准气相反应法中煅烧温度对ZrO2微球结构特性的影响

采用新颖的准气相反应法,合成出了球形度好、表面光滑的ZrO2微球.通过对产物的SEM,TEM和XRD表征,研究了煅烧温度对ZrO2球结构特性的影响.结果表明经600～800℃煅烧后,生长完好的ZrO2球,其显微结构为均匀多孔结构,纳米晶粒呈花生样的长条形状;ZrO2球的相由主要的立方相和少量的四方相组成.     

ZrO2中空微球的模板法制备及吸附性能研究

以油菜花粉为生物模板,通过温和易控的水浴-陈化法制备了纳/微米结构ZrO2中空微球.利用扫描电子显微镜(SEM)、红外光谱(FTIR)、X射线能谱(EDS)、X射线衍射(XRD)、比表面孔隙度分析、热分析等对所制备的产物和前驱体进行了表征,并对产物的吸附性能进行了初步的研究.结果表明,ZrO2中空微球的球壳由纳米粒子构筑并形成介孔结构.花粉模板前处理方式不同,其模板作用不同,可以获得两种不同球壳厚度、表面形貌和比表面积的ZrO2中空微球.其中"镂空"结构的ZrO2微球对铬黑T有良好的吸附性能.对ZrO2中空结构形成的机理进行了分析和讨论.     

Template Synthesis and Adsorption of Hollow Zr02 Microspheres

以油菜花粉为生物模板,通过温和易控的水浴-陈化法制备了纳/微米结构ZrO2中空微球.利用扫描电子显微镜（SEM）、红外光谱（FTIR）、X射线能谱（EDS）、X射线衍射（XRD）、比表面孔隙度分析、热分析等对所制备的产物和前驱体进行了表征,并对产物的吸附性能进行了初步的研究.结果表明,ZrO2中空微球的球壳由纳米粒子构筑并形成介孔结构.花粉模板前处理方式不同,其模板作用不同,可以获得两种不同球壳厚度、表面形貌和比表面积的ZrO2中空微球.其中＂镂空＂结构的ZrO2微球对铬黑T有良好的吸附性能.对ZrO2中空结构形成的机理进行了分析和讨论.     

Au/ZrO2催化CO氧化反应中ZrO2纳米粒子的尺寸效应

从同一ZrO(OH)2出发制备了三种不同尺寸的ZrO2纳米颗粒(ZrO2-CP：40-200nm,ZrO2-AN;18～25nm,ZrO2-AD：10～15nm),采用沉积-沉淀方法制备了相应的Au/ZrO2催化剂,用XRD,XRF,TEM和低温N2吸附对ZrO2和Au/ZrO2进行了表征．XRD和TEM分析表明Au/ZrO2样品中Au粒子的平均尺寸为4～5nm,而Zr02的晶相和颗粒大小没有因为“负载”Au粒子而发生变化．CO催化氧化反应的结果表明,Au／ZrO2催化活性随着ZrO2纳米粒子尺寸的减小活性明显增加．TEM／HRTEM结果表明,Au／ZrO2催化剂中Au粒子与ZrO2颗粒接触界面随ZrO2颗粒尺寸的减小而明显增加,这很可能是含有更小尺寸ZrO2纳米粒子的Au／ZrO2催化剂具有更高催化活性的重要原因。     

固体超强酸S2O8^2-／ZrO2-CeO2催化剂的结构与性能表征

用共沉淀法制备了固体超强酸S2O8^2-／ZrO2-CeO2催化剂,通过XRD,FTIR,BET,TEM,DSC／TG等分析手段对其结构进行了表征,并考察了其对乳酸丁酯合成反应的催化活性。结果表明．Ce的引入可以有效地抑制ZrO2晶粒由四方相向单斜晶相转变和催化剂表面含硫物种的流失;当焙烧温度高于500℃时,体系内部有四方相Ce0.16Zr0.84O2固溶体形成,最佳焙烧温度为600℃。在n（乳酸）：n（正丁醇）=1．0：3．0,。（S2O8^2-／ZrO2-CeO2）=12．0％,反应温度145℃,反应时间2．0h的条件下,S2O8^2-/ZrO2-CeO2催化剂对乳酸的酯化率达96．6％。     

TiO2和ZrO2担载的钒氧化物对柴油炭黑催化燃烧的原位紫外激光拉曼光谱研究

利用紫外激光拉曼（UV-Raman）光谱表征了担载TiO2或ZrO2表面的钒氧化物催化剂的分子结构,采用原位UV—Raman光谱考察了V4/TiO2和V4/ZrO2催化剂对柴油炭黑催化燃烧的真实反应状态．结果表明：随着反应温度的升高,TiO2发生了从锐钛矿相到金红石相的晶相转移;然而,ZrO2载体没有观察到明显的相转移过程发生．担载钒氧化物的结构也与钒的载量有关,当钒的载量m（m是每100个载体金属离子中所含的钒离子数）等于4时,钒氧化物在TiO2或ZrO2载体上达到了单层饱和分散,此时催化剂的氧化还原能力最强．所以,在TiO2或ZrO2担载的钒氧化物催化剂中,V4／TiO2和V4／ZrO2是各自系列催化剂中对炭黑燃烧活性最高的催化剂．在炭黑的催化燃烧过程中,原位UV—Raman光谱检测到表面含氧络合物（SOC）的形成,而且SOC主要以羧基功能团的形态存在．反应气体中NO的存在能够促进SOC的生成．     

