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。     

浆态床FT合成／固定床ZSM－5改质的合成液体燃料工艺的研究和开发

从合成气制取液体燃料的浆态床ＦＴ合成／固定床２ＳＭ－５改质的反应系统由Ⅰ段鼓泡浆液反应器（内径４０ｍｍ，高４５０Ｏｍｍ）和Ⅱ段固定床ＺＳＭ－５反应器（内径４０ｍｍ，高９００ｍｍ）组成，在温度２５０～２８０℃（Ⅰ段），３００～３４０℃（Ⅱ段），压力１．５～２．５ＭＰａ，空速２．０ＮＬ／ｇＦｅ·ｈ（Ⅰ段），５００～１０００ｈ￣－１（Ⅱ段），Ｈ＿２ＣＯ比０．５～１．５和气速１～２ｃｍ／ｓ范围内，考察了工艺参数对反应性能的影响，１０００ｈ以上的寿命试验的平均结果为：合成气单程转化率６５．１％，产率１００ｇ／Ｎｍ￣３（Ｃｏ＋Ｈ＿２），总烃生产达３５０ｇ／Ｆｅ。使用富ＣＯ合成气时，达１１０ｇ／Ｎｍ￣３（ＣＯ＋Ｈ＿２）。实测的ＦＴ合成反应热为２９３８；５ｋＪ／Ｎｍ￣３（ＣＯ＋Ｈ＿２）。长期运转试验表明，工艺流程合理，设备操作和温度控制可靠。采用的浆液循环回路方法可初步分离蜡中的催化剂。     

钛系Ziegler－Natta催化剂下的丙烯／α－烯烃的共聚合

研究了ＴｉＣｌ＿４／ＭｇＣｌ＿２－三乙基铝（ＴＥＡ）高效载体催化体系下的丙烯／癸烯－１共聚及δ－ＴｉＣｌ＿３－－氯二乙基铝（ＤＥＡＣ）催化体系下的丙烯／辛烯－１共聚合的基本反应规律，考察了铝钛比、温度、共聚单体浓度等对共聚合的影响；对比了两种催化体系的不同，利用非均相Ｚｉｅｇｌｅｒ－Ｎａｔｔａ催化体系下共聚合的非稳态扩散动力学的观点，解释了观察到的共聚合催化效率增加，共聚物粒子增大等实验现象．     

T302锌锰系脱硫剂脱除H2S微观动力学研究

用热重法研究了Ｔ３０２锌锰系脱硫剂脱除Ｈ＿２Ｓ的微观动力学行为。实验表明，该过程对Ｈ＿Ｓ８为一级反应。在２００～４２０℃的温度范围，反应初期受反应本身控制，中后期转移为颗粒扩散控制。反应速率常数及有效扩散系数可分别表示为：ｋ＿Ｓ＝０．８９１×１０￣（－４）ｅｘｐ（－１９８００／８．３１４Ｔ）Ｄ＿（ｅｇ）＝５．６４×１０￣（－１０）ｅｘｐ（－３４５３７／８．３１４Ｔ）指出在较低温度下存在最大转化率，并分析了影响最大转化率的因素，讨论了校正系数Ｂ＿１的物理意义。     

我国煤加氢热解研究Ⅲ．神府煤加氢、催化加氢及H_2－CH_4气氛下热解的研究

本文在５ｇ固定床反应器中对神府榆家梁煤的加氢，ＭｏＳ＿２催化加氢及模拟焦炉气（５０％Ｈ＿２－５０％ＣＨ＿４）下的热解进行了研究，反应温度７９３～９７３Ｋ，压力０．１～１５ＭＰａ，升温速率５Ｋ／ｓ。实验结果表明，由于煤加氢热解反应受传质控制，因此，不同反应器与工艺参数对热解反应影响很大；热解产物的焦油／气体收率比值可较好反映氢的有效利用率；高温和高压有利于煤加氢气化反应，导致氢耗增加，氢有效利用率下降；催化剂的存在不仅促进加氢反应，而且也加快了芳环开环及加氢气化反应；甲烷在本研究的温度和压力条件下相当于惰性组分，加氢热解反应取决于氢分压，说明以焦炉气代替氧气进行煤加氢热解是可行的。     

水溶性铑－膦配合物催化长链烯烃氢甲酰化反应研究──反应条件的影响

本文研究了两相催化体系中，在ＣＴＡＢ（Ｃ＿（１６）Ｈ＿（３３）ＮＭｅ＿３Ｂｒ）存在下，水溶性铑－膦配合物ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）＿２对１－己烯氢甲酰化反应的催化性能，详细考察了反应温度、压力、膦／铑比等对催化活性的影响。结果表明，在１．０ＭＰａ恒压下，反应温度１００℃，膦／铑摩尔比为１６，Ｈ＿２：ＣＯ＝１：１的条件下，１－己烯氢甲酰化的转化频率（ＴＯＦ）可达到３９．８ｍｉｎ￣（－１）。在此反应条件下，有机相和水相容易分离，铑－膦配合物流失到有机相中的量极小。     

