溶剂法由羧酸直接合成腈

报道了芳羧酸在氨基磺酸存在下 ,在溶剂中同尿素反应生成芳腈的新的合成方法 ,并同熔融法的实验结果进行了对比。结果表明 ,溶剂法的产率高 ,反应条件温和 ,易于工业化。     

无催化剂微波促进下C-N交叉偶联反应研究

文章研究内容的是在无金属催化剂的条件下,利用微波加热促进C-N交叉偶联反应。实验发现以DMSO为溶剂,t-BuOK为碱,利用微波加热,活化的氯代芳烃能与各类亲核试剂顺利反应,得到中等及优良的产率。     

Selective access to novel aryl alkyl disulfonates via photosulfochlorination process: An eco-benign approach to a highly active class of surfactants

In this work we report the synthesis of a new family of surfactants based on aryl alkyl disulfonates; the latter compounds were derived from a mixture of linear alkylbenzene with the resulting disulfonate groups residing on the linear alkyl side-chain rather than the usual aromatic ring structure. The Reed sulfochlorination reaction was successfully utilized to selectively promote the formation of disulfonates on the alkyl group. A number of analytical methods in the form of liquid chromatography–mass spectrometry (LC–MS), gas chromatography–mass spectrometry (GC–MS), Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) were used to characterize the resulting compounds and intermediates. The critical micelle concentration, the surface tension at the critical micelle concentration, the surface excess concentration at surface tension, and the area per molecule were measured at different concentrations and temperatures. Thermodynamic parameters and Krafft temperature were also determined. The obtained results were compared to those of commercial n-dodecylbenzene sulfonates and linear alkylbenzene sulfonates surfactants, showing that these new synthesized surfactants present good surface properties.     

Iodination of stable aromatic diazonium salt using crosslinked poly (4‐vinylpyridine)‐supported iodide

In this article, a series of carboxylated acrylate copolymer latices were prepared based on the semicontinuous emulsion polymerization via the pure monomer dropwise manner with three different kinds of carboxylic monomers in presence of reactive emulsifier. The effects of the carboxylic monomers [acrylic acid, methacrylic acid, and monobutyl itaconate (MBI)] on the conversion and the properties of acrylate latices and films have been investigated. The carboxylic groups ( COOH) distribution of these three kinds of latices were investigated as well. The results show that the concentration of surface  COOH (C_S) and embedded  COOH (C_b) both increase with the increase of the amount of carboxylic monomers. It shows that MBI, the most hydrophobic of the three carboxylic monomers used, tends to be concentrated inside the particle core, and the latex particles have a narrow size distribution. The results of common stability test have demonstrated that the stability of the latex is satisfactory. Moreover, the water absorption and the acid and alkaline resistance of the latex depend on the kind of carboxylic monomer. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

铑（I）催化芳基三氟硼酸钾与芳基羧酸酐偶联反应的研究

考察了铑（I）催化芳基三氟硼酸钾与芳基羧酸酐生成芳酮的偶联反应。结果表明,低剂量[1．0％（mol]的RhCl（PPh3）3在催化芳基三氟硼酸钾与芳基羧酸酐的偶联反应方面表现出非常高的催化活性。不论是供电子基团还是吸电子基团取代的芳基三氟硼酸钾和芳基羧酸酐都可在较短的反应时间内得到良好的反应产率,但具有空间位阻基团取代的芳基三氟硼酸钾和芳基羧酸酐反应的产率较低。     

A Highly Practical and Reliable Nickel Catalyst for Suzuki–Miyaura Coupling of Aryl Halides

We disclose that [1,3‐bis(diphenylphosphino)methane]nickel(II) chloride [NiCl₂(dppp)] is a highly active, universally applicable, cheap, and stable catalyst for Suzuki–Miyaura cross‐coupling reactions of aryl halides with a catalyst loading of lower than 1 mol%, and more notably, in the absence of extra supporting ligands. Under the optimized reaction conditions, a broad range of aryl bromides as well as the notoriously unreactive aryl chlorides, including activated, non‐activated, deactivated, and heteroaromatic and sterically hindered substrates can be coupled smoothly with various boronic acids (47 examples, 48–98% yields). In addition, the transformation is tolerant of various functional groups such as ether, ester, ketone, aldehyde, cyano, and unprotected amino and hydroxy groups. Finally, the potential utilization of the methodology was further demonstrated by the gram‐scale synthesis of several core structures of commercialized antihypertensive drugs and fungicides. Thus, the combination of high activity, broad applicability, cheapness, and high stability of NiCl₂(dppp) presented in this work constitutes one of the few prominent catalysts which allow for practical and reliable construction of biaryls and heterobiaryls with structural diversity from readily available aryl halides and boronic acids.     

