超临界流体色谱用的固定相

正申请公布号:CN 107430100A申请公布日:2017.12.01申请人:株式会社大赛璐摘要本发明的课题在于提供具有良好的分子识别能力、特别是不仅对于酸性化合物或碱性化合物而且对于稠环芳族化合物或芳族异构体也具有良好的分离特性的超临界流体     

含苯并呋喃、苯并噻吩环的聚苯基-1,2,4-三嗪

本文首次合成了几种含苯并呋喃苯并噻吩环的新的芳香族四羰基化合物,并对它们进行了元素分析和红外光谱测定。将所合成的芳族四羰基化合物分别与芳族双酰胺腙反应,得到了一系列含氧、硫杂原子的新的聚苯基-1,2,4-三嗪。这些高聚物均可以浇铸成膜。对聚合物所进行的一般性能测试的结果表明,它们具有良好的力学性能和较好的耐温性。     

含磷全芳族热致液晶共聚酯的合成及热性能

全芳族热致液晶聚酯因其优良的力学性能、热稳定性及较低的熔融粘度而倍受关注 ,是当今最有前途的特种高分子材料之一 .但是 ,全芳族聚酯的刚性结构使其熔点较高 ,难以加工 ,因而通过分子设计制备熔点较低的热致全芳香族聚酯液晶成为研究的热点 .在主链型热致液晶高分子的分子设计中 ,通常采用共聚或在高分子链中引入取代基、柔性链段、扭结成分等方法来达到降低聚合物相转变温度的目的[1～ 6 ] .本文以对羟基苯甲酸、对苯二甲酸、间苯二甲酸和含磷二元酚化合物为单体 ,合成了一类具有较低熔点或流动温度的新型全芳族热致共聚酯液晶 ,其分子…     

聚四苯基卟啉及其金属配合物的XPS研究

用XPS 研守了聚四苯基卟啉及其18 种金属化合物, 证实了这些金属化合物为金属配合物. 由π→π* 激发能, 跃迁几率和N18 位移证明这些金属化合物是金属离子镶嵌在芳族大π体系共轭环中而成的金属配合物. 初步表明这些金属配合物的稳定性金属原子半径的增大而降低.     

直接合成吲哚的简单方法

硝基芳族化合物在金属催化反应中可以被炔还原为吲哚 ,反应经过Ｎ—中心还原、Ｃ—Ｈ活化和Ｃ—Ｎ与Ｃ—Ｃ键的形成等过程 ,收率中等。　　研究者曾发现 ,亚硝基芳族化合物也能与炔的衍生物反应生成吲哚 ,所以认为在上述的催化还原环化反应中 ,亚硝基化合物可能是反应的中间体。这个反应具有立体选择性 ,选择性地生成 3 位取代的吲哚 ,取代基来自炔基上的基团。　　研究者目前正在致力于探索该反应的范围和机制 ,并计划用于合成某些具有生物活性的吲哚类化合物。ＮＯ2+ＲＲ′ＲＲ′ＮＨ直接合成吲哚的简单方法@宋琦     

热致性液晶聚合物芳族聚甲亚胺的研究

本文介绍了几种具有中介相结构及非中介相结构的双-甲亚胺的模型化合物及三种芳族聚亚胺的合成。研完了分子链的柔性、分子结构和共轭度对中介相转变温度的影响。     

稳定而且有选择性的氟化剂

Clemson大学化学教授D.D.DesMarteau和他的助手们合成了一系列N-氟代全氟烷基磺酰亚胺。这是一种可用来直接取代芳族化合物中的氢原子的新型氟化剂。虽然合成此试剂时要用纯氟,因而要求操作者有良好     

Kishner-Wolff改良法——Ⅹ.邻芳族羟基羰基化合物的还原

研究了邻芳族羟基羰基化合物的Kishner-Wolff改良法还原,并讨论了它们的反应机制.萘酚系羰基化合物5与6中的R为H或C₆H₅(5a、6a、6b)时,还原后得高得率的正常还原物;如R为C₆H₅CH₂,C₆H₆CH₂CH₂(5b、5c、6c),则除得正常还原物外,还得含氮环化物;如R为CH₃、CH₃CH₂、CH₃CH₂CH₂、(CH₃)₂CH(5d～g),则同时得正常还原物及含氮环化物,增加R中碳原子数,似乎使正常还原物减少,而含氮环化物增加.当R为CH₃(CH₂)₆(5h),则仅得含氮环化物.苯酚系羰基化合物7中的R为烷烃基或芳族基时,均得高得率的正常还原物.     

