有机电合成中活性镁的产生及其反应

通过低还原电位的含活泼氢的烃类化合物及苯腈在消耗性镁阳极存在下的有机电解反应证实了阴极上高分散活性镁的存在, 且其活性比以往方法所得的活性镁的活性更高。     

消耗性镁阳极在有机电合成中的应用(I)——羰基化合物的还原偶联

羰基化合物的还原偶联是形成C-C键的重要方法.早在本世纪初,有人就研究了醛酮的电解还原偶联反应,但所用的电极为Hg、Pd、Pt、Cd等,且电解过程有诸多不便.八十年代中期出现了一种以消耗性金属Mg、Al、Zn为阳极,石墨等为阴极的有机电极合成方法[1].     

异氰酸酯的反应≠

我们研究了芳基和烷基异氰酸酯在消耗性镁阳极存在下的有机电解反应。芳基异氰酸酯电解得N,N’-二取代脲,烷基异氰酸酯则还原偶联为N,N’-二取代草酰胺。我们认为这是由于烷基异氰酸酯从阴极得到电子发生双分子偶联,芳基异氰酸酯则是与阴极析出的高分散的活性镁起作用。     

活性镁及活性氢化镁的合成

研究了在真空下90-150℃间使蒽镁分解生成高活性镁. 再常压加氢, 制得氢化镁的方法. 这一过程中, 镁的活化可循环使用蒽, 基本上不消耗任何试剂, 在分解前用过渡金属化合物掺杂到蒽镁中去可改善活化镁的氢化行为. 当蒽镁中掺杂5%的Cp2TiCl2时, 吸氢温度可降至90℃.     

二茂镁的原位合成及其与羰基化合物的反应

研究了通过萘锂还原法制得的活性镁与环戊二烯原位合成环戊二烯基镁(Cp~2Mg)的方法。Cp~2Mg的存在是由它与醛酮反应生成富烯得到证实。此法产率高, 方法简单, 条件温和。     

单活泼氢手性配体生成的原位镁催化剂及其在不对称合成中的应用

本文对原位镁催化剂近年的工作进行了总结,对由单活泼氢手性配体生成的原位镁催化剂在不对称合成中的应用进行了系统归纳和分类。介绍了由单氮氢键、单酚羟基和单醇羟基构成的手性配体的设计和发展及其在原位镁催化剂中的应用,实现了多种类型的不对称催化反应过程和化学键的形成方式。对于原位镁催化策略的进一步探索,将有助于研究和推广更多类型廉价环保金属资源催化的化学转化过程。     

6H－1，2－氧硫杂环己烷并［5，6－c］异苯并吡喃类衍生物的合成及其抗炎活性

６Ｈ－１，２－氧硫杂环己烷并［５，６－ｃ］异苯并吡喃类衍生物的合成及其抗炎活性王进军，崔昌亿，韩光范，魏永慧，姜贵吉（吉林化工学院精细化工系吉林１３２０２２）（吉林医学院检验系吉林）（延边大学化学系延吉）关键词异苯并二氢吡喃，杂环化合物，抗炎活性可用...     

Novel and Efficient Hydrogenative Cleavage of Azo Compounds to Amine(s) Using Chitosan-Supported Formate and Magnesium

A convenient and efficient method for the hydrogenative cleavage of azo compounds to corresponding amine (s) using chitosan-supported formate as hydrogen donor in conjunction with low-cost magnesium powder is reported. This method was found to be highly facile with selectivity over several other functional groups, such as halogen, alkene, nitrile, carbonyl, ether, amide, methoxy, and hydroxyl groups. Furthermore, this mild, exceedingly efficient, and highly chemoselective method simplifies the handling and separation procedures.     

Formal Synthesis of (+)-Altholactone by Stereoselective Epoxidation Using Magnesium Monoperoxyphthalate (MMPP)

( + ) Ａｌｔｈｏｌａｃｔｏｎｅ ,ａｍｅｍｂｅｒｏｆｎｅｗｔｙｐｅｏｆｃｙｔｏ ｔｏｘｉｃｎａｔｕｒａｌｓｔｙｒｙｌｌａｃｔｏｎｅ ,ｈａｓｂｅｅｎｋｎｏｗｎｔｏｐｏｓｓｅｓｓａｎｔｉｔｕｍｏｒａｃｔｉｖｉｔｙａｇａｉｎｓｔｍｕｒｉｎｅＰ338ｌｅｕｋｅｍｉａａｎｄｓｈｏｗｌｅｔｈａｌｉｔｙｔｏｂｒｉｎｅｓｈｒｉｍｐ .1Ｒｅｃｅｎｔｌｙ ,ａｒｅｐｏｒｔｏｎｉｔｓｓｔｒｕｃ ｔｕｒｅ ａｃｔｉｖｉｔｙｒｅｌａｔｉｏｎｓｈｉｐ2 ａｎｄｐａｐｅｒｓｏｎｔｈｅａｐｐｌｉｃａｔｉｏｎｏｆｎｅｗｓｙｎｔｈｅｔｉｃｍｅ…     

