树脂法分离纯化邻硝基苯甲醛

本文报道树脂法从混合物中分离纯化邻硝基苯甲醛的方法。研究说明，通过伯胺树脂与醛的反应对邻硝基苯甲醛进行化学吸附，可以将邻硝基苯甲醛从含有邻硝基甲苯、邻硝基苯甲醛、邻硝基溴苄、邻硝基－α，α─二溴苄、以及邻硝基苄醇的混合物中有效地分离出来。     

锇-聚乙烯吡啶复合物与辣根过氧化物酶分子多层膜的制备及电化学性质研究

基于分子间静电相互作用力,将锇-聚乙烯吡啶复合物(PVP-Os)与辣根过氧化物酶(HRP)交替沉积于固体基质表面,制得了包含生物成分的分子多层膜.膜层间的聚合物分子起到了粘接与导电的双重作用.用紫外-可见光谱法跟踪了石英基片上的组装过程,研究了多层膜电极对过氧化氢的电催化还原性能,并描述了多层膜电化学行为.     

利用层层自组装技术制备聚电解质多层膜高效液相色谱固定相

以聚(乙烯-alt-马来酸)的苯乙胺衍生物与聚烯丙基胺盐酸盐为原料,通过层层自组装技术(LBL)在色谱硅胶表面交替沉积得到聚电解质多层膜高效液相色谱(HPLC)固定相;利用紫外光谱、红外光谱和元素分析研究了HPLC固定相的结构和组成.结果表明,聚电解质多层膜HPLC固定相被成功构筑在硅胶颗粒表面;制备的多层膜固定相可方便地用于6种芳香烃类及4种烷基苯类物质的分离分析.本文的研究结果说明LBL技术在制备HPLC固定相方面具有一定的应用价值.     

2-硝基-5-(N-甲基-N-十八烷基)氨基苯甲酸多层膜的制备和性质

用2-硝基-5-(N-甲基-N-十八烷基)氨基苯甲酸(NMOB)和花生酸制备了200层的交替多层膜,测得其二次谐波信号强度与NMOB层数的平方成正比.论文着重讨论了NMOB的Y型膜和它与花生酸的交替膜中的取向,并对两者之间的不同作了初步的解释.     

层层静电自组装构筑壳聚糖/磷钨酸复合膜的研究

将正电荷的壳聚糖与负电荷的磷钨酸溶液通过静电作用交替沉积在基底上组装复合多层膜。使用紫外可见光谱(UV-Vis)、红外光谱(FTIR)、X-射线光电子能谱(XPS)、原子力显微镜(AFM)和循环伏安法(CV)等手段对复合膜进行了表征。UV-Vis结果显示多层膜在特征吸收峰处的吸光度数值随膜双层数增加逐渐增大，呈良好的线性关系，表明多层膜是均匀组装的；XPS和FTIR结果证实了壳聚糖和磷钨酸被组装到膜上，AFM图形显示膜表面有一定的粗糙度，CV结果说明多层膜保留了磷钨酸的电化学性质。     

表面印迹交替层状组装薄膜

在简要概述非常规交替层状组装这一进展后,重点总结了如何利用非常规交替层状组装以实现表面印迹膜的制备.模板分子与聚电解质在溶液中组装形成超分子复合物,然后以此超分子复合物为构筑基元,与感光性高分子,如重氮树脂,通过常规交替层状组装形成聚合物多层膜.利用聚合物多层膜之间的光化学反应形成稳定的多层膜,然后去除模板分子得到分子...     

2-硝基-5-(N-甲基-N-十八烷基)氨基苯甲酸多层膜的制备和性质

用2-硝基-5-(N-甲基-N-十八烷基)氨基苯甲酸(NMOB)和花生酸制备了200层的交替多层膜, 测得其二次谐波信号强度与NMOB层数的平方成正比。论文着重讨论了NMOB的Y型膜和它与花生酸的交替膜中的取向, 并对两者之间的不同作了初步的解释。     

纳米尺度氧化石墨烯层作为高效碳催化剂用于苄醇与芳香醛的绿色氧化

合成了纳米尺度氧化石墨烯(NGO)层,用作碳催化剂高效催化苄醇与芳香醛的氧化反应.对于醇氧化反应,当80℃时H2O2存在下,NGOs(20 wt％)可高效催化醇选择性生成醛,其反应速率和产率取决于醇上取代基的性质.对于4-硝基苄醇,反应24 h后,只有10％可转换为相应羧酸.相反,4-甲氧基苄醇和二苯基甲醇分别反应仅9和3h则可完全转化为对应的羧酸和酮.NGO碳催化剂上芳香醛氧化速率高于醇氧化速率.对于所有的醛,采用7 wt％ NGO作催化剂,在70℃反应2-3 h后,就可完全转化为相应羧酸.我们讨论了NGO催化剂结构对苄醇和芳香醛氧化反应影响的可能机理.     

纳米尺度氧化石墨烯层作为高效碳催化剂用于苄醇与芳香醛的绿色氧化（英文）

合成了纳米尺度氧化石墨烯(NGO)层,用作碳催化剂高效催化苄醇与芳香醛的氧化反应.对于醇氧化反应,当80℃时H_2O_2存在下,NGOs(20 wt%)可高效催化醇选择性生成醛,其反应速率和产率取决于醇上取代基的性质.对于4-硝基苄醇,反应24 h后,只有10%可转换为相应羧酸.相反,4-甲氧基苄醇和二苯基甲醇分别反应仅9和3h则可完全转化为对应的羧酸和酮.NGO碳催化剂上芳香醛氧化速率高于醇氧化速率.对于所有的醛,采用7 wt%NGO作催化剂,在70℃反应2-3h后,就可完全转化为相应羧酸.我们讨论了NGO催化剂结构对苄醇和芳香醛氧化反应影响的可能机理.     

氯霉素相似化合物的合成——Ⅳ.3-(邻羥基-对硝基苯基)-2-二氯乙酰氨基-丙醇

本文叙述自邻乙酰氧基-对硝基溴化苄(Ⅶ)或邻甲氧基-对硝基溴化苄开始合成氯霉素的相似化合物——3-(邻羟基-对硝基苯基)-2-二氯乙酰氨基-丙醇(V)及其有关化合物。化合物V对金色葡萄球菌及大肠杆菌均无明显的抑制作用。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.