Palladium nanoparticles as reusable catalyst for the synthesis of N-aryl sulfonamides under mild reaction conditions

An efficient palladium nanoparticles-catalyzed N-arylation of sulfonamides and sulfonyl azides is described. This procedure serves as an active protocol for intermolecular C–N bond formation using Pd(OAc)₂ in PEG-400 under air. Aryl bromides and triflates react at 35°C, while aryl chlorides require heating to 50°C and give the desired products only in low yields. This reaction proceeds smoothly in acceptable yields using low catalyst loading.     

取代二芳基甲胺“一锅法”合成研究和改进

由芳基锂盐、硫代甲酰胺和芳基格氏试剂一锅法合成了取代二芳基甲胺。通过将含有吸电子基团的芳香溴代物制成格氏试剂,将含有给电子基团的芳香溴代物制成锂盐,显著提高了取代二芳基甲胺的收率。     

无配体无催化剂下的C-S反应

吡啶与硫酚的偶联反应,该反应以DMSO为溶剂100℃条件下反应24 h,高产率地得到了一系列硫醚衍生物,发展出条件温和,环境友好,实验室操作容易和更为经济性的偶联反应。     

聚芳醚酮化学改性研究进展

介绍了聚芳醚酮的物理化学性质,主要对近年来研究的热点超支化聚醚酮改性、化学改性和磺化改性等进行了综述.     

Rheological properties in blends of poly(aryl ether ether ketone) and liquid crystalline poly(aryl ether ketone)

Rheological properties of the blends of poly(aryl ether ether ketone) (PEEK) with liquid crystalline poly(aryl ether ketone) containing substituted 3‐trifluoromethylbenzene side group (F‐PAEK), prepared by solution precipitation, have been investigated by rheometer. Dynamic rheological behaviors of the blends under the oscillatory shear mode are strongly dependent on blend composition. For PEEK‐rich blends, the systems show flow curves similar to those of the pure PEEK, i.e., dynamic storage modulus G′ is larger than dynamic loss modulus G″, showing the feature of elastic fluid. For F‐PAEK‐rich systems, the rheological behavior of the blends has a resemblance to pure F‐PAEK, i.e., G″ is greater than G′, showing the characteristic of viscous fluid. When the PEEK content is in the range of 50–70%, the blends exhibit an unusual rheological behavior, which is the result of phase inversion between the two components. Moreover, as a whole, the complex viscosity values of the blends are between those of two pure polymers and decrease with increasing F‐PAEK content. However, at 50% weight fraction of PEEK, the viscosity‐composition curves exhibit a local maximum, which may be mainly attributed to the phase separation of two components at such a composition. The changes of G′ and G″ with composition show a trend similar to that of complex viscosity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4040–4044, 2006     

N-芳基-N-异丙基-2-羟基乙酰胺的合成

以 4个不同结构的芳胺为原料 ,经过N 烷基化 ,N 氯乙酰化 ,酯化 ,酯交换反应合成了 4个 2 羟基乙酰胺类化合物 ,它们都是重要的农药中间体。其中N (4 三氟甲基苯基 ) N 异丙基 2 羟基乙酰胺的合成 :控制温度在 10～ 2 0℃ ,向 4 三氟甲基苯胺 ,冰醋酸与丙酮的混合液中慢慢加入硼氢化钾 ,加完后 2 0℃反应 2h得到产品N 异丙基 4 三氟甲基苯胺 ,产率 86 .0 %。升温至40℃ ,向N 异丙基 4 三氟甲基苯胺、甲苯混合液中滴加氯乙酰氯 ,滴完后升温至 75℃ ,通氮气反应 2h得到产品N (4 三氟甲基苯基 ) N 异丙基 2 氯乙酰胺 ,产率 92 .9%。N (4 三氟甲基苯基 ) N 异丙基 2 氯乙酰胺 ,甲醇 ,醋酸钾 ,三乙胺 ,碳酸钾 ,回流反应 17h ,得到产品N (4 三氟甲基苯基 ) N 异丙基 2 羟基乙酰胺 ,产率 88.2 % ,总收率为 70 .5 %。产品结构经质谱和核磁确定     

Alkyl aryl ethers in lignite solubilization. 1. Study of the process

The chemistry of solubilization of a lignite has been investigated with anisole, 3-methyl anisole and 1,3-dimethoxybenzene catalysed by SbCl₃, ZnCl₂, AlCl₃ and BF₃ as boron trifluoride etherate, at atmospheric pressure and temperatures < 220 °C. 60% of lignite was solubilized in a toluene-ethanol azeotropic mixture. During the process, the solvent is incorporated as an alkylated substratum. The yield increased with activity of the aromatic ether ring and catalyst acidity.     

