2+) complexes and researching catalytic properties of ethylbenzene Two N-containing tetradentate ligands, L1(C30H32I2N4O2) and L2(C30H32N4O2) and their metal complexs [CuL1CH3CN](ClO4 )2(4), [CoL1(CH3CN)2](ClO4)2 (5), [MnL1Cl2] (6), [MnL2Cl2] (7) were synthesized. All the compounds were characterized by IR, UV-Vis, mass spectrometry and elemental analysis. The crystal structures of complexs 4-7 were determined by X-ray single crystal diffraction. These compounds were used as catalysts to catalyse the oxidation of ethylbenzene with oxone as oxidant. Our results show that complexe 6 exhibited the best catalytic efficacy with a yield of 87% among complexes 4-6. Compound 7 possesses no iodine benzene and it catalytic activity is much lower with a yield of 16%. Aerobic oxidation of benzyl bromide into benzyl aldehyde. Designing and synthesizing of seven benzyl bromide complexs to explor benzyl aldehyde with oxygen of air as oxidant. Our results show that under the conditions of tungsten light and bases, some benzyl bromide can be oxided to benzyl aldehyde with oxygen of air at room temperature. This oxidation reaction is a ra