金属络合物制备分子筛负载金属催化剂的CO加氢反应性能

应用Ｙ分子筛吸附Ｆｅ（ＣＯ）５、Ｃｏ（ＣＯ）３ＮＯ和Ｍｏ（ＣＯ）６的温和热分解制备分子筛负载金属催化剂，从分子筛交换阳离子和吸附金属络合物之间的相互作用说明其ＣＯ加氢产物的分布特点。实验结果表明，分子筛内阳离子和吸附金属络合物间的相互作用显著影响制得催化剂的结构和反应的产物分布。由于金属络合物和分子筛内阳离子间的电子转移，使ＮｉＹ附载金属催化剂显示出高的ＣＯ转化率和甲烷选择性。在ＣｕＹ中，这种电子     

不同阳离子Y分子筛上金属络合物吸附和分解Ⅰ.Co(CO)3NO吸附性质表征

Ｃｏ（ＣＯ）３ＮＯ吸附进入Ｙ分子筛超笼，笼中不同交换阳离子对其吸附和分解起不同作用。研究不同交换阳离子Ｙ分子筛上Ｃｏ（ＣＯ）３ＮＯ的吸附和热分解发现，吸附金属络合物部分脱羰基或脱亚硝基，并伴有少量吸附物种的脱附。ＮａＹ上的热分解产物主要为金属钴；ＮｉＹ，尤其是ＣｕＹ上，阳离子和吸附物种作用较强，甚至发生电子转移，热分解产物为Ｃｏ（０）和Ｃｏ（Ⅱ）混合物。     

不同阳离子Y分子筛上金属络合物的吸附和分解 Ⅰ.Co(CO)_3NO吸附性质表征

Ｃｏ（ＣＯ）３ＮＯ吸附进入Ｙ分子筛超笼，笼中不同交换阳离子对其吸附和分解起不同作用．研究不同交换阳离子Ｙ分子筛上Ｃｏ（ＣＯ）３ＮＯ的吸附和热分解发现，吸附金属络合物部分脱羰基或脱亚硝基，并伴有少量吸附物种的脱附．ＮａＹ上的热分解产物主要为金属钴；ＮｉＹ，尤其是ＣｕＹ上，阳离子和吸附物种作用较强，甚至发生电子转移，热分解产物为Ｃｏ（０）和Ｃｏ（Ⅱ）混合物     

不同阳离子Y分子筛上金属络合物吸附和分解Ⅱ.Co(CO)3NO吸附和分解和红外光谱表征

采用红外光谱表征了含不同阳离子的Ｙ分子筛上Ｃｏ（ＣＯ）３ＮＯ的吸附和分解及其和阳离子的作用。结果表明，Ｃｏ（ＣＯ）３ＮＯ吸附后主要形成Ｃｏ（ＣＯ）ｘＮＯ（ｘ＝２，３），并出现热稳定性较高的Ｃｏ（ＮＯ）２＾２＋。产生Ｃｏ（ＮＯ）２＾２＋的机制和最终分解产物与分子筛阳离子的性质有关。ＮａＹ上Ｃｏ（ＮＯ）ｘＮＯ歧化产生少量Ｃｏ（ＮＯ）２＾２＋，分解产物主要为Ｃｏ（０）；ＣｏＹ中Ｃｏ＾２＋的存在部分避免了     

杂原子ZSM－5分子筛催化剂上C_3H_6催化还原NO反应的研究

杂原子ＺＳＭ－５分子筛催化剂上Ｃ_３Ｈ_６催化还原ＮＯ反应的研究张文祥，贾明君，张春雷，吴通好，敖雪桔（吉林大学化学系，长春，１３００２３）（齐齐哈尔环境监测中心站）关键词杂原子分子筛，一氧化氮，催化还原ＮＯｘ对环境的危害已引起了人们的广泛重视。自Ｉｗ...     

