2-苯基-9,10-双取代蒽的合成研究

采用2-溴蒽醌,溴苯,2-溴萘为原料,丁基锂为锂化试剂,通过对羰基加成还原再发生Suzuki偶联,反应制备出2-苯基-9,10-双苯基蒽和2-苯基-9,10-双(2-萘基)蒽,收率分别为96.40％和95.70％,液相色谱检测纯度(254nm)为99.42％和99.40％,通过红外光谱对其主体骨架结构进行了表征.热重分...     

过渡金属配合物催化的烯烃自由基反应进展

近年来,通过烯烃官能团化构建有机化合物成为有机合成领域的研究热点之一.当选择种类、晶体结构和性能多样的过渡金属配合物作为催化剂时,这类反应具有高效、高选择性和原子经济性高的特点.该文总结了近5年来具有代表性的利用过渡金属盐及其配合物作为催化剂,经过自由基反应历程实现烯烃官能团化的研究进展,其反应特点是在过渡金属催化下烯烃参与自由基反应,再与其他底物或试剂偶联成键,从而实现官能团化.催化剂除了贵重金属铑、钯和钌等的配合物之外,还有普通金属,如铁、镍、铜和钴的盐及其配合物.过渡金属配合物催化烯烃的自由基反应拓宽了烯烃官能团化的研究领域,为有机合成工作者提供了新方法和思路,还为烯烃官能团化合成各种功能化合物的产业化生产提供新方案.     

9-蒽甲胺的合成

以9-蒽甲醇为原料,通过溴化、叠氮基亲核取代、催化氢化3步反应制备了9-蒽甲胺,总收率达60%。利用1HNMR、质谱、元素分析对产物的组成和结构进行了确认和鉴定。研究结果表明,以Pd/C为催化剂,催化氢化在常温常压下能够快速进行,40min就可完全反应。     

羧脒盐桥介导的单重态能量传递直接观察

设计构建了以羧脒盐桥联接的萘和蒽超分子组装体系,NA-(脒基-羧基)-An以及相应的模型体系.稳态和时间分辨荧光光谱研究表明,置于羧脒盐桥两端的萘和蒽基团之间发生了从萘到蒽的单重态能量传递,NA-(脒-羧)-An超分子体系中单重态能量传递效率和速率常数分别大于0.99和9.9×109s-1.推测羧脒盐桥介导了体系中的单重态能量传递过程,单重态能量传递‘通过键’以电子交换机制进行.     

从Ⅰ蒽油中连续提取粗蒽的工艺研究

文章针对传统的粗蒽制取工艺中制取粗蒽质量不稳定,结晶机设备多,效率低下,生产周期长等问题,提出了从Ⅰ蒽油中连续提取粗蒽的新工艺路线,简化了生产设备和工艺路线,通过严格控制Ⅰ蒽油原料质量、降温结晶条件和离心操作等真正实现了粗蒽的连续化生产,缩短了生产周期,提高了粗蒽的产率和蒽含量,同时降低了粗蒽中的油含量和水含量,保证了产品达到一级品95%以上。     

硫杂蒽酮化合物的合成研究

用2,2'-二硫代水杨酸在浓硫酸的催化作用下合成了 O-(硫杂蒽酮-[2]-基)-氧乙酸、2-氯硫杂蒽酮、1-氯-4-羟基硫杂蒽酮以及2-羟基硫杂蒽酮等硫杂蒽酮类化合物.并且通过元素分析、红外光谱、紫外光谱、核磁氧谱、碳谱及差热热重分析等实验方法进行表征.结果表明,所合成的硫杂蒽酮类化合物具有所述的特征结构.     

