金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ、Ｃｏ、Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征．研究了它们的光化学性质．结果表明．在ＴＥＯＡ中光照使Ｍ·ＴＣＭＰＰ—ｍｖ￣２＋发生了分子内从卟啉到甲基紫精的电子迁移反应．在ＺｎＴＣＭＰＰ－ｍｖ￣２＋／ＴＥＯＡ／ＤＭＳＯ—Ｈ２Ｏ体系中可发生光敏化还原ｍｖ２＋反应，生成较稳定的ｍｖ＋．在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ｍｖ２＋／ＣＨ３ＯＨ／Ｈ２Ｏ体系中可发生光助氧化甲醇反应，并检出了氧化产物甲醛．     

Ni/Al2O3催化剂上甲烷部分氧化制合成气反应机理

用变应答／质谱在线检测技术研究了Ｎｉ／Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气的反应要理，研究结果指出，在常压９７３Ｋ条件下，Ｎｉ／Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气按直接氧化机理进行，Ｈ２和Ｃ烛甲烷部分氧化的一次产物，其主要反应可表示如下：１．ＣＨ４＋ｘＮｉ－ＮｉｘＣ＋２Ｈ２，２．Ｏ２＋２Ｎｉ－２ＮｉＯ，３．ＮｉｘＣ＋ＮｉＯ－ＣＯ＋（ｘ＋１）Ｎｉ。     

Ni－Cu和TiO_2－SiO_2间的相互作用及其对催化性能的影响

用表面反应改性法制备了ＴｉＯ２－ＳｉＯ２（ＴＳＯ）表面复合物载体．采用ＴＰＲ，ＩＲ，ＴＰＤＭＳ和ＴＰＳＲ－ＭＳ等技术研究了ＮＩ－Ｃｕ／ＴＳＯ间的相互作用及其对ＣＯ加氢反应的催化性能．结果表明，ＮｉＯ－ＣｕＯ与ＴＳＯ间的相互作用导致ＣｕＯ的还原温度降低和ＮｉＯ的还原温度升高，并有少量表面物种生成；还原后的Ｎｉ－Ｃｕ／ＴＳＯ催化剂表面上存在着两类活性中心，即合金相中的Ｎｉ及载体相中的Ｔｉｎ＋（或Ｔｉｎ＋－Ｏ）；ＣＯ在催化剂表面存在孪生、线式、桥式和卧式等４种吸附态；Ｈ２在催化剂表面上发生解离吸附形成Ｎｉ－Ｈ和Ｔｉｎ＋－Ｈ，前者比较活泼，是加氢反应的主要Ｈ源；卧式吸附态极易在催化剂表面裂解形成Ｎｉ－Ｃ和Ｔｉｎ＋－Ｏ，前者是加氢反应的Ｃ源，使ＣＯ加氢生成烃类的反应在Ｎｉ中心上按＂表面碳＂机理进行，其生成乙烯的选择性大于６０％．Ｈ２Ｏ的生成反应在Ｔｉｎ＋中心上按Ｔｉｎ＋－Ｏ与Ｔｉｎ＋－Ｈ或Ｎｉ－Ｈ反应的途径进行．     

Ni－Cu和MgO－SiO_2间的相互作用及其对催化性能的影响

本文用ＴＰＲ，ＩＲ，ＴＰＤ和ＴＰＳＲ等技术研究了以表面改性法制备的ＭｇＯ－ＳｉＯ２（ＭＳＯ）表面复合物担载的Ｎｉ－ＣＵ合金间的相互作用及其对ＣＯ加氢反应催化性能的影响．结果表明，ＮｉＯ－ＣｕＯ与ＭＳＯ间的相互作用导致部分ＭＯ与ＭＳＯ形成表面物种从而使金属组分氧化物还原温度明显升高；还原后的Ｎｉ－Ｃｕ／ＭＳＯ表面上存在着两类活性中心，即合金相中的Ｎｉ与载体相中的Ｍｇ２＋（或Ｍｇ２＋－Ｏ）；在两类活性中心的协同作用下，ＣＯ吸附除有孪生、线式和桥式吸附态物种外，还有一种新的卧式吸附态（Ｎｉ．．．Ｃ＝Ｏ→Ｍｇ２＋）．这种吸附态的活化程度较高，易在表面上发生裂解形成Ｎｉ－Ｃ和Ｍｇ２＋－Ｏ，其中Ｎｉ－Ｃ是加氢反应的碳源；Ｈ２在催化剂表面上发生解离吸附形成Ｎｉ－Ｈ和Ｍｇ２＋－ＯＨ，前者比较活泼，是加氢反应的氢原．ＣＯ加氢生成烃类的反应在Ｎｉ中心上按＂表面碳＂机理进行，其生成ＣＺＨ４的选择性高于８０％；Ｈ２Ｏ的生成反应按２（Ｍｇ２＋－ＯＨ）－→Ｍｇ２＋＋（Ｍｇ２＋－Ｏ）＋Ｈ２Ｏ方式进行．     

金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ，Ｃｏ，Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征。研究了它们的光化学性质。结果表明，在ＴＥＯＡ中光照使Ｍ。ＴＣＭＰＰ－ｍｖ＾２＋发生了分子内从卟啉到甲基紫精的电子迁移反应。在ＺｎＴＣＭＰＰ－ｍｖ＾２＋／ＴＥＯＡ／ＤＭＳＯ－Ｈ２Ｏ体系中可发生光敏化还原ｍｖ＾２＋反应，生成较稳定的ｍｖ＾＋。在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ＭＶ＾２＋／ＣＨ３     