不同阳离子Y分子筛上金属络合物的吸附和分解 Ⅱ.Co(CO)_3NO吸附和分解的红外光谱表征

采用红外光谱表征了含不同阳离子的Ｙ分子筛上Ｃｏ（ＣＯ）３ＮＯ的吸附和分解及其和阳离子的作用．结果表明，Ｃｏ（ＣＯ）３ＮＯ吸附后主要形成Ｃｏ（ＣＯ）ｘＮＯ（ｘ＝２，３），并出现热稳定性较高的Ｃｏ（ＮＯ）２＋２．产生Ｃｏ（ＮＯ）２＋２的机制和最终分解产物与分子筛阳离子的性质有关．ＮａＹ上Ｃｏ（ＣＯ）ｘＮＯ歧化产生少量Ｃｏ（ＮＯ）２＋２，分解产物主要为Ｃｏ（０）；ＣｏＹ中Ｃｏ２＋的存在部分避免了Ｃｏ（ＣＯ）ｘＮＯ的歧化，分解得到的Ｃｏ（０）含量较高；ＮｉＹ，尤其ＣｕＹ阳离子和吸附物种发生电子转移，形成ＮＯ＋中间物种，氧化Ｃｏ（０）产生Ｃｏ（ＮＯ）２＋２，分解产物为Ｃｏ（０）和Ｃｏ（Ⅱ）的混合物．     

铜分子筛Cu(Ⅰ)物种上吸附CO的漫反射红外光谱

应用漫反射红外光谱测定了不同的铜分子筛经真空自还原后吸附ＣＯ的基频,组频和泛频谱带,结果表明,ＣＯ压力较低时,形成Ｃｕ（Ⅰ）（ＣＯ）吸附物种,其种类与分子筛的结构特性有关。随ＣＯ２压力增高,部分吸附物种转变为Ｃｕ（Ⅰ）（ＣＯ）２,分析Ｃｕ（Ⅰ）（ＣＯ）基频和组频谱带可得到比Ｃ－Ｏ伸缩振动更灵敏的反映Ｃｕ（Ⅰ）和ＣＯ作用的Ｃｕ（Ⅰ）－Ｃ伸缩振动频率。     

TS分子筛催化剂上烯丙基氯的环氧化性能

在ＴＳ－１分子筛催化剂上，研究了以Ｈ２Ｏ２为氧源的烯丙基氯液固多相环氧化反应。结果表明，ＴＳ－１３２分子筛是该反应的有效催化剂，Ｈ２Ｏ２转化率达８０％，目的产物氧氯丙烷选择性达９０％，用程序升温脱附（ＴＰＤ）和程序升温表面反应（ＴＰＳＲ）研究了Ｈ２Ｏ２和烯丙基氯在催化剂表面的吸附状态，结果表明，ＴＳ－１－３２分子筛对Ｈ２Ｏ２和烯丙基氯有较大吸附容量和吸附强度，使它们在反应温度下有较大的表面浓度，     

不同制备方法对Cu-ZSM-5沸石分子筛上NO分解反应活性的影响

不同制备方法对Ｃｕ┐ＺＳＭ┐５沸石分子筛上ＮＯ分解反应活性的影响＊韩一帆汪仁（华东理工大学工业催化研究所，上海２００２３７）关键词Ｃｕ－ＺＳＭ－５沸石分子筛，一氧化氮，催化分解，直接粘混法，离子交换法如何减少各类污染源所排放的氮氧化物（ＮＯｘ）对环境...     

氧化铝基表层镁铝尖晶石的研究──Ⅲ．Pd／MgAl_2O_4－γ－Al_2O_3

氧化铝基表层镁铝尖晶石的研究──Ⅲ．Ｐｄ／ＭｇＡｌ＿２Ｏ＿４－γ－Ａｌ＿２Ｏ＿３上ＮＯ的吸附态及其与ＣＯ的反应刘希尧（石油化工科学研究院，北京１０００８３）关键词钯催化剂，表层镁铝尖晶石，一氧化氮吸附态，一氧化氮还原氧化铝载耙催化剂上的ＣＯ还原ＮＯ反...     

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.