CH自由基和NO2反应研究Ⅰ.反应的热力学计算

探讨了CH自由基与NO2反应的可能路径,通过计算确定了反应物,产物和稳定中间体的电子状态和平衡构型,并运用Gaussian-3方法和MRCISD方法对可能的反应路径进行了热力学计算.在多数情况下与实验值符合较好.对于个别与理论计算差别较大的实验值进行了评述.     

CH自由基和NO~2反应研究: I. 反应的热力学计算

探讨了CH自由基与NO~2反应的可能路径,通过计算确定了反应物,产物和稳定中间体的电子状态和平衡构型,并运用Gaussian-3方法和MRCISD方法对可能的反应路径进行了热力学计算。在多数情况下与实验值符合较好。对于个别与理论计算差别较大的实验值进行了评述。     

CH自由基和NO~2反应研究: I. 反应的热力学计算

探讨了CH自由基与NO~2反应的可能路径,通过计算确定了反应物,产物和稳定中间体的电子状态和平衡构型,并运用Gaussian-3方法和MRCISD方法对可能的反应路径进行了热力学计算。在多数情况下与实验值符合较好。对于个别与理论计算差别较大的实验值进行了评述。     

均四甲苯氧化制二酐宏观动力学分析

为了提高均四甲苯氧化制均苯四甲酸二酐的收率,以某二酐生产企业生产的高效钒钛催化剂,在固定床反应器中对均四甲苯气相氧化制均苯四甲酸二酐反应体系的动力学进行了研究。首先提出了可能的反应网络,然后设计相关动力学测试实验,建立均四甲苯氧化反应的幂函数宏观动力学模型。进一步的实验和统计分析表明,模型计算值与实验值吻合较好。宏观动力学方程的建立为后续将其用于相应的固定床反应器模拟提供了基础保证。     

燃煤过程中CaO固氟反应特性的模型研究

采用部分烧结晶粒模型建立了燃煤过程中CaO固氟反应的数学模型；并在WCT－1型热天平上对CaO固氟反应特性进行了试验研究，结果表明，CaO/HF反应对HF为一致，本征反应和产物层扩散活化能分别为18．73kJ/mol和32．46kJ/mol，分析了反应温度，HF浓度，煤颗粒微孔结构等对CaO转化率的影响，经与热重实验结果比较表明，计算值与实验值基本吻合。     

化学浴沉积cawo4薄膜的动力学

对化学浴沉积法制备的CaWO4薄膜进行了动力学研究。采用Avrami-Erofeev方程进行计算,得到反应温度40~80℃和反应溶液pH值为8~12条件下,CaWO4薄膜的动力学方程。结合实验分析各动力学参数的变化,发现反应温度越高,反应速率常数k越大,薄膜趋向于自发形核生长;反应溶液pH值越高,反应速率常数k显著减小,Avrami指数n则几乎不变。结果可见,pH值对反应速率的影响大,而对成核和生长方式影响小。pH值对反应速率的影响主要在于改变了Ca-EDTA螯合体的络合稳定性,进而影响整个反应的进行速度。通过动力学研究可以明确反映反应参数对薄膜生长的影响,体现了薄膜生长过程的本质,有助于达到有效控制反应过程的目的。     

应用纤维催化剂双烯选择加氢动力学

应用理想喷淋床反应器模型,从实验结果计算了使用Pd-Al_2O_3纤维催化剂时,在低温下裂解汽油中双烯加氢的速度常数及活化能。结果表明,双烯加氢反应基本上可按一级反应处理。按照串行一级反应模型,从实验结果计算了不同温度下的选择因子,从而进一步计算了单烯加氢的速度常数和活化能。此外,还按上述模型计算了单烯选择性。计算值与实验值大体上一致。同时对单烯选择性较好的原因也作了解释。     

HNCO+HCO→NCO+CH2O氢转移反应的从头算及动力学研究

在UMP2(Full)/6-311G(d,p)计算水平上,优化了标题反应的反应物、过渡态、产物的几何结构,沿最小能量途径讨论了异氰酸(HNCO)和甲酰自由基(HCO)发生氢转移反应位能面上驻点的结构以及相互作用分子结构变化.指出该反应是一个N-H键断裂和C-H键生成的协同反应.进一步采用UQCISD(T,Full)方法对反应途径上的驻点进行了单点能量校正,得出该反应的计算位垒是91.47 kJ/mol,与实验值108.92 kJ/mol接近在500～2500K实验温度范围内,运用变分过渡态理论(CVT)计算得到的速率常数与实验观测值进行了比较     

搅拌釜中制备草酸铈的团聚尺寸模型研究

以硝酸铈和草酸铵反应生成草酸铈沉淀为研究对象，探讨了搅拌釜中输入功率、溶液过饱和度与产物团聚尺寸之间的变化关系并在团聚和破碎动力学的基础上建立了团聚尺寸模型。根据草酸铈沉淀实验中得到的实验结果求得了一定反应体系浓度下的模型K1，K2和K3值，最后通过－↑LtE,max的模型计算值与实验值，ε--↑LtE的模型曲线与实验曲线的比较初步证明了该模型的实际适用性。     

卟啉化合物的电催化行为V.金属卟啉化合物电极上胱氨酸还原反应的动力学及反应机理研究

采用循环伏安法及带环的旋转圆盘电极技术,在经热处理的载于石墨粉上的四(对甲氧基苯基)卟啉钴(Co-TMPP/石墨)电极上研究了溶液pH值对胱氨酸还原反应的影响.实验结果表明,在不同pH值溶液中经热处理的Co-TMPP/石墨对 胱氨酸还原反应均有较好的催化活性且该电极上胱氨酸还原反应为不可逆的简单电荷传递反应.测出了不同pH值溶液中胱氨酸剂原反应的标准速度常数.当pH<4时,胱氨酸还原对[H^+]的反应级数为1;pH>9时,反应与[H^+]无关.提出了不同pH值溶液中胱氨酸还原反应的机理.     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.