Fe－Mn－K催化剂FT合成反应的研究

研究了Ｆｅ－Ｍｎ－Ｋ催化剂ＦＴ合成动力学及产物分布规律，并探讨了反应条件对（ＣＯ＋Ｈ＿２）转化率及α－己烯／正己烷比的影响。结果表明，该催化剂的产物分布需用两个α才能较好地描述；反应温度及反应气氛下Ｈ＿２／ＣＯ比对α－己烯／正己烷比具有较大影响：最后获得的动力学方程为：－ｒ＿（Ｈ＿２＋ＣＯ）＝ａＰ＿（ＣＯ）Ｐ＿（Ｈ＿２）／（Ｐ＿（ＣＯ）＋ｂＰ＿（Ｈ＿２Ｏ）），从活化能的角度看，该粒度催化剂存在着内扩散效应。     

连续流动化学发光法测定水中总有机碳的研究

基于Ｋ２Ｓ２Ｏ８氧化水中有机碳为二氧化碳，二氧化碳能增强Ｌｕｍｉｎｏｌ－Ｈ２Ｏ２－Ｃｏ＾２＋体系化学发光强度，建立了连续流动化学光测定水中总有机碳的新方法。方法线性范围为０．１０－１２μｇ／ｍＬＣ，检出限量为０．０４μｇ／ｍＬＣ。所建立方法简便、灵敏，适合于应用于水中总有机碳的测定。     

CO2／H2和（CO／CO2）＋H2低压合成甲醇催化过程的本质

通过在Ｃｕ／ＺｎＯ／Ａｌ２Ｏ３催化剂上ＣＯ２＋Ｈ２，ＣＯ＋Ｈ２和（ＣＯ／ＣＯ２）＋Ｈ２催化反应动力学研究对合成甲醇动力学和反应机理进行了细致分析，提出合成甲醇的反应机理，解释了在（ＣＯ／ＣＯ２）＋Ｈ２合成甲醇过程中少量ＣＯ２的作用及合成甲醇的直接碳源。     

聚醋酸乙烯酯与铜（Ⅱ）离子的配位反应及其催化作用

以ＥＳＲ、ＵＶ和ＩＲ表征Ｃｕ（２＋）离子与ＰＶＡＣ的配位反应。根据ＣＵＣｌ２·２Ｈ２Ｏ乙醇溶液与ＰＶＡｃ－ＣｕＣｌ２·２Ｈ２Ｏ乙醇溶液的电导率差值随Ｃｕ（２＋）离子摩尔浓度变化的明显转析点得知，１个Ｃｕ（２＋）离子大约能与ＰＶＡｃ４个链节单元配位。证实ＭＭＡ在Ｃｕ（Ⅱ）－ＰＶＡｃ配合物／Ｎａ２ＳＯ３体系的聚合体是无规ＰＭＭＡ，得率为７０％。讨论了ＭＭＡ在Ｃｕ（Ⅱ）－ＰＶＡｃ配合物／Ｎａ２ＳＯ３体系络合催化引发下的游离基反应历程。     

超高比表面炭载钼煤气甲烷化催化剂

以沥青中间相为原料，氢氧化钾直接活化，获得了比表面达２３６３ｍ￣２／ｇ的超高比表面炭分子筛（ＣＭＳ）。分别以ＣＭＳ、ＳｉＯ＿２、活性炭和θ－Ａｌ＿２Ｏ＿３为担体，制备了负载钼催化剂，并研究其加压甲烷化反应性能，发现活性依下面顺序增加：θ－Ａｌ＿２Ｏ＿３＜ＳｉＯ＿２＜活性炭（ＡＣ）＜ＣＭＳ。还分别以钼酸铵和磷钼酸（ＨＰＭｏ）为前驱体，制备了ＣＭＳ负载钼催化剂，并考察了其煤气甲烷化活性，发现不同的催化剂前驱体对催化剂反应活性影响很大。根据产物中ＣＨ＿４／ＣＯ＿２的变化，推测ＣＯ在钼催化剂上的甲烷化反应包括如下两个步骤：（１）３Ｈ＿２＋ＣＯ→ＣＨ＿４＋Ｈ＿２Ｏ，（２）ＣＯ＋Ｈ＿２Ｏ→ＣＯ＿２＋Ｈ＿２。     

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.     

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.     

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.     

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.     

关于"对‘燃料电池物理及化学性能的有限时间热力学分析方法'的讨论”答复

把有限时间热力学理论用于化学过程的研究,将会得到一系列新的结论,开展这方面的研究是很有意义的.文献[1]以燃料电池为例,在同时考虑化学反应及传热不可逆性的情况下,研究了燃料电池的性能界限,文献[2]指出了文献[1]计算化学反应及传热不可逆性而引起系统与有关环境的总熵产生率的错误以及由此而导致的结论所存在的问题,并进行了富有启发性的分析与讨论.但文献[2]对于系统与有关环境的总熵产生率的计算也是不正确的,由此得到的其它结论自然不能成立.本文将就此情况下系统与有关环境的总熵产生率的计算再次进行讨论,并给出电池功率和效率的有限时间热力学性能界限.