以活性碳纤维为载体的催化剂对NO的催化还原作用：二.镍系催化剂

前文报导了活性碳纤维（ＡＣＦ）载体催化剂Ｃｕ（ＮＯ３）２－ＡＣＦ在较低温度下就可催化ＮＨ３还原ＮＯ成为Ｎ２，但这种催化剂活性在高温时有随时间而明显下降的缺点。为了进一步探索新型高效长寿命催化剂，本工作研究了另一组催化剂体系－镍系ＡＣＦ载体催化剂外ＮＯ的催化还原作用，探讨了催化剂的结构以及各种影响催化效果的因素，实验结果再次表明ＡＣＦ在催化剂中起到活性载体的作用。Ｎｉ（ＮＯ３）２－ＶＡＣＦ催化剂在较高温度时对ＮＯ具有良好催化还原效果，在２５０～４００℃之间，其ＮＯ较化率比相同温度下的Ｎｉ（ＮＯ３）２－ＳｉＯ２对ＮＯ转化率高３０～４０％。Ｎｉ（ＮＯ３）２－ＶＡＣＦ催化剂的催化组分主要是单质镍，它的寿命比Ｃｕ（ＮＯ３）２－ＡＣＦ有明显的改善。催化剂负载量及催化剂用量增加或ＡＣＦ比表面积减少，ＮＯ转化率增加；载气流量及ＮＯ流量增加或ＮＨ３流量减少，ＮＯ转化率降低。     

水滑石焙烧产物Mg（Al）O为载体的Pt催化剂的正己烷临氢反应性能

制备了以水滑石焙烧产物－Ｍｇ－Ａｌ复合氧化物为载体的Ｐｔ催化剂，并考察了它在氢存在下的烃类转化反应性能，表明此类催化剂具有比一般的Ｐｔ／Ａｌ２Ｏ３更好的正己烷脱氢环化和异构化反应活性和选择性，更低的氢解反应活性。分别制备了以Ｈ２ＰｔＣｌ６、Ｐｔ（ＮＨ３）４（ＯＨ）２和Ｐｔ（ＮＨ３）４Ｃｌ２为浸渍剂的催化剂，其中以用Ｐｔ（ＮＨ３）４Ｃｌ２和Ｐｔ（ＮＨ３）４（ＯＨ）２制备的催化剂的脱氢环化反应和异构化     

异丁烷催化脱氢制异丁烯Cr2O3／Al2O3体系催化剂

对异丁烷催化脱氢催化剂进行了研究。助催化剂Ｋ２Ｏ,ＣｕＯ的引入改进了Ｃｒ２Ｏ３／Ａｌ２Ｏ３催化剂的活性和抗积炭性能。同时考察了原料气空速、反应温度以及催化剂制备的焙烧温度对Ｋ２Ｏ－ＣｕＯ－Ｃｒ２Ｏ３／Ａｌ２Ｏ３催化剂反应性能的影响。ＸＲＤ谱图表明,Ｃｒ２Ｏ３在催化剂中高分散,７００℃焙烧的催化剂中出现的ＫＣｕＯ晶相对催化剂活性不利。用ＮＨ３－ＴＰＤ和ＣＯ２－ＴＰＤ检测了催化剂表面的酸碱中心,表明助     

3—巯基—2—丁醇合成方法的改进及其异构体组成的分析鉴定

以丁酮、氨、硫为原料，通过综合反应合成２，４，５－三甲基－２－乙基噻唑淋－△＾３，再经水解、还原共三步反应合成了３－巯基－２－丁醇。考察反应温度、催化剂、时间等因素对反应的影响，确定了优化条件：在３５℃进行缩合反应，以磷酸作为催化剂在３５℃下水解４ｈ，以ＫＢＨ４作为还原剂在２５℃下还原。简化了操作，缩短了反应时间，降低了成本，收率达５４％。通过ＧＣ，ＧＣ－ＭＳ，＾１ＨＮＭＲ等手段确定了产品的组成及     

CuCl催化剂上合成气液相合成甲醇和甲酸甲酯(英文)

在低温和浆态反应条件下,于同一个反应器中考察了由合成气一体化合成甲醇和甲酸甲酯的反应。结果表明,由碱金属醇化物和ＣｕＣｌ组成的混合催化体系具有甲醇合成活性,在比较温和的条件下（３６３～４０３Ｋ, ３～６ ＭＰａ）进行合成反应时,甲醇的空时收率可达到２０８ ｇ·Ｌ~(－１)·ｈ(－１)（３６３ Ｋ, ５．０Ｍｐａ）和４３．８ｇ·Ｌ~（－１）．ｈ~（－１）（添加氢化物助剂）。甲醇的选择性与反应温度有关。一体化合成反应与分步反应有较大差异。反应历程可能为甲醇首先均相催化羰化为甲酸甲酯,然后甲酸甲酯再多相催化氢解为甲醇。     