Well‐Defined Molecular Magnesium Hydride Clusters: Relationship between Size and Hydrogen‐Elimination Temperature

A new tetranuclear magnesium hydride cluster, [{ NN ‐(MgH)₂}₂], which was based on a N? N‐coupled bis‐β‐diketiminate ligand ( NN ^2?), was obtained from the reaction of [{ NN ‐(MgnBu)₂}₂] with PhSiH₃. Its crystal structure reveals an almost‐tetrahedral arrangement of Mg atoms and two different sets of hydride ions, which give rise to a coupling in the NMR spectrum (J=8.5 Hz). To shed light on the relationship between the cluster size and H₂ release, the thermal decomposition of [{ NN ‐(MgH)₂}₂] and two closely related systems that were based on similar ligands, that is, an octanuclear magnesium hydride cluster and a dimeric magnesium hydride species, have been investigated in detail. A lowering of the H₂‐desorption temperature with decreasing cluster size is observed, in line with previously reported theoretical predictions on (MgH₂)_n model systems. Deuterium‐labeling studies further demonstrate that the released H₂ solely originates from the oxidative coupling of two hydride ligands and not from other hydrogen sources, such as the β‐diketiminate ligands. Analysis of the DFT‐computed electron density in [{ NN ‐(MgH)₂}₂] reveals a counterintuitive interaction between two formally closed‐shell H^? ligands that are separated by 3.106 Å. This weak interaction could play an important role in H₂ desorption. Although the molecular product after H₂ release could not be characterized experimentally, DFT calculations on the proposed decomposition product, that is, the low‐valence tetranuclear Mg(I) cluster [( NN ‐Mg₂)₂], predict a structure with two almost‐parallel, localized Mg? Mg bonds. As in a previously reported β‐diketiminate Mg^I dimer, the Mg? Mg bond is not characterized by a bond critical point, but instead displays a local maximum of electron density midway between the atoms, that is, a non‐nuclear attractor (NNA). Interestingly, both of the NNAs in [( NN ‐Mg₂)₂] are connected through a bond path that suggests that there is bonding between all four Mg^I atoms.     

Synthesis of a Dimeric Magnesium(I) Compound by an MgI/MgII Redox Reaction

The synthesis of dimeric magnesium(I) compounds of the general type RMgMgR (R=monoanionic substituent) is still a challenging synthetic task and limited to few examples with sterically demanding ligands with delocalized CN‐frameworks that all have been accessed by Na or K metal reduction of magnesium(II) halide precursors. Here we report on the synthesis of a novel diiminophosphinato magnesium(I) compound that has been synthesized by a facile redox reaction using a known magnesium(I) complex. The synthetic strategy may be applicable to other ligand systems and can help expand the class of low oxidation state magnesium complexes even if reductions with Na or K are unsuccessful. The new dimeric magnesium(I) complex has been structurally characterized and undergoes a C? C coupling reaction with tert‐butylisocyanate.     

固体氧化物燃料电池阳极材料研究及其在高温水电解制氢方面的应用

本文综述了固体氧化物燃料电池阳极材料的研究现状和进展。详细地介绍了国内外固体氧化物燃料电池阳极材料的制备、改性、微观结构与性能关系以及阳极反应动力学机理,并对各种材料适用的条件和优缺点进行了比较。对阳极材料在高温电解制氢领域阴极上的应用前景进行了展望。     

Structure and Reaction Chemistry of Magnesium Organocuprates Derived from Magnesiacyclopentadienes and Copper(I) Salts

The chemistry of magnesium organocuprates, including their synthesis, structures, and reactions, remains underexplored. In this work, by taking advantage of the high reactivity and ready availability of magnesiacyclopentadienes, a series of magnesiacyclopentadiene‐based organocuprates were synthesized and structurally characterized. A variety of CuX salts (X=Cl, Br, I, or alkynyl) were successfully applied to react with magnesiacyclopentadienes. Besides CuX salts, AgX salts (X=Cl, alkynyl) also undergwent the above reaction to afford the corresponding magnesium organoargentates. Single‐crystal X‐ray structural analysis and DFT calculations of these butadienyl magnesium organocuprates revealed unique structural characteristics and bonding modes. These results are also very useful to understand the transmetalation process, since the product can be viewed as the resting‐state intermediate of a transmetalation reaction between organomagnesium compounds and coinage‐metal salts. Preliminary information on the reaction chemistry of these magnesium organocuprates is provided by their reactions with allyl bromide, benzoyl chloride, and CO₂.     

高比表面积活性炭的制备及其储氢性能的研究进展

简要分析各种储氢材料和技术的基础上,重点介绍了高比表面积活性炭的制备方法,目前最常用的活化方法是以氢氧化钾为活化剂的化学活化法;并总结了近年来前人在高比表面积活性炭储氢方面的研究结果,同时简要分析了高比表面积活性炭储氢机理方面的研究进展.