过渡金属配合物催化烯烃的自由基反应进展

近年来，通过烯烃官能团化构建有机化合物成为有机合成领域的研究热点之一。当选择种类、晶体结构和性能多样的过渡金属配合物作为催化剂时，这类反应具有高效、高选择性且成本低的特点。本文总结了近五年来利用过渡金属盐及其配合物作为催化剂，经过自由基反应历程实现未活化烯烃官能团化的研究进展，其反应特点是在过渡金属催化下，烯烃生成自由基并与其它底物或试剂偶联成键，从而实现官能团化。其中，催化性能优异的催化剂除了贵重金属铑、钯和钌等的配合物之外，还有普通金属，如铁、镍、铜和钴的盐及其配合物。这些方法拓展了烯烃官能团化的研究领域，为有机合成工作者提供新方法和思路，还为将来的产业化生产提供新方案。     

9-蒽硼酸的合成研究

蒽衍生物被认为是很有开发前景和实用价值的一类发光材料,9-蒽硼酸是合成其他蒽衍生物重要的中间体。本文以蒽为原料,经溴化得到9-溴蒽,再采用丁基锂法得到9-蒽硼酸。并对影响反应的重要因素进行了考察和讨论。反应需要在低于-70℃下进行,得到的收率达到79.8%。本文采用的工艺路线合理,反应时间短,产品收率高。     

新型复合工艺制取蒽系产品的研究

研究了用复合工艺制取蒽系产品的新方法,该法可同时得到纯度９９．１４％的蒽、９６ ２８％的菲和９６．８８％的咔唑,具有流程简单、投资低和无环境污染等特点。     

9-乙烯基蒽/二苯基碘鎓盐体系敏化甲基丙烯酸甲酯光聚合

通过对9-乙烯基蒽单组分及其与氯化二苯基碘鎓盐(DPIOC)组成的双组分光敏体系引发甲基丙烯酸甲酯光聚合的研究,发现DPIOC的加入明显增大了9-乙烯基蒽光引发聚合速度.它们在引发MMA光聚合的同时,也参与聚合反应而自身进入聚合物链中.     

Copper, silver, and gold complexes in hydrosilylation reactions

The reduction of diverse functional groups is an essential protocol in organic chemistry. Transition-metal catalysis has been successfully applied to the reduction of olefins, alkynes, and many carbonyl compounds via hydrogenation or hydrosilylation; the latter presenting several advantages over hydrogenation. Notably, hydrosilylation generally occurs under mild reaction conditions, and consequently over-reduced products are rarely detected. Moreover, the great majority of hydrosilanes employed in this reaction are easily handled, inexpensive, or both. A large number of multiple bonds can be involved in this context, and the hydrosilylation reaction can be regarded as a useful method for the synthesis of silicon-containing organic molecules or a convenient way of reducing organic compounds. Furthermore, the silyl group can also be retained as a protecting group, a strategy that can be of great usefulness in organic synthesis. Since the first Wilkinson's catalyst-mediated hydrosilylation of ketones in 1972, metals such as rhodium and iridium have attracted most of the attention in this area. A wide array of catalytic systems for hydrosilylation reactions is nowadays available, which has allowed for a great expansion of the synthetic scope of this transformation. After having been overlooked in the early years, group 11 metals (Cu, Ag, and Au), especially copper, have emerged as appealing alternatives for hydrosilylation. The use of a stabilized form of copper hydride, the hexameric [(Ph3P)CuH]6, by Stryker represented a breakthrough in copper-catalyzed reduction reactions. Nowadays, several copper-based catalytic systems compare well with a variety of reported rhodium-based catalysts, which generally suffer from the high cost of the catalyst. Tertiary phosphine ligands are the most widely used in these transformations. However, other families such as N-heterocyclic carbenes (NHCs) have shown promising activities. Compared with copper, little attention has been paid to silver- or gold-based catalysts. Silver salts have been considered inert towards hydrosilylation, and they are often employed as innocent anion exchange reagents for the in situ generation of cationic transition metal catalysts. Despite the rare reports available, they have already shown interesting reactivity profiles, for example, in the chemoselective reduction of aldehydes in the presence of ketones. Furthermore, 1,2-hydride delivery is favored over 1,4-reductions for alpha,beta-unsaturated carbonyl compounds, in contrast with most copper-based systems.     