生物质热解、加氢热解及其与煤共热解的热重研究

在加压热天平上用非等温热重法进行生物质（锯末、稻壳）在Ｎ２气氛下的热解和加氢热解研究。考察了升温速率（５～２５℃／ｍｉｎ）和压力（０．１～７ＭＰａ）的影响，求取了热解动力学参数，并研究了生物质与煤在常压Ｎ２气下的共热解过程。研究结果表明：生物质在４００℃左右即完成热解反应，总失重率大于７０％（Ｗ％，ｄａｆ．），热解时仅一个峰位于３００℃左右；与煤热解行为相同，随升温速率及压力的升高，转化率下降，ＤＴＧ峰移向高温，但由于热解反应在较低温度下进行，氧气的存在对生物质热解ＴＧ和ＤＴＧ的影响远小于煤热解。证明生物质热解以其内部氢对自由基的饱和及分子重排反应为主。生物质热解可用一级反应动力学处理，主要热解阶段及表现活化能分别为：锯末，２６７～３１４℃，６９．６６ｋＪ／ｍｏｌ；稻壳，２８３～３１０℃，５３．４５ｋＪ／ｍｏｌ；生物质由于与煤的热分解温度相差很大，因而在其共热解过程中无协同作用。     

一种对异戊二烯立体控制聚合较敏感的稀土催化体系

发现了一种对异戊二烯聚合立体选择性较敏感的稀士催化体系：（β－ＣＨ＿３－ａｌｌｙｌ）＿２ＬｎＣｌ＿５Ｍｇ·２Ｔ的ＥＤ（Ｌｎ）－Ｒ＿３Ａｌ（Ａｌ）（Ｌｎ＝Ｎｄ、Ｃｅ和Ｌａ，Ｔ的ＥＤ：Ｎ，Ｎ，Ｎ′，Ｎ′－四甲基乙二胺；Ｒ＝Ｍｅ一，Ｅｔ一，ｉ－Ｂｕ一和Ｏｃｔ一）．该催化体系在改变聚合温度、聚合时间、Ａｌ／Ｌｎ摩尔比、溶剂等时，可使聚异戊二烯的立体现整度有较大的改变，其中顺式－１，４、反式－１，４和３，４－链节含量的变化范围分别为１９％～７９％、１７％～７８％和０％～３．５％，还可获得较低分子量的聚合物。     

水杨醛－L－甲硫氨酸希夫碱钴（Ⅱ）配合物的热分解动力学

本文合成了一种新的希夫碱配合物，水杨醛－Ｌ－甲硫氨酸—水合钴（Ⅱ），Ｃｏ（ｓａｌｍｅｔ）·Ｈ２Ｏ，并用非等温热重法研究了它的热分解反应动力学。ＴＧ及ＤＴＧ曲线表明配合物按两步分解：Ｃｏ（ｓａｌｍｅｔ）·Ｈ２Ｏ１４２－１７５℃（１）→Ｃｏ（ｓａｌｍｅｔ）１７５－８２０℃（２）→ＣｏＯ用Ａｒｃｈａｒ微分法和Ｃｏａｔｓ－Ｒｅｄｆｅｒｎ积分法联合求出两步骤的动力学。步骤（１）、（２）的动力学方程分别表示如下：ｄα／ｄｔ＝Ａ·ｅ－Ｅ／ＲＴ（１－α）［－ｌｎ（１－α）］ｄα／ｄｔ＝Ａ·ｅ－Ｅ／ＲＴ（１－α）２［（１－α）－１－１］     

一氟二氯代甲烷热解离动力学的理论研究

利用从头算和ＲＲＫＭ理论研究了一氟二氯代甲烷热解离动力学，并得到了一套热力学和动力学参数。研究了三种不同的解离通道：（１）ＨＣｌ＋ＣＦＣｌ_２，（２）Ｃｌ＋ＣＨＦＣｌ，（３）ＨＦ＋ＣＣｌ_２，它们的活化能分别为：２４３．３、２５８．９、３０９．８ｋＪ／ｍｏｌ。研究结果表明，氯化氢消除反应和碳氯键简单断键反应是两个主要的并且是竞争的通道，三个反应通道的高压速率常数分别为ｋ_１＝８．７４×１０~（１４）ｅｘｐ（－２９１６３Ｔ）_ｓ~（－１），ｋ_２＝７．０９×１０~（１５）ｅｘｐ（－３１１２１／Ｔ）_ｓ~（－１），Ｒ_３＝３．８７×１０~（１１）ｅｘｐ（－３７０３９／Ｔ）_ｓ~（－１），它们都具有明显的温度和压力依赖关系。     

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.