苯偶氮罗丹宁类显色剂的合成及其与铜的显色反应

报道５－（４＇－氯－２＇－羧基苯偶氮）罗丹宁（２），５－（４＇－溴－２＇－羧基苯偶氮）罗丹宁（３）和５－（４＇－碘－２＇羧基苯偶氮）罗丹宁（４）的合成及在水溶液中的离奶常数Ｋ和Ｋ研究它们与铜的显色反应，在弱酸性时，３种显色剂与铜均形成配位比为２：１的配合物，２与铜的显色反应，当铜浓度在０～２．５μｇ／ｍＬ范围内符合比耳定律。用分光光度法测定了合金中铜的含量。     

两种偶氮苯冠醚的合成及其光致变色机理

报道了4-氮杂15-冠-5-4'-甲氧基偶氮苯和4-氮杂15-冠-5-4'-硝基偶氮苯的合成及其分子内扭曲电荷转移的光致变色机理.     

过渡金属与二取代冠醚固态配合物的制备

由４＇，５＇－二碘苯并１５冠５，４＇，５＇－二溴苯并１５冠５，４＇－溴－５＇－硝基苯并１５冠５，四溴二苯并１８冠６与过渡全属Ｍｎ（Ⅱ）、Ｃｏ（Ⅱ）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）、Ａｇ（Ⅱ）、Ｃｄ（Ⅱ）的硝酸盐、高氯酸盐、气化物合成了１９个未见报道的固态配合物。用元素分析、红外光谱、摩尔电导和差热－热重分析等表征了它们的组成和性质。     

冠醚修饰型手性固定液的合成及其气相色谱性能的研究

合成了两种含冠醚功能基的手性固定液：（１Ｓ,２Ｓ）－１－对硝基苯基－２－（４＇－西佛碱基苯并１５－冠－５）－丙烷－１,３－烯丙氧基聚硅氧烷和３－甲基－２－（４＇－甲酰胺－苯并１５－冠－５）－丁酸乙酯。用它们涂制的石英毛细管柱呈强极性,色谱性能良好。并探讨了固定液的结构对分离能力的影响。     

RE（Ⅲ）与5—（2‘—羧基苯偶氮）绕丹宁及其衍生物的配合物稳定常数

采用ｐＨ－电位滴定法研究了乙醇溶液中ＲＥ（Ⅲ）与新型荧试剂Ｈ２Ｌ［５－（２＇－羧基苯偶氮）］绕丹宁（Ｂｒ－ＲＡＣＰ）、５－（４＇－氯代－２＇－羧基苯偶氮）绕丹宁（Ｃｌ－ＲＡＣＰ）、５－（４＇－溴代－２＇－羧基苯偶氮）绕丹宁定常数大小为ＲＡＣＰ＞Ｃｌ－ＲＡＣＰ＞Ｂｒ－ＲＡＣＰ。而与Ｎｄ（Ⅲ）的累积生成常数ｌｇβｍｌｈ随原子序数Ｚ增大时，研究了浓度对ｌｇβｍｌｈ的影响，测定了１５种稀土与ＲＡＣＰ的ｉｇ     

腙型双冠醚的合成和性质Ⅱ.

４’－甲酰基苯并－１５－冠－５、４’－乙酰基苯并－１５－冠－５分别与肼和芳杂环二肼缩合得到五种新的腙型双冠醚．用电导法研究了它们与碱金属离子的配位性质．     

不对称冠醚碲碳菁染料的合成

合成了５种不对称冠醚碲碳菁染料．对合成关键中间体冠醚苯并碲唑所用的４－硝基苯并１５－冠－５的还原酰化方法进行了改进，比较和研究了杂原子在同一主族的４个菁染料的可见吸收光谱，计算了它们的“Ｂｒｏｏｋｅｒ偏差”     

长链烷基氨基苯并冠醚的合成

采用４′－氨基苯并－１５－冠－５与长链卤代烷反应，合成了一系列Ｎ－单长链烷基取代及Ｎ，Ｎ－双长链烷基取代的氨基苯并－１５－冠－５。通过１ＨＮＭＲ、ＩＲ、ＭＳ、ＵＶ和元素分析证明了产物的结构     

含苯氧基萘并萘醌和偶氮苯双变色基化合物的合成和性质

通过６－氯－５，１２－萘并萘醌与４－羟基偶氮苯及其衍生物的反应合成了３种含苯氧基萘并萘醌和偶氮苯光致变色基的双变色基化合物，６－［４－（苯偶氮基）苯氧基］－５，１２－萘并萘醌（５），６－［４－（ｐ－乙氧基苯偶氮基）苯氧基］－５，１２－萘并萘醌（６）和６－［４－（ｐ－硝基苯偶氮基）苯氧基］－５，１２－萘并萘醌（７）．这些化合物的苯氧基萘并萘醌变色基的ＵＶ诱导光致变色性较弱；基于氨与苯氧基萘并萘醌ａｎａ显色体的不可逆反应，化合物５和６ＤＭＳＯ溶液在３６５ｎｍ紫外光辐照光稳态（ＰＳＳ）下的ａｎａ醌式摩尔分数估计分别为２２％和１７％．这些结果说明，苯偶氮基对苯氧基萘并萘醌变色基的光致变色性质有着极强的影响．另一方面，与４－羟基偶氮苯母体不同，这些双变色基化合物在ＤＭＳＯ中偶氮苯变色基的顺式异构体是相对稳定的     

N,N''''-二乙酸取代含噻吩环氮杂冠醚配体及其稀土配合物的合成与表征

N－功能化大环不仅环的空腔大小及环上配位原子种类对不同离子具有配位选择性，其功能化的官能团也会对大环配体的性质和选择性有很大影响，这类大环及其金属配合物，在药物试剂犤１犦，金属离子的分离与回收犤２犦，环境保护和新材料犤３犦等方面都有着广泛的应用前景。人们对N－功能化氮氧杂大环及其配合物研究较多犤４～６犦，而对N－功能化的氮氧硫杂大环研究并不多。为了进一步研究和开发这类大环配体及其性质，我们合成了一个新的功能化的大环配体（４，５：１４，１５二苯并－３，１６－二氧－２１－硫－７，１２－二氮双环犤１６…     

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.