Preparation of sodium salts of N‐sulfonic acids by sulfomethylation of nitro oligomers obtained from waste rubbers

The sulfomethylation of nitro oligomers obtained from waste rubbers (NO‐GWR) with sodium hydroxymethane sulfonate was studied in aqueous–alkali solutions from 50 to 80°C for reaction times of 3.5–5.5 h with weight ratios of 1.0:0.3–0.6. The initial NO‐GWR was produced by the oxidation/destructive nitration of waste rubbers with nitric acid in a heterogeneous medium. The influence of the reaction conditions on the yields and functional compositions of the sodium salts of two types of N‐sulfonic acids was investigated. Some of the nitro groups transformed into sulfaminate groups at 80°C or lower. One type of N‐sulfonic acid was isolated from its sodium salt by ion exchange. The oligosulfo derivatives were characterized by elemental and thermal analyses, IR and ¹H‐NMR spectroscopy, and the number‐average molecular weight. The sodium salts of the N‐sulfonic acids obtained from NO‐GWR possessed functional compositions similar to those of sodium salts from butadiene–styrene nitro oligomers prepared from butadiene–styrene latexes. Therefore, NO‐GWR obtained from available raw materials can be used as the initial derivative for the preparation of salts of N‐sulfonic acids instead of the nitro oligomers used now from elastomers. The salts can be used in galvanic coating techniques as brighteners. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1002–1013, 2005     

超交联多孔离子聚合物的研究进展

超交联多孔离子聚合物（hyper-crosslinked porous ionic polymers，HCPiPs）是一类兼具多孔结构、大比表面积、高电荷密度的新型离子有机功能材料，具有制备方式多样、条件温和、易于功能化等特点，在气体捕集/存储、分离、催化、能源环境等方面取得了显著成绩。本文综述了HCPiPs的基本合成原理和方法，系统总结了含离子单体的一步交联法、交联-离子化同步合成法、后修饰法3种制备HCPiPs常用方法的优缺点，以及近年来在气体捕集与分离、异相催化、能量存储与转化、污染物吸附分离等领域的研究进展，并对今后的发展进行了展望，指出了加强HCPiPs的孔结构和活性位点的设计及调控、解决HCPiPs的功能离子的含量与比表面积相互矛盾的问题以及制备各种新型功能性HCPiPs以不断拓展其在催化和电池等领域的应用三个主要研究方向。     

β‐Aryl Nitrile Construction via Palladium‐Catalyzed Decarboxylative Benzylation of α‐Cyano Aliphatic Carboxylate Salts

The palladium‐catalyzed decarboxylative benzylation of α‐cyano aliphatic carboxylate salts with benzyl electrophiles was discovered. This reaction exhibits good functional group compatibility and proceeds under relatively mild conditions. A diverse range of quaternary, tertiary and secondary β‐aryl nitriles can be conveniently prepared by this method.     

Cooperative Catalysis: A New Development in Heterogeneous Catalysis

Whereas cooperative effect in catalysis, in which multiple chemical interactions participate cooperatively to achieve significant enhancement in catalytic activity and/or selectivity, is common in enzymatic reactions, it has been sparingly employed in heterogeneous catalytic systems. Here, some recent literature examples of abiotic catalysis, with emphasis on heterogeneous systems, that employ cooperation between acid and base and two metal centers are briefly described to demonstrate the principles involved. Since effective cooperation places strict demand on the positions of the different functional groups, new synthetic methods and strategies are needed to design and construct structures useful for cooperative catalysis. Recent progress in our laboratory in synthesizing new nanocage structures that possess molecular-size cavities, atomic layer thick, porous shells with internal functional groups is described. These recent developments suggest possibilities of new catalytic transformations that have not been attempted before. This is illustrated with two speculative examples utilizing cooperative catalysis: oxidative hydrolytic desulfurization and terminal carbon activation of hydrocarbon molecules.     

An overview of some reactions of thianthrene cation radical. Products and mechanisms of their formation

A comprehensive review of recent chemistry of thianthrene cation radical is presented. Particularly, products and mechanisms of their formation from reactions with azo compounds, hydrazones, oximes, sulfonamides, alcohols, phenols, alkenes, alkynes and organometallics are discussed. Also, reactions of 5-(substituted)thianthrenium salts are reviewed.     

