中位-四(对烷氧苯基)卟啉Co2+、Cu2+、Zn2+、Pb2+配合物的合成与表征

卟啉类化合物由于其独特的结构和特有的性能,使得它在众多领域受到人们的高度重视,有关研究非常活跃［１～２］。目前液晶卟啉的研究受到广泛关注,许多液晶卟啉已经被合成出来［３～４］。Ｓｈｉｎ－ｉｃｈｉ等人于１９９０年研究了两个四（ｐ－ｎ－烷氧苯基）卟啉及其配合物的液晶性［５］,Ｓｈｉｍｉｚｕ等人于１９９３年系统研究了四（对烷基苯基）卟啉的液晶性［６］,这些现象引起了人们对卟啉类化合物液晶性能研究的极大兴趣。我们合成了十四种未见文献报道的新的ＣＯ２＋、Ｃｕ２＋、Ｚｎ２＋、Ｐｂ２＋四个系列的中位－四（对烷…     

水溶性卟啉还原甲基紫精动力学的研究

利用跟踪法测定了碘化四－（对甲基异烟酰基苯基）［ＴＭＩａｐｐＩ］等五种水溶性卟啉在还原甲基紫精过程中［ＭＶ＾＋］深度的变化，获得了［ＭＶ＾＋］／［Ｐｏ］～ｔ及［Ｍｖ＾＋］／［Ｍｖ＾２＋］～ｔ的关系曲线。由稳态近似原理推出的动力学方程求得了几种求得了几种卟啉的动态学参数Ａ、诱导时间ｔｉ及起始速率ｖ０。通过稳态转化率得知５种水溶性卟啉的光敏强度有如下顺序：ＺｎＴＭｐｙＰ＞ＺｎＴＭＩＡＰＰＩ＞ＺｎＴＭＮ     

新型氨基酸尾式卟啉及莫锌配合物的合成与表征

金属卟啉配合物作为主体分子对氨基酸酯及其衍生物的分子识别研究是当今卟啉仿生化学的重要课题［１－６］。这一领域的研究成果在生物传感器的研制,癌症的诊断和治疗,模拟含卟啉生物大分子的功能以及在生物大分子构象和类型的识别研究中具有潜在的应用价值［７］。氨基酸是弱的电子授体,将其连接在卟啉分子中可以改变卟啉配体的受授性质,同时氨基酸尾式卟啉更接近天然卟啉。另外,氨基酸是蛋白质的主要组成部分,在蛋白质的生物合成过程中,对氨基酸及其衍生物的识别是关键的一步。酰胺转移ｔ－ＲＮＡ合成酶对氨基酸表现出极为专一的立…     

Schiff碱型和仲胺型壳聚糖冠醚对金属离子的络合吸附性能

壳聚糖（ＣＴＳ）可有效地去除废水中的有毒金属离子［１］,但其分子中的氨基可接受质子成盐,造成在酸性介质中溶解流失,使应用受到限制．近年来国内外学者对壳聚糖的改性进行了广泛的研究,制备了许多理化特性和用途不同的壳聚糖衍生物［２～８］,扩大了其应用范围,...     

几种对称镍卟啉配合物的合成、表征和电化学性质

卟啉试剂是一类重要的离子配位显色剂,在生物体中具有重要作用．作为自然界存在的金属卟啉之一,镍卟啉的电化学研究具有化学和生物学意义．四对羟基苯基卟啉合成已有不少报道［１,２］,但产率较低,只有１０％左右．Ｌｉｎｄｓｅｙ等发现用ＢＦ３作催化剂,在ＣＨ２Ｃ...     

血红素修饰电极及其催化氧还原性质

金属大环络合物（卟啉、酞箐、维生素Ｂ_(１２)等）修饰电极对氧、一氧化氮和其它生物物质的催化作用［１－３］引起了化学工作者的极大兴趣,血红素是一种重要的铁卟啉化合物,是血液中血红蛋白的重要组成部分,承担携氧的任务,由于其特殊的生理功能,研究血红素修饰电极的性质和作用对进一步研究开发燃料电池具有很重大的意义．卟啉在电极上的修饰有多种方法,当卟啉或金属卟啉环侧链上具有苯氨基、苯酚基、乙烯基或吡咯等取代基时［３］,可采用电氧化聚合法制备聚卟啉膜．本文采用循环伏安法在水溶液中制备了聚血红素膜电极,研究了聚…     

卟啉类化合物与人血清白蛋白相互作用的研究进展

卟啉类化合物与人血清白蛋白的相互作用研究可以为制备新型金属卟啉与蛋白质的结合体及卟啉类化合物的功能开发研究提供重要的理论基础,是当前仿生化学、生物有机、医药化学等领域中的热门研究课题。本文综述了近几年来具有不同结构特点的卟啉类化合物与人血清白蛋白间的相互作用,并展望了该研究方向的发展趋势和应用前景。     

烯丙醇电还原自由基中间产物的ESR研究

烯丙醇电还原自由基中间产物的ＥＳＲ研究张敬东，旷亚非，黄树坤，谢乃贤（湖南大学化学化工系，长沙４１００８２）汪风珍，陈德文（中南工业大学测试中心，长沙４１００８３）（中国科学院化学研究所，北京１０００８０）Ｈｏｒａｎｙｉ［１］、陈剑［２］等人对酸性水...     

N-错位卟啉的研究进展

N-错位卟啉既是卟啉的同分异构体又是异卟啉的典型代表,也是一类非常重要的卟啉类化合物.因其独特的化学结构及反应活性,近年来引起化学工作者的广泛关注.介绍了N-错位卟啉研究的意义、N-错位卟啉的结构和性质.重点综述了N-错位卟啉的合成及其在催化化学、生物化学和材料化学领域的应用进展.同时对N-错位扩展卟啉和其它错位异卟啉的发展现状作了简要概述,并对N-错位卟啉化学的发展进行了展望.     

四种新型单取代氨基酸四苯基卟啉锌配合物的合成和光谱表征

本文合成了四种新的单取代氨基酸四苯基卟啉锌配合物Zn［Val-TPP］、Zn［Glu-TPP］、Zn［Tyr-TPP］和Zn［Trp-TPP］。通过化学分析和元素分析确定了配合物的组成，研究了它们的紫外、红外、荧光和激光拉曼光谱。     

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.     

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.     

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.