高温煤焦油组成的毛细管气相色谱／傅立叶变换红外光谱研究─—中油馏分的分析

 在原有研究工作基础上，采用气相色谱／傅立叶变换红外光浴保留指数（ＧＣ／ＦＴＩＲ－ＲＩ）技术，结合同系物保留指数与沸点的关联式中斜率因子的重要作用，研究了高温煤焦油中油馏分的化学组成。分别从Ｆ＿３、Ｆ＿４、Ｆ＿５、Ｆ＿６中分离并鉴定出４１，５３，６４，６０种化合物，获得了有价值的实验数据和结果，为煤焦油的深度加工与处理提供了重要的理论依据。     

高温煤焦油组成的毛细管气相色谱／傅立叶变换红外光谱研究─—中油馏分的分析

在原有研究工作基础上，采用气相色谱／傅立叶变换红外光浴保留指数（ＧＣ／ＦＴＩＲ－ＲＩ）技术，结合同系物保留指数与沸点的关联式中斜率因子的重要作用，研究了高温煤焦油中油馏分的化学组成。分别从Ｆ＿３、Ｆ＿４、Ｆ＿５、Ｆ＿６中分离并鉴定出４１，５３，６４，６０种化合物，获得了有价值的实验数据和结果，为煤焦油的深度加工与处理提供了重要的理论依据。     

气相色谱保留指数通用数据库的研究（三）不同柱温模式下保留指数的相互转换

 由于升温模式（Ｔ_０，ｒ）、色谱柱和操作参数（Ａ，Ｔ_ｂ，β）的差别，使得Ｔ_Ｒ不同而影响Ｉ_（ＴＰ）的可比性，其影响的大小随恒温保留指数ＲＩ的温度系数的增加而增加。同时，由于Ｔ_Ｒ与ｎ偏离了线性关系，采用保留温度线性插值方法计算Ｉ_（ＴＰ），方法本身就在一定程度上会使Ｉ_（ＴＰ）的可比性差，即使恒温ＲＩ的温度系数为零，Ｉ_（ＴＰ）也会随ＧＣ条件而改变。根据恒温与线性程升的保留值方程建立的各种柱温模式下的保留指数相互转换方法能准确快速地预测不同柱温模式下的保留指数，以此来建立通用数据库以适应不同的分析条件的需要。     

程序升温毛细管气相色谱保留指数的计算

 ]本文提出了一种由程序升温保留值计算恒温保留指数的方法，对载气稳压型毛细管气相色谱仪在升温过程中流速变化对保留值的影响进行了校正。由两种升温速度的保留值可计算出某一特定温度下的保留指数，便于用文献保留指数数据进行定性。对三十多种不同类型化合物测定的结果表明，计算结果与恒温测定结果很符合。     

GC／MS分析煤抽出物中的含硫多环芳香化合物

煤的索氏抽出物中的含硫多环芳香化合物（ＰＡＳＨ）由硅胶柱色谱与配体交换薄层色谱（ＰｄＣｌ＿２／ＳｉＯ＿２）两步分离，用毛细管气相色谱（ＦＩＤ与ＦＰＤ）和色质联用仪分析其组成、结构。通过与文献的色谱保留指数相比较、质谱数据验证，鉴定出贵定煤含硫芳香化合物以三、四环结构为主，主要是二苯并噻吩及其Ｃ＿１～Ｃ＿３烷基取代物、苯并萘并噻吩及其烷基取代物，其它稠环含硫芳香化合物较少。     

气相色谱保留指数通用数据库的研究（三）不同柱温模式下保留指数的相互转换

由于升温模式（Ｔ_０，ｒ）、色谱柱和操作参数（Ａ，Ｔ_ｂ，β）的差别，使得Ｔ_Ｒ不同而影响Ｉ_（ＴＰ）的可比性，其影响的大小随恒温保留指数ＲＩ的温度系数的增加而增加。同时，由于Ｔ_Ｒ与ｎ偏离了线性关系，采用保留温度线性插值方法计算Ｉ_（ＴＰ），方法本身就在一定程度上会使Ｉ_（ＴＰ）的可比性差，即使恒温ＲＩ的温度系数为零，Ｉ_（ＴＰ）也会随ＧＣ条件而改变。根据恒温与线性程升的保留值方程建立的各种柱温模式下的保留指数相互转换方法能准确快速地预测不同柱温模式下的保留指数，以此来建立通用数据库以适应不同的分析条件的需要，特别是从２种升温模式出发预测其它柱温模式下的保留值能更方便地对复杂样品的分离条件进行优化。     

程序升温毛细管气相色谱的保留指数计算

Kovats提出的保留指数原系用于恒温分析,但由于要分析的样品越来越复杂,往往必须使用程序升温操作。van den Dool采用保留温度来计算程序升温下的保留指数,虽然计算方法简单,但只适用于单纯直线升温而不含恒温阶段的操作过程,其应用受到很大限制。Majlat等人的方法可应用于多阶升温,多阶恒温的过程,论述十分详尽。其关键是采用了Takacs等人推导的压力校正因子计算式:     

气相色谱保留指数定性方法研究进展

综述了程序升温气相色谱保留指数,I^T与Kovats恒温保留指数,之间的关系、I^T的标准化和重现性问题以及定量结构保留指数关系(QSRR)研究进展;对于应用特殊检测器和极性柱定性、对多环芳烃和多氯联苯类物质利用保留指数定性的情况,选择非正构烷烃类同系物作为参考标准时准确性大为提高,比较了由此得到的保留指数与Kovats保留指数的关系;展望了利用保留指数定性的前景。     

液态结构与Al-Fe-Ce合金短程有序的相关性

采用Ｘ射线衍射技术研究了Ａｌ＿０．９Ｆｅ＿０．１和Ａｌ＿０．９Ｆｅ＿０．０５Ｃｅ＿０．０５合金的液态结构及Ａｌ＿０．９Ｆｅ＿０．０５Ｃｅ＿０．０５合金的非晶结构,并采用ＤＳＣ热分析研究了非晶合金的晶化行为．发现液态和非晶态合金的结构因子曲线上都存在明显的预峰,所对应的化学短程有序结构随温度降低,尺寸不断增大,但其结构单元的尺寸保持不变．Ｃｅ的加入使液态合金中化学短程有序及其结构单元的尺寸增大,并有利于原子间交互作用增强,从而提高非晶形成能力．预峰所对应的化学短程有序结构单元是以Ｆｅ原子为中心的二十面体准晶结构,这种结构在液态已形成,并保留在非晶中．     

C_（60），C_（70）液相色谱分离方法的研究

较系统地考察了不同柱系统及不同流动相组成下Ｃ＿（６０）,Ｃ＿（７０）的保留规律。在实验的基础上,提出了分离Ｃ＿（６０）,Ｃ＿（７０）的最佳柱系统及流动相组成。并在此分离条件下,对高分子量的富勒烯组分进行了分离。     

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.     

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.     

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.     

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.