Micellar-improved synthesis of bis-quaternary ammonium salts by the epichlorohydrin route

A convenient procedure for the synthesis of bis-quaternary ammonium salts from long-chain alkyldimethylamines and epichlorohydrin is studied. An improved preparation of bis-quaternary ammonium salts from N,N-dimethyloctylamine, N,N-dimethyldodecylamine or N,N-dimethyloleylamine, their amine hydrochlorides, and epichlorohydrin can be achieved by carrying out the reaction in an aqueous micellar medium. The amine hydrochlorides are used as functional surfactants to produce the self-micellization and solubilization of reactants. The formation of micelles is a necessary condition for a successful quaternization. Comparison of the quaternization performance in ethanol, ethanol/water mixtures, and aqueous micellar medium leads to the conclusion that this micellar-improved synthesis enables easier and cheaper access to bis-quaternary ammonium salts by avoiding the formation of the mono-quaternary ammonium salts as intermediates, and by using water as solvent under mild reaction conditions. Mechanistic aspects of the quaternization reaction in micellized medium are also suggested.     

Iminium Salts in Solid‐State Syntheses Giving 100% Yield

Numerous reaction types in the field of iminium salts are performed in the gas‐solid and solid‐solid techniques in order to reach 100% yield. The stoichiometric runs are waste‐free and do not require costly workup. Frequently, iminium salts were avoided, as acid catalysis was dispensable. Thioureas and α‐halogenated ketones give a variety of 2‐aminothiazoles via thiuronium salts in quantitative yield. A new intramolecular solid‐state thermal condensation is reported. Enaminoketones are synthesized quantitatively from anilines and 1,3‐diketones without catalysis and those can be used for quantitative solid‐state 4‐cascade reactions. Solid paraformaldehyde is used to produce methylene imines and internally trapped methylene iminium salts. Benzoylhydrazones are produced again without catalysis in the solid state. Vacuum and ball‐mill techniques are particularly useful in the production of highly sensitive iminium salts. Hexahydro‐1,3,5‐triazines cyclorevert upon exposure to HCl gas to give solid arylmethylene iminium chlorides as new versatile reagents. These are used in arylaminomethylations of β‐naphthol and of themselves to give Troeger's bases in 3‐cascades. More direct are 4‐cascade Troeger's base syntheses by dissolving hexahydro‐1,3,5‐triaryltriazines in trifluoroacetic acid. Alkylations of imines with trimethyloxonium tetrafluoroborate and triphenylmethyl cation give highly sensitive quaternary iminium salts in the ball‐mill. The products are characterized by spectroscopic techniques and density functional theory (DFT) calculations at the B3LYP 6‐31G* level. Molecular movements in the crystal and surface passivation are investigated with atomic force microscopy (AFM) techniques.     

含磷多孔有机聚合物的合成及其在多相催化中的应用

含磷多孔有机聚合物不仅具有发达的孔隙和表面结构,还具有很强的可调变性和可修饰性,在多相催化中有着广泛的应用前景。目前还没有概述含磷多孔有机聚合物的制备及其在多相催化中应用的综述,本文对该领域近十年来的研究进展进行了归纳和梳理。指出含磷多孔有机聚合物的合成方法发展十分迅速,包括偶联缩聚、锂盐参与的缩聚、Friedel-Crafts缩聚、溶剂热烯烃聚合、Scholl缩聚、酚醛聚合、醛胺缩合、聚吡喃盐的磷代以及多段式聚合等。基于其骨架中含有大量膦配体,含磷多孔有机聚合物能负载一系列金属化合物制成负载型金属纳米颗粒催化剂,甚至单原子或单位点金属催化剂。表明聚合物基催化剂中,膦配体不仅能诱导金属在聚合物中均匀分布,并且在调控金属的表面电子性质和位阻性质等方面发挥重要作用,进而对催化剂的活性和选择性产生影响。