镧-钼复合氧化物超细微粒催化剂结构和甲苯选择氧化催化性能

镧－钼复合氧化物超细微粒催化剂结构和甲苯选择氧化催化性能匡文兴范以宁陈开东邱金恒王镇浦＊陈懿（南京大学化学系，南京２１００９３；＊南京化工大学应化系，南京２１０００９）关键词：镧－钼复合氧化物超细微粒结构甲苯选择氧化近年来，有关甲苯选择氧化方面的文献...     

La-Mo系列复合氧化物超细微粒催化剂的制备

在催化研究领域，人们一直在寻找新的高效催化剂，由于超细微粒催化剂具有高比表面和表面能，活性点多，因而其催化活性和选择性大大高于传统催化剂．目前，催化工作者已在超细微粒催化剂的应用和开发方面做了许多有益的工作［’－’］；但是作为烃类选择氧化中研究较多的白钨矿（CaW。）结构的超细微粒催化剂报导甚少＊．文献报导La－Mo二元复合氧化物具有优良的甲苯选择氧化性能问．本工作采用溶胶一凝胶法，制得具有白鹤矿结构的La－Mo二元复合氧化物超细微粒，并初步探讨了制备条件对LaMo二元复合氧化物超细微粒组成、结构、粒子大…     

杂多酸固载催化剂催化氧化合成2,3,5—三甲基苯醌

探索了固载磷－钼－钒杂多酸Ｈ３＋ｎＰＭｏ１２－ｎＯ４ｏ（ＨＰＡ－ｎ，ｎ＝１～３）催化氧化２，３，６－三甲基苯酚合成２，３，５－三甲基苯醌的工艺过程，考察了杂多酸、载体以及搅拌速度对催化氧化反应的影响。     

Co-Ce-O超细微粒催化剂的结构与催化性能

应用ＴＥＭ、ＸＲＤ、ＸＰＳ、ＢＥＴ表面积测试和微型催化反应装置研究了Ｃｏ－Ｃｅ－Ｏ复合氧化物超细微粒催化剂结构及其４－甲基苯酚（ＰＭＰ）选择氧化制４－羟基苯甲醛（ＰＨＢ）的催化性能,结果表明Ｃｏ－Ｃｅ－Ｏ复合氧化物超细微粒催化剂的选择氧化催化活性与催化剂粒子大小、组成和结构密切相关,在Ｃｏ／（Ｃｏ＋Ｃｅ）原子比为０．３３时选择氧化催化活性达极大值,Ｃｏ－Ｃｅ－Ｏ复合氧化物超细微粒催化剂优良的选择氧化催化活性不仅仅是因为其粒子较小、比表面积较大,而且还因为高分散粒催化剂优良的选择氧化催化活性不仅仅是因为其粒子较小、比表面积较大、而且还因为高分散的Ｃｏ、Ｃｅ组份发生了相互作用,催化剂具有较主贩表面吸附态氧物浓度,经高温（〉５００℃）处理,Ｃｏ－Ｃｅ－Ｏ复合氧化物超细微粒发生烧结、比表面积减小且Ｃｏ－Ｃｅ相互作用遭到     

微乳液反应法制备氧化铝（含水）超细微粒

研究了水，辛烷基苯酚聚氧乙烯醚（ＴｒｉｔｏｎＸ－１００），正己醇，环己烷微乳液体系的组成和性质，当正己醇和ＴｒｉｔｏｎＸ－１００的重量比为２：３时，该微乳液体系有较宽且稳定的微乳液相区，是一种制备超细微粒的理想反应体系。在该体系，通过氢氧化铝的氨沉淀时了含水氧化铝（α－ＡｌＯＯＨ）超细微粒，粒子的平均直径约为６ｎｍ，有较好的均匀性。加热转化得到的γ－Ａｌ２Ｏ３超细粉的比表面为１５９．２ｍ＾２．ｇ＾     

位阻型钴卟啉的结构及其在催化氧化2,6—二叔丁基苯酚反应中活性的研究

本文报道了在４０℃和０．１ＭＰａ氧气的条件下，以系列带有不同吸电子基团的位阻型钴卟啉作催化剂，研究２，６－二叔丁基苯酚的催经氧化反应，根据实验数据及对反应动力学的研究，提出了该催化氧化反应的机制，结果表明，钴卟啉催化氧化２，６－二叔丁基苯酚的反应符合酶的催化反应机制，催化剂的催化活性随着取代基团的吸电子效应和位阻效 增加而降低，即：ＴＰＰＣｏ（Ⅱ）〉ＴＰ－ＣＩＰＰＣｏ（Ⅱ）〉Ｔｏ－ＣＩＰＰＣｏ（Ⅱ     

2,3,6-三甲基苯醌的合成(英)

由 ２，３，６三甲基苯酚催化氧化合成了 ２， ３，６三甲基苯醌，确定了最佳工艺条件，使产率达到了 ８８．１％ 。     

Co－B非晶态合金超细微粒催化剂的研究

Ｃｏ－Ｂ非晶态合金超细微粒催化剂的研究姚凯文，范以宁，陈懿，李新生（南京大学化学系，南京２１００９３；中国科学院大连化学物理研究所催化基础国家重点实验室，大连１１６０２３）关键词非晶态，超细微粒，钴基合金，硼合金，一氧化碳，加氢非晶态合金超细微粒兼有...     

纳米钙钛矿型复合氧化物La_(1-x)Sr_xFeO_(3-λ)晶格氧与催化甲烷完全氧化性能研究

纳米钙钛矿型复合氧化物Ｌａ１－ｘＳｒｘＦｅＯ３－λ晶格氧与催化甲烷完全氧化性能研究１）钟子宜２）陈立刚颜其洁３）傅献彩（南京大学化学系南京２１００９３）关键词钠米氧化物钙钛矿型复合氧化物甲烷完全氧化氧物种我们在前文［１］曾报导纳米钙钛矿型复合氧化物Ｌ...     

化学发光—流动注射—胶束增敏连续测定钴铬研究

基于钴（Ⅱ）和铬（Ⅲ）对鲁米诺－过氧化氢化学发光反应均有催化作用，加入ＣＴＭＡＢ能明显提高发光的信噪比，可测定亚纳克量的钴和铬，加入ＥＤＴＡ掩蔽钴（Ⅱ）测得铬（Ⅲ）量，再由钴和铬总量求得钴（Ⅱ）量，实现钴和铬的不经分离而流动注射连续测定。此法线性范围宽达４个数量级（１０－１１～１０－７ｇ／ｍＬ），检测下限低（Ｃｏ２＋１．２×１０－１１ｇ／ｍＬ，Ｃｒ３＋１．０×１０－１１ｇ／ｍＬ），再现性好，工效高（１２０个样品／ｈ），用于三种矿泉水中痕量钴（Ⅱ）、铬（Ⅲ）连续测定，结果良好     

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.