烷基芳基磺酸盐对不同原油油-水界面张力行为的研究

选择了系列表面活性剂烷基芳基磺酸盐中的一个Ay -2 ,合成了Ay -2并考察了其与大庆采油一厂、二厂、三厂、四厂和大港油田港西和羊三木原油的油水界面张力特性。结果表明 :烷基芳基磺酸盐Ay -2与大庆采油四厂原油能形成较好的界面张力范围 ,与采油一厂、二厂、三厂原油形成超低界面张力的能力略差 ;烷基芳基磺酸盐Ay -2能与大港油田羊三木原油和港西原油间形成较好的界面张力范围     

桂皮酰哌啶的合成路线改进

通过改变溶剂的方法合成桂皮酰哌啶,以减轻有毒试剂对环境的污染和对人体的伤害。分别选用苯、甲苯、乙酸乙酯、二氯乙烷作为溶剂合成桂皮酰哌啶,结果表明甲苯作为溶剂时产品纯度高,收率高,可用于大规模生产。     

离子液体中合成芳香磺酸酯

磺酸酯类化合物是重要的有机合成中间体,同时有着很好的药理活性。在离子液体中合成一系列标题化合物,该方法与传统的方法相比,具有反应步骤简单,条件温和,反应时间短,产率高,环境友好等优点。     

芳基异硫氰酸酯的合成与应用

芳基异硫氰酸酯是一类应用极为广泛的有机中间体和重要试剂,用于合成多种含氮、含硫、或含氧等杂环化合物,广泛应用于农药、医药和精细化工等领域。其合成方法及应用受到化学家的广泛重视。文章综述了芳基异硫氰酸酯的多种合成方法及其在化合物合成、医药方面的应用。     

耐高温含氟聚芳醚酮和聚芳醚砜的合成与性能研究

通过三步反应合成新的含氟双酚单体3,4-二氟苯基对苯二酚,由该含氟双酚单体、4-氟苯基对苯二酚、邻苯基对苯二酚分别与4,4′-二氟二苯酮、4,4′-二氯二苯砜经亲核缩聚反应,制备了一系列新型聚芳醚酮和聚芳醚砜。采用 FT-IR、DSC、TGA及XRD手段等对聚合物的结构和性能进行了表征和研究,结果表明：合成的聚芳醚酮和聚芳醚砜具有优异的耐热性能,玻璃化转变温度分别在150~159 ℃和177~196 ℃之间,氮气中5 %热失重温度分别在527 ℃和507 ℃以上。合成的聚芳醚酮和聚芳醚砜具有良好的溶解性,室温下能溶解在N-甲基吡咯烷酮、二甲基乙酰胺、氯仿等有机溶剂中。     

Fluorinated poly(aryl thioether)s and poly(aryl sulfone)s derived from 2,3,4,5,6‐pentafluorobenzoic acid

Poly(aryl thioether)s (F‐PTEs) containing 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety and polar moiety, such as 1,3,4‐ozadiazole, ether ketone, and amide groups, were synthesized by nucleophilic aromatic substitution reaction of aryl fluorides and 4,4′‐thiobisbenzenthiol. F‐PTEs were amorphous with good thermal properties including high glass transition temperature (T_g) and thermal stability, solubility, and hydrophobicity. F‐PTEs were transformed into poly(aryl sulfone)s (F‐PSs) by the oxidation reaction with hydrogen peroxide in acetic acid. Because of the sulfone group, the T_gs of the F‐PSs were 30–40°C higher than those of the corresponding F‐PTEs. F‐PSs maintained solubility in polar aprotic solvents and exhibited hydrophobicity in spite of the content of polar sulfone groups due to the highly substituted fluorine atoms. These F‐PTEs and F‐PSs were a new class of high‐performance polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008