柱撑化合物Zn2Al-PW11Z的结构模型及酯化活性

杂多化合物是性能优异的酸型和氧化型或双功能催化剂[1－4]，而通式为的阴离子粘土通常具有减催化或还原催化性能[5，6]．因此，从在分子及原子水平上设计催化剂，调控催化性能观点出发，人们期望将体积较大的杂多阴离子嵌入阴离子粘土层间，合成大层间距的新型柱撑微孔材料．1988年Pinnavaia等人[7]首次报导了Zn2Al－V10O28是具有2．0nm孔径分布的中微孔材料．最近，笔者将单取代型Keggin结构杂多阴离子GeW11O39Z（H2O）6－（其中Z＝Ni2 和Cu2 ）和缺位Keggin结构的GeW11O嵌入Zn2Al－NO3层间，合成了通道高度为0．9nm的新型柱撑…     

ZnCuCoAlNO_3型四元水滑石及其多氧阴离子柱撑物的合成与催化氧化性能

ＺｎＣｕＣｏＡｌＮＯ３型四元水滑石及其多氧阴离子柱撑物的合成与催化氧化性能郭军＊黄兰芳＊＊矫庆泽张斌蒋大振（吉林大学化学系，长春１３００２３）闵恩泽（石油化工科学研究院，北京１０００８３）关键词：ＺｎＣｕＣｏＡｌＮＯ３四元水滑石杂多阴离子柱撑物合成催...     

过渡金属取代型杂多阴离子柱撑水滑石上环己烯的催化氧化性能

类水滑石及杂多阴离子柱撑水滑石具有可调变的二维孔道结构,活性组分可在较宽的范围内进行调变,从而使其成为有应用前景的氧化催化剂'·'．迄今,以完整结构形态的水滑石为催化剂的催化氧化研究尚未见报道．我们发现［'－'j,含可变价元素的类水滑石和过渡金属取代型杂多阴离子柱撑水滑石具有在较低温度下活化分子氧,从而实现活泼烃类a－H氧化的能力·本文报道了M。AIXW;;ZO。。（M＝Mg'",Zn'";X＝p,St;Z＝Mn2＋,Fe2＋,C。2＋,Ni'",Cll'"）层柱材料上环己烯的催化氧化行为．1实验部分M。AI－XW;;ZO。。系列杂多…     

新型层柱微孔材料—钨镓钴杂多阴离子嵌入阴离子粘土的合成、表征及催化研究

新型层柱微孔材料—钨镓钴杂多阴离子嵌入阴离子粘土的合成、表征及催化研究余新武，张继余，张淑云，王恩波（东北师范大学化学系，长春１３００２４）关键词杂多阴离子，嵌入，层柱化合物，催化活性阴离子粘土又称水滑石（ＬａｙｅｒｅｄＤｏｕｂｌｅＨｙｄｒｏｘｉｄｅ...     

杂多阴离子柱撑水滑石层柱相互作用(Ⅰ)

杂多阴离子柱撑水滑石层柱相互作用（Ⅰ）李兴林＊佘益民郭军蒋大振（中国科学院长春应用化学研究所长春１３００２２）（吉林大学化学系长春）关键词杂多阴离子，柱撑水滑石，ＸＰＳ，ＩＲ，ＸＲＤ１９９６－０６－１８收稿，１９９６－１０－１２修回国家自然科学基金资...     

类水滑石及其杂多阴离子柱撑物的合成与表面酸性研究

合成了一些类水滑石和过渡金属取代型杂多酸盐，并由此制备了相应杂多阴离子柱撑水滑石层柱材料。用ＸＲＤ，ＩＲ和元素分析等手段对合成产物进行组成和结构表征，用ＮＨ３－ＴＰＤ，Ｐｙ－ＩＲ研究了合成产物的表面酸性和酸类型，并在异丙醇反应中考察了合成物的酸碱催化行为，结果表明，水滑石和柱撑水滑石均同时存在酸碱中心，且酸碱相对强度与柱阴离子类型密切相关。杂多阴离子进入水滑石层，同时改变了水滑石和杂多酸盐的酸强度     

新型层柱材料Zn2Al-SiW9M3的合成、表征及催化性能研究

杂多阴离子柱撑粘土是一类新型层柱催化材料.本文采用水热合成与离子交换方法首次将三取代Keggin结构杂多阴离子α-[SiW9O37M3(H2O)3]n-(简写为SiW9M3,M＝Mn2+,Cr3+,Ti3+,Fe3+)嵌入到Zn-Al型阴离子粘土层间,并通过XRD、IR、DTA和元素分析等手段对其结构进行了表征,考察了它们在顺丁烯二酸环氧化反应中的催化活性.     

FePVAsMo杂多化合物膜催化低碳醇选择氧化反应的研究

用组合法合成HxFe01.7P1.1V1.1As0.44-1.1Mo2Oy杂多化合物，并将其以浸渍法负载于多孔钛片上制成催化剂膜，在自制膜式反应釜中选择性催化氧化低碳醇，探讨了As,Fe含量及不同膜焙烧温度对催化剂催化性能的影响；用TPR，IR，TG－DTA对杂多化合物进行表征。结果表明，Fe的引入，可大大提高催化剂的活性和反应的选择性；As的引入，使催化剂的氧化脱氢能力大幅提高；膜焙烧温度为400℃时，催化剂的活性，选择性与稳定性最佳。组成为HxFe0.84P1.1V1.1As0.75Mo12Oy的杂多化合物膜催化剂对低碳醇具有良好的催化氧化活性，稳定性及再生能力。在适宜的条件下催化乙醇氧化，乙醛收率可达95．2％，对丙醇，丁醇也有良好的催化活性。     

几种杂多阴离子柱撑水滑石的合成与吸附行为

柱撑水滑石类层柱状阴离子粘土是一类新型层柱材料，由于其二维孔道结构的可调变性及潜在的择形催化性能，已引起人们的重视[1-3]．迄今，人们已合成了包括无机和有机阴离子，同多和杂多阴离子（Polyoxometalates，简称POMs）以及配合物阴离子在内的多种柱撑水滑石，其中同多和     

异丁醛一步氧化制甲基丙烯酸的杂多酸盐催化剂的氧化还原性

异丁醛一步氧化制甲基丙烯酸的杂多酸盐催化剂的氧化还原性＊贾继飞吴通好＊＊于剑锋王国甲杨宏茂姜玉子郑莹光（吉林大学化学系，长春１３００２３）关键词异丁醛，一步氧化，甲基丙烯酸，杂多钼磷酸盐，氧化还原性异丁醛（ＩＢＡＬ）一步氧化制甲基丙烯酸（ＭＡＡ）是最...     

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.