等瓣置换反应的研究——手性簇合物[η^—MeO2CC5H4）（CO）2Mo…

用Ｘ射线衍微法测定了由η＾５－ＭｅＯ２ＣＣ５Ｈ４（ＣＯ）３ＭｏＮａ和〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ－（ＣＯ）３Ｃｏ（ＣＯ）３（μ３－Ｓ）的等瓣置换反应所生成的手性簇合物－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｍｏ〕－〔（η＾５－ＭｅＯ２ＣＣ５Ｈ４）（ＣＯ）２Ｗ〕Ｆｅ（ＣＯ）３（μ３－Ｓ）的分子结构及晶体结构。晶体属Ｐ１空间群，晶胞参数ａ＝０．８７１６２（５）ｎｍ，ｂ＝０．８     

沉淀法制备CeO2超微粉末

采用过氧化氢－－氨水沉淀法在较低温度下制备ＣｅＯ２超微粉末。试验表明，溶液起始浓度及焙烧温度以形成粉素晶体粒径有一定影响。焙烧温度在２２０－８５０℃，所得ＣｅＯ２微粉均为立方晶系，透射电测试表明，粒子基本呈球形，晶体平均粒径随焙烧温度升高而增大。控制适当条件，可制得粒径范围在５－１３ｎｍ，比表面积１１１．８ｍ＾２／ｇ的ＣｅＯ２超微粉末。     

蝶状铁硒簇合物双（μ—p—甲苯硒基）六羰基二铁双膦取代…

测得并解析了２个蝶状铁硒取代衍生物（μ－ｐ－ＭｅＣ６Ｈ４Ｓｅ）２Ｆｅ２（ＣＯ）２（Ｐｈ２ＰＣＨ２ＣＨ２ＰＰｈ２）（Ａ）和（μ－ｐ－ＭｅＣ６Ｈ４Ｓｅ）２Ｆｅ２（ＣＯ）４（ｃｉｓ－Ｐｈ２ＰＣＨ＝ＣＨＰＰＨ２）（Ｂ）的＾１Ｈ－＾１ＨＣＯＳＹ谱和＾１Ｈ－＾１５ＣＣＯＳＹ谱以及Ａ的＾１Ｈ－＾１ＨＮＯＥＳＲ谱，从而进一不确证了它们的结构。     

裉色光度法测定SO^2—3的研究

本文研究了ＳＯ＾２－３褪色碱蓝６Ｂ的反应，在ｐＨ５．２Ａｃ－ＮａＡｃ缓冲介质中，ＳＯ＾２－３浓度在０．３９－１２ｍｇ／Ｌ范围内符合比尔定律，仅Ｆｅ＾３＋，Ｎｉ＾２＋，Ｃｒ＾３＋干扰测定，用于食品中ＳＯ＾２－３的测定，结果令人满意。     

金属键有机化合物的研究—非对称型η^5—取代环戊二烯…

通过η＾５－Ｒ＾１Ｃ５Ｈ４（ＣＯ）３ＭＨａ与η＾５－Ｒ＾２Ｃ５Ｈ４（ＣＯ）２ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η＾５－Ｒ＾１Ｃ５Ｈ４（ＣＯ）３ＭｏＮａ与η＾５－Ｒ＾２Ｃ５Ｈ４（ＣＯ）３ＷＮａ在Ｆｅ２（ＳＯ４）３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η＾５－Ｒ＾１Ｃ５Ｈ４（ＣＯ）３Ｍｏ－Ｍｏ（ＣＯ）３Ｃ５Ｈ４Ｒ＾２－η＾５（Ｒ＾１，Ｒ＾２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η＾５     

Ce0.5Zr0.5O2固溶体的原位拉曼光谱

控制合成条件以湿化学法制备了Ｃｅ－Ｚｒ－Ｏ（Ｃｅ）／ｎ（Ｚｒ）＝１固溶体,ＸＲＤ结果证实催化剂前体经９２３Ｋ焙烧后可获得立方相Ｃｅ０．５Ｚｒ０．５Ｏ２固溶体,ＴＥ倒固溶体颗粒大小均一、分散、呈纤毛状、在氧化和还原气氛条件下分别对固溶体进行了原位拉曼光谱研究,结果表明,除４５０－４７０ｃｍ＾－１处出现而心立方晶格Ｆ２ｇ拉曼地应的强拉曼谱峰外,２９０－３２０ｃｍ＾－１,５７－６２０ｃｍ＾－１,７７０－     

1987年以来国外Ge-132生物学作用研究的新进展

综述了Ｇｅ－１３２的生物学作用研究的新进展。包括：１．免疫调节作用，可增强强的松增高血浆超氧化物清除活性，抗癌抗艾滋病活性，能有效地缓解晚期癌症疼痛。２。对＾６０Ｃｏ射白细胞生成超氧化物有保护作用，可刺激白细胞的Ｏ２＾－释放，防止＾６０Ｃｏ照射白细胞Ｏ２＾－生成减少，在高浓度时具有膜稳定作用。３．防止白内障的发生。４对抗白血病细胞的细胞毒作用，５．活化神经作用，有利于中风瘫患者的恢复。     

碘量法测定冶金物料中铁

系统地研究了Ｆｅ＾３＋与Ｉ＾－定量反应的条件，共存离子的干扰及消除方法，在ＨＣｌ和ＫＩ存在下，Ｆｅ＾３＋与Ｉ＾－定量反应，Ｃｕ＾２＋，ＡｓＯ４＾３－，ＶＯ２＾＋，等定量干扰，使用ＮａＦ或Ｈ３ＰＯ４制备参比液可抵消干扰。可不经分离直接测定大部分冶金物料中的高含量铁。     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２〕２／（μ－ＣＯ）２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

光化学反应在流动注射分析中的应用研究：Ⅲ.甲基橙光化学反应…

基于ＮＯ２＾－，ＮＯ３＾－和Ｆｅ（Ⅲ）对甲基橙光化学褪色反应的催化作用，利用自制流通式光化学反应应器，建立了流动注射光化学反应同时测定ＮＯ２＾－和ＮＯ３＾－以及测定Ｆｅ（Ⅲ）的新方法。测定ＮＯ２＾－和ＮＯ３＾－的线性范围都是０．１－３．２ｍｇ／Ｌ，每小时可测３０－４０个样品。测定Ｆｅ（Ⅲ）的线性范围为０．０６－１．２ｍｇ／Ｌ，进样频率为６０－８０次／ｈ。应用于蔬菜中ＮＯ２＾－，ＮＯ３＾－的测定和茶     

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.