WO3/ZrO2固体强酸催化剂上异丁烷/丁烯的烷基化反应 Ⅱ.过渡金属的助催化作用

 制备了一系列用过渡金属M（M＝Pt,Co,Ni,Mn,Fe,Cu）活化的WO3／ZrO2固体强酸催化剂,用XRD,DTA－TG,H2－TPR,NH3－TPD等测定了其晶型结构、表面状态和酸量．结果表明,各样品中的ZrO2主要以T晶相存在,但T晶相ZrO2所占的比例因过渡金属不同而异,比表面积比WO3／ZrO2稍有下降;金属Pt的引入使呈单层分散的WO3的表面状态发生了改变．研究了异丁烷／丁烯烷基化反应,其反应活性与酸量的测定结果有对应关系;与WO3／ZrO2相比,M－WO3／ZrO2上的丁烯转化率均稍有下降,但具有更高的i－C08选择性．从反应机理分析了添加过渡金属无显著效果的原因．     

制备方法对负载型纳米ZrO2/Al2O3复合载体性能的影响

采用浸渍-沉淀法制备了负载型纳米ZrO2/Al2O3复合载体.采用X射线衍射、N2物理吸附、差示扫描量热(DSC)和程序升温脱附等技术考察了浸渍方式和干燥方法对复合载体的表面性能、热稳定性和晶相结构的影响.结果表明,ZrO2/Al2O3复合载体中没有生成ZrO2-Al2O3复合氧化物或固溶体,纳米ZrO2仅负载在Al2O3的表面.微波干燥法制备的ZrO2/Al2O3复合载体的比表面积(158.7 m2/g)较大,最可几孔径为19.4 nm,ZrO2的粒度为4.2 nm,晶相结构为四方相ZrO2.微波诱导作用使ZrO2/Al2O3复合载体表面产生了新的酸碱中心,微波干燥法制备的ZrO2/Al2O3复合载体具有较强的热稳定性,在873~1 073 K范围内DSC曲线没有出现吸热峰,而其它干燥方法制备的复合载体在903~1 023 K范围内出现了较明显的吸热峰,表明复合载体表面的部分四方相ZrO2转变为单斜相ZrO2(m-ZrO2).对超声波处理过的复合载体进行微波干燥能进一步提高纳米ZrO2与Al2O3之间的相互作用,纳米粒子的粒度(3.4 nm)更小,分布更均匀,但没有改变ZrO2的晶相结构.     

硫酸化剂和制备方法对锆基固体酸催化剂的结构和性能的影响

采用沉淀法制备ZrO2氧化物,用氯磺酸和硫酸对其进行改性制备了Zr基固体酸催化剂,以XRD、BET和NH3-FTIR等手段考察了制备条件对催化剂晶相结构和表面性质的影响,研究了催化剂结构与其对棕榈油酯化反应的催化活性之间的关系.NH3-FTIR表明催化剂表面有B酸和L酸中心的生成.硫酸化剂的种类及其引入顺序都将影响催化剂的晶相结构和孔结构.酸的引入将阻止ZrO2·nH2O在焙烧时直接向单斜相ZrO2转变,氯磺酸将使ZrO2·nH2O转变为四方相ZrO2,而硫酸将导致四方相ZrO2和Zr(SO4)2·5H2O的生成.以氯磺酸改性的四方相和单斜相ZrO2基催化剂均具有很高的催化酯化活性,比硫酸改性的S-Z固体酸催化活性高.CS-ZrO2固体酸催化活性最高,在醇油比6:1、催化剂用量7 wt%、温度338 K和常压下反应2 h,棕榈油的酯化率可达98.9%.     

两种新型反相高效液相色谱填料疏水选择性能的比较

以层接层自组装法制备的TiO2/SiO2和ZrO2/SiO2微球为基质,分别与十八烷基三氯硅烷在甲苯溶液中加热回流36 h 制备了两种碳十八键合固定相。两种固定相的含碳量分别为11.51%和9.62%。对两种固定相的作用机理进行研究,并以9 种芳香类化合物对其色谱性能进行评价。结果表明,两种固定相都是较好的反相固定相,其疏水选择性差异不大,对芳香 性化合物均有较好的选择性,TiO2/SiO2的含碳量略高于ZrO2/SiO2。     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.