模化城市生活垃圾衍生燃料制备及热解特性的研究

为保证城市固体废弃物（MSW）或垃圾衍生燃料（RDF）研究过程中所用样品的典型性和可重复性,首先根据我国城市生活垃圾的典型组成人工配制了垃圾衍生燃料（aRDF）,分析了aRDF的组成,采用热重 傅立叶变换红外光谱(TG-FTIR)联用技术研究了aRDF的热解特性,并采用差减微商法计算了热解动力学参数。结果表明,aRDF体现了我国MSW构成的主要特点,且与实际焚烧等过程的垃圾原料更为接近;aRDF在低温热解过程中,氯的释放与芳族化合物的产生处于不同的温度区间,并且缓慢的升温速度加大了HCl和芳族化合物释放的温度区间差异。这为避免高温下HCl对设备的腐蚀、减少甚至消除PCDD/Fs的形成提供了可能。aRDF的热解反应为一级反应,其活化能在64.6 kJ/mol～136kJ/mol的范围内变化。     

厌氧性粘合剂

将少量的有机过氧化物加入以式(Ⅰ)表示化合物的多价金属盐和分子中含丙烯酸根或甲基丙烯酸根的化合物的混合物中,必要时加入少量的水或多元醇或胺类,即得厌氧性粘合剂。 CH_2=COOR_2—OOC--COOH (Ⅰ)式中R_1表示氢或甲基,R_2表示卤代、羟代或含醚键的脂族、脂环或芳族多元醇残基。     

Cu(II) 2-quinoxalinol salen catalyzed oxidation of propargylic,benzylic, and allylic alcohols using tert-butyl hydroperoxide in aqueous solutions

The synthesis of carbonyl compounds by oxidation of alcohols is a key reaction in organic synthesis. Such oxidations are typically conducted using catalysts featuring toxic metals and hazardous organic solvents. Considering green and sustainable chemistry, a copper(II) complex of sulfonated 2-quinoxalinol salen (sulfosalqu) has been characterized as an efficient catalyst for the selective oxidation of propargylic, benzylic, and allylic alcohols to the corresponding carbonyl compounds in water when in combination with the oxidant tert-butyl hydroperoxide. The reactions proceed under mild conditions (70 °C in water) to produce yields up to 99% with only 1 mol % of catalyst loading. This reaction constitutes of a rare example of propargylic alcohol oxidation in water, and it makes this process greener by eliminating the use of hazardous organic solvents. Excellent selectivity was achieved with this catalytic protocol for the oxidation of propargylic, benzylic, and allylic alcohols over aliphatic alcohols. The alcohol oxidation is thought to go through a radical pathway.     

Iron‐catalyzed one‐pot oxidation/Knoevenagel condensation reaction using air as an oxidant

A green and highly efficient iron‐catalyzed one‐pot oxidation/Knoevenagel tandem reaction for the synthesis of α, β‐unsaturated nitriles from secondary alcohols and malononitrile has been achieved. The reaction performed under mild conditions with air as an oxidant, and provided the corresponding oxidation/Knoevenagel prudocts in good to excellent yields within short times avoiding the use of noble metal catalysts and bases. Remarkably, water is the only byproduct in this methodology. The reaction could be performed on a gram scale under the standard reaction conditions.     

The Mg-oppenauer oxidation as a mild method for the synthesis of aryl and metallocenyl ketones

Magnesium alkoxides undergo a hydride-transfer oxidation with benzaldehyde as the oxidant. This magnesium variant of the Oppenauer oxidation was used for the synthesis of polyfunctional biaryl ketones. LiCl was found to promote this reaction by enhancing the solubility of magnesium alkoxides. This mild oxidation method was especially useful for preparing ketones bearing a metallocenyl unit as well as various new ferrocenyl ketones and tricarbonylchromium complexes. This last class of ketones was reduced with the CBS catalyst (CBS=Corey-Bakshi-Shibata, diphenyl oxazaborolidine) to chiral benzhydrol complexes with high enantioselectivity enabling an asymmetric synthesis of electron-rich or -poor benzhydryl alcohols (up to 94 % ee).     

Selective aerobic oxidation of hydroxy compounds catalyzed by photoactivated ruthenium-salen complexes (selective catalytic aerobic oxidation)

Selective oxidation of alcohols to the corresponding carbonyl compounds is one of the most fundamental reactions in organic synthesis. Traditional methods for this transformation generally rely on stoichiometric amount of oxidants represented by Cr(VI) or DMSO reagents, though their synthetic utility is encumbered by unpleasant waste materials. From ecological and atom-economic viewpoints, catalytic aerobic oxidation is much more advantageous because molecular oxygen is ubiquitous and the byproduct is basically non-toxic water or hydrogen peroxide. On the other hand, phenol derivatives undergo oxidative coupling, forming C-C or C-O bond, through radical intermediates coupled with an electron-transfer process. Molecular oxygen is also well known to serve as electron acceptor in this reaction. Thus, a variety of transition metal complexes have so far been examined for aerobic oxidations of alcohols and phenols, and high catalytic activities have been achieved in some cases. However, stereo- and chemo-selective aerobic oxidations are still limited in number and are of current interest. Presented in this paper is our recent studies on catalytic aerobic oxidations with photoactivated nitrosyl ruthenium-salen complexes, including asymmetric oxidation of secondary alcohols to ketones (kinetic resolution), enantioselective oxidative coupling of 2-naphthols to binaphthols and oxygen-radical bicyclization of 2,2'-dihydroxystilbene, chemoselective oxidation of primary alcohols to aldehydes and diols to lactols, and asymmetric desymmetrization of meso-diols to lactols.     

Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds

The direct oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has often posed serious challenges in organic synthesis and has constrained chemists to adopting an indirect route, such as a protection/deprotection strategy, to attain their goal. Described herein is a highly chemoselective aerobic oxidation of unprotected amino alcohols to their amino carbonyl compounds in which 2‐azaadamantane N‐oxyl (AZADO)/copper catalysis is used. The catalytic system developed leads to the alcohol‐selective oxidation of various unprotected amino alcohols, carrying a primary, secondary, or tertiary amino group, in good to high yield at ambient temperature with exposure to air, thus offering flexibility in the synthesis of nitrogen‐containing compounds.     

Synthesis and characterization of a Ni nanoparticle stabilized on Ionic liquid‐functionalized magnetic Silica nanoparticles for tandem oxidative reaction of primary alcohols

In this research, preparation of the magnetic nanoparticle, coating by a silica shell using (3‐aminopropyl) triethoxysilane and synthesis of a novel sulfonic acid‐substituted imidazolium‐based ionic liquid onto the surface of these particles via a multi‐component reaction, is described. The functionalized nanoparticles was loaded by Ni nanoparticles and characterized by means of techniques such as XRD, FTIR, SEM, EDX, TEM, TGA and ICP‐OES. The nanostructures have spherical shapes that ranged in size from 80 to 100 nm. The catalytic activity of these nanoparticles was tested in aerobic oxidation of primary alcohols that showed good performance in the wide range of primary alcohols in water at mild reaction conditions. As a second step of this work, the tandem oxidative synthesis of alkylacrylonitriles and bisindolylmethanes were investigated using primary alcohols under oxidation conditions. This catalyst system can be recovered using external magnet and reused for five consecutive cycles without significantly less of its activity.     

Synthesis of homoallylic chiral tertiary alcohols via chelation-controlled diastereoselective nucleophilic addition on alpha-alkoxyketones: application for the synthesis of the C(1)-C(11) subunit of 8-epi-fostriecin

[reaction: see text] Chiral beta-syn-alkoxyhomoallylic alcohols derived from alkoxyallylboration of aldehydes upon oxidation provided the corresponding chiral ketones. Chelation-controlled nucleophilic addition to these ketones occurred in a highly stereoselective manner to afford anti-homoallylic tertiary alcohols. This methodology has been applied for the synthesis of the C(1)-C(11) subunit of C(8)-epi-fostriecin.     

Synthesis of Quinolines via a Metal‐Catalyzed Dehydrogenative N‐Heterocyclization

Efficient ruthenium‐, rhodium‐, palladium‐, copper‐ and iridium‐catalysed methodologies have been recently developed for the synthesis of quinolines by the reaction of 2‐aminobenzyl alcohols with carbonyl compounds (aldehydes and ketones) or the related alcohols. The reaction is assumed to proceed via a sequence involving initial metal‐catalysed oxidation of 2‐aminobenzyl alcohols to the related 2‐aminobenzaldehydes, followed by cross aldol reaction with a carbonyl compound under basic conditions to afford α,β‐unsaturated carbonyl compounds. These aldehydes or ketones can be also generated in situ via dehydrogenation of the related primary and secondary alcohols. In the final step cyclodehydration of the α,β‐unsaturated carbonyl compound intermediates gives quinolines. Good yields of quinolines were also obtained by reacting 2‐nitrobenzyl alcohols and secondary alcohols in the presence of a ruthenium catalyst. Finally, aniline derivatives afforded also a useful access to quinolines by the reaction with 1,3‐propanediol or 3‐amino‐1‐propanol, or in a three‐component reaction with benzyl alcohol and aliphatic alcohols.     

A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols

Selective oxidation of higher alcohols using heterogeneous catalysts is an important reaction in the synthesis of fine chemicals with added value. Though the process for primary alcohol oxidation is industrially established, there is still a lack of fundamental understanding considering the complexity of the catalysts and their dynamics under reaction conditions, especially when higher alcohols and liquid-phase reaction media are involved. Additionally, new materials should be developed offering higher activity, selectivity, and stability. This can be achieved by unraveling the structure–performance correlations of these catalysts under reaction conditions. In this regard, researchers are encouraged to develop more advanced characterization techniques to address the complex interplay between the solid surface, the dissolved reactants, and the solvent. In this mini-review, we report some of the most important approaches taken in the field and give a perspective on how to tackle the complex challenges for different approaches in alcohol oxidation while providing insight into the remaining challenges.     

非过渡金属催化体系NHPI/DDQ/NaNO2催化分子氧选择氧化醇

考察了N-羟基邻苯二甲酰亚胺(NHPI),2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)与NaNO2组成的非金属催化体系,催化分子氧选择氧化醇的反应性能.结果表明,该体系可有效地催化芳香醇等生成相应的醛(酮).在80℃反应6h,苯甲醇转化率达到65%,苯甲醛选择性为99%.此外,该催化体系也能有效地催化其它醇的选...