SO4^2—TiO2—Hβ—Al2O3催化剂的制备及催化性能研究

以Ｈβ沸石为，通过ＴｉＯ２改性及硫酸铵处理制备了ＳＯ４＾２－－ＴｉＯ２－Ｈβ－Ａｌ２Ｏ３催化剂，并由ＸＲＤ、ＸＰＳ、ＮＨ３－ＴＰＤ、ＦＴＩＲ及化学吸附等手段考察了不同焙烧温度对该催化剂表面性质、酸性及催化性能的影响。结果表明；适宜的焙烧温度使ＳＯ４＾２－－ＴｉＯ２－Ｈβ－Ａｌ２Ｏ３的酸量大幅度增加，强酸比例增大，并产生部分增强酸中心，高强度的酸性中心中，以Ｌ酸中心为主；５５０℃焙烧的样品能使沸石表     

新型固体酸催化剂SO42-/Fe2O3-ZrO2-SiO2的研究

研制了新型三元ＷＯ４＾２－／ＦｅｗＯ３－ＺｒＯ２－ＳｉＯ２固体酸催化剂并用于催化剂并用于催化乙酸／丁醇酯化反应;考察了制备方法、Ｆｅ,Ｚｒ摩尔比、Ｓｉ原子百分含量、沉淀ｐＨ值、陈化时间、预焙烧温度、浸渍液Ｈ２ＳＯ４溶液浓度、焙烧温度、焙烧气氛等对催化性能的影响。实验结果表明,使用Ｓｉ含量为２％,ｍｏｌＦｅ：ｍｏｌＺｒ＝０．２５由共沉淀－浸渍法在氧气气氛中制得的该类催化剂,乙酸的转化率、乙酸丁酯收率     

PdCl_2－CuCl_2－PPh_3催化剂立体选择催化烯烃氢酯基化反应

研究了以ＰｄＣｌ２－ＣｕＣｌ２－ＰＰｈ３为催化剂体系，甲基乙基酮、乙二醇二甲醚为溶剂，苯乙烯与一氧化碳及甲醇立体选择生成２－苯基丙酸甲酯的反应．对不同的催化剂前体催化烯烃氢酯基化反应进行了研究，得知ＣｕＣｌ２在此催化反应中起着立体控制作用．同时考察了影响反应的各种因素如溶剂、反应温度、反应压力、不同的膦配体等．实验结果表明，该反应的最佳条件是：反应温度８０℃，反应压力４．０—６．０ＭＰａ，反应时间２４ｈ，最好的溶剂是乙二醇二甲醚及甲基乙基酮．利用该催化剂体系对不同结构的烯烃催化反应进行了研究，发现该体系仅仅对苯乙烯类有较高的立体选择催化活性     

异丁烷-丁烯烷基化反应催化剂的研究

制备了一系列不同焙烧温度的Ｚｒ（ＳＯ４）２及Ｚｒ（ＳＯ４）２负载量不同的Ｚｒ（ＳＯ４）２／Ａｌ２Ｏ３（ＳｉＯ２）固体强酸催化剂,用ＸＲＤ、ＩＲ、ＢＥＴ、ＴＧ－ＤＴＡ、ＮＨ３－ＴＰＤ、Ｈａｍｍｅｔｔ指示剂等方法研究了该催化体系的晶型、结构、比表面、酸量及酸强度随负载量和焙烧温度的变化规律。将Ｚｒ（ＳＯ４）２负载在Ａｌ２Ｏ３和ＳｉＯ２两种载体上呈现不同的特性。在Ａｌ２Ｏ３上明显地延缓了Ｚｒ（ＳＯ４）２     

以活性碳纤维为载体的催化剂对NO的催化还原作用 三、铜-钴复合催化剂

采用多种催化剂组份复合往往可以弥补单一组份催化剂存在的某些不足之处。本工作在铜系和镍系ＡＣＦ催化剂研究的基础上，进一步研究了铜－钴复合型ＡＣＦ催化剂对ＮＯ的催化还原作用，系统研究了复合催化剂的制备方法、反应条件等对催化剂活性的影响，并采用各种仪器分析方法研究复合型催化剂的结构以及与催化活性的关系。实验结果表明，Ｃｕ（ＮＯ３）２－Ｃｏ（ＮＯ３）２－ＡＣＦ复合催化剂两种组份有协同效应，它比单组份催化剂不仅具有更高的催化还原ＮＯ活性，ＮＯ转化率可高达９４％，而且温度适应范围广，催化剂寿命长。以５０：５０（Ｃｕ（ＮＯ３）２：Ｃｏ（ＮＯ３）２）混合溶液浸渍后热处理获得的催化剂具有最佳的催化效果。催化剂活性组份主要为单质铜和Ｃｏ。并观察了催化剂负载量、催化剂用量、载气流量、ＮＯ及ＮＨ３流量等对ＮＯ转化率有影响。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.