基于Willgerodt-Kindler反应的两种二茂铁羧酸的合成及机理研究

以Na2S•9H2O为催化剂, 通过Willgerodt-Kindler反应分别合成了二茂铁乙酸和1,1’-二茂铁二乙酸, 用IR, 1H NMR, MS和元素分析对产物分别进行了结构表征, 并利用GC-MS研究了该反应机理, 推测反应是由多硫阴离子进攻羰基α碳所引发, 同时讨论了影响反应的各种因素.     

Layered Transition Metal Electride Hf2Se with Coexisting Two-Dimensional Anionic d-Electrons and Hf–Hf Metallic Bonds

Electrides are unique materials,whose anionic electrons are confined to interstitial voids,and they have broad potential applications in various areas.In contrast to the majority of inorganic electrides,in which the anionic electrons primarily consist of s-electrons of metals,electrides with anionic d-electrons are very rare.Based on first-principles electronic structure calculations,we predict that the layered transition metal chalcogenide Hf₂Se is a novel electride candidate with anionic d-electrons.Our results indicate that the anionic electrons confined in the Hf₆ octahedra vacancy between [Hf₂Se] layers mainly come from the Hf-5 d orbitals.In addition,the anionic electrons coexist with the Hf-Hf multiple-center metallic bonds located in the center of neighboring Hf₄ tetrahedra.The calculated work function(3.33 eV) for the(110) surface of Hf₂Se is slightly smaller than that of Hf₂S,which has recently been reported to exhibit good electrocatalytic performance.Our study of Hf2 Se will enrich the electride family,and promote further research into the physical properties and applications of electrides.     

2-甲基-4-甲氧基苯基苯胺的合成

邻硝基甲苯在甲醇、乙酸和硫酸混合溶液中, 在Pt/C的催化下发生氢化和Bamberger重排生成2-甲基-4-甲氧基苯胺. 后者在Pd/C的存在下以苯酚为反应介质与环已酮缩合生成2-甲基-4-甲氧基苯基苯胺, 反应总产率63.0%. 文中给出了产物与中间产物的核磁共振氢谱和质谱, 同时讨论了影响反应的因素.     

可见光催化偕二氟烯烃碳-氟键官能化反应的研究进展

单氟烯烃结构单元广泛存在于药物及天然产物等复杂功能分子中,同时也是重要的有机合成子,在医药、生物和材料等领域具有广泛的应用.因此,开发绿色、经济且高效的合成单氟烯烃化合物的方法具有重要的科学意义和现实价值.偕二氟烯烃C—F键官能化是制备单氟烯烃化合物的有效手段,总结了在可见光氧化还原催化、可见光氧化还原/过渡金属协同催化条件下实现偕二氟烯烃C—F键官能化反应的研究进展,主要介绍了底物适用范围、反应机理和合成应用,并对它的发展前景进行了展望.