几个新的席夫碱合铜(Ⅱ)配合物的合成及性质研究

有关席夫碱类配体及配合物的合成研究非常多,Padhye S.等曾概括过变更席夫碱配合物活性方式^[1],β－二酮席夫碱形成的金属配合物具有仿酶催化活性,在仿生研究中有重要意义;此外,氨基酸类席夫碱含有多个强电负性配位原子,具有较强的配位能力和多样的配位模式的优点,因此,我们合成结构较为复杂的氨基酸席夫碱及其与生命金属铜（II）的配合物,并对合成的配合物的抗菌活性进行了初步研究。     

几个新的席夫碱合铜配合物的合成及性质研究

有关席夫碱类配体及配合物的合成研究非常多ＰａｄｈｙｅＳ．等曾概括过变更席夫碱配合物活性方式１。β二酮席夫碱形成的金属配合物具有仿酶催化活性在仿生研究中有重要意义此外氨基酸类席夫碱含有多个强电负性配位原子具有较强的配位能力和多样的配位模式的优点因此我们合成结构较为复杂的氨基酸席夫碱及其与生命金属铜的配合物并对合成的配合物的抗菌活性进行了初步研究。１实验部分１．１仪器和试剂ＣａｒｌｏＥｒｂａ１１０６型元素分析仪意大利ＰｅｒｋｉｎＥｌｍｅｒ６８３型红外分光光度计美国ＤＤＢ６２００型电导率仪上海雷磁仪器…     

微波无溶剂法合成香草醛氨基酸席夫碱

氨基酸席夫碱是制备特殊生物活性物质的重要中间体。氨基酸席夫碱中的亚胺(C=N)结构与亚磷酸烷基酯加成的化合物具有良好的抗植物病毒,除草,杀菌等性能[1-3]。氨基酸席夫碱中的羟基,羧基和亚胺等多个活性基团,可以与多种金属离子配位,其配合物具有抗菌,抗病毒,抗癌等性能[4-9],     

牛磺酸缩3,5-二溴水杨醛席夫碱镁配合物[Mg(Br_2TSSB)(Phen)(H_2O)]·H_2O的合成及晶体结构

0引言含硫席夫碱及其金属配合物具有抑菌、抗癌和抗病毒的生物活性[1￣3],有些含O、N席夫碱金属配合物具有仿酶催化活性[4,5]。而氨基酸席夫碱配合物具有良好的生物生理活性,近年来得到人们的普遍重视[6,7]。同α-氨基酸席夫碱相比,β-氨基酸席夫碱由于氨基位置的变化而引起不同的配位特征,但研究此类席夫碱的报道目前还不多[8￣10]。2-氨基乙磺酸(牛磺酸)作为生物体内一种特殊的氨基酸,目前对它的研究主要集中在生理和病理方面,它的席夫碱及其配合物的研究或牛磺酸金属配合物的研究刚起步[2,10￣17]。研究表明,-SO32-可以与碱金属、碱土…     

新型大分子席夫碱配合物的合成和表征

本文用胺基封端聚四氢呋喃(Mn=862)与水杨醛反应，生成新型席夫碱遥爪配体，再与金属离子(Fe³⁺, Co²⁺, Cu²⁺)反应，得到新型大分子席夫碱配合物。用IR、ESR、UV、循环伏安法、拉伸和动态粘弹谱等表征手段对配合物进行了研究。证明所得配合物的配位结构与血红蛋白分子的功能片段的配位结构相似，钴配合物具有与血红蛋白分子相近的可逆化学吸附功能。     

过渡金属-二芳基希夫碱配位稳定常数的QSPR研究

金属离子与有机配体形成配合物的稳定性与金属离子的特性和有机配体的分子结构密切关系。为了探讨席夫碱与金属离子配位的稳定性规律,本文以二芳基希夫碱为模型配体化合物,选用部分过渡金属离子(Ni~(2+)、Mn~(2+)、Fe~(3+)、Cu~(2+)、Cr~(3+))为配位对象,将金属离子的特性参数和配体中取代基X的电子效应参数Hammett常数作为变量,对模型化合物与金属离子形成的配合物的稳定常数logβ_2进行定量构效关系研究,得到具有良好相关性的定量方程并通过实验验证了方程的可靠性。结果表明,金属离子的能量密度(X_P/P_(M~+))是影响配合物稳定性的主要因素;对同一金属离子,取代基的吸电子效应增强配合物的稳定性;而金属离子电荷Q和离子半径R需在一个合适的范围内,才利于配合物的稳定。     

冠醚配合物的研究XV．若干席夫碱及仲胺型双冠醚和碱金属离子的配位反应

本文运用微量电导滴定及计算机拟合技术，研究了若干席夫碱及仲胺型双冠醚和减金属离子的配位反应，测定了配合物的组成及稳定常数，并对实验结果进行了讨论．     

稀土-氨基多羧酸配合物的配位结构及变化规律的研究Ⅱ.二乙三胺五乙酸(dtpa)和三乙四胺六乙酸(ttha)系列

在前文的基础上，本文继续综述了氨基多羧酸类-dtpa和ttha配体与一系列稀土金属离子形成配合物的分子结构和配位结构。发现了dtpa和ttha配体与稀土金属离子的配位规律和结构变化规律。研究结果表明，稀土金属离子与dtpa和ttha配体形成配合物的配位数和配位结构明显地取决于稀土金属离子的离子半径，电子结构和氧化态以及配体的形状。     

酰基吡唑啉酮缩邻苯二胺希土配合物的合成、表征及生物活性

酰基吡唑啉酮缩二胺是近年开发的双席夫碱试剂,对希土离子具有较高的萃取性能,并表现出一定的抗菌、抗病毒生物活性。由于这类试剂含有活性的羟基和亚胺基官能团,适于同各种金属离子配位。最近我们研究了酰基吡唑啉酮缩乙二胺配合物,发现它们具有一定的传递电子作用、光致发光作用和较强的抗菌生物活性。但缩芳香二胺双席夫碱配合物的研究较少,为进一步拓宽酰基吡唑啉酮类配合物的研究领域,本文合成了11种未见报道的希土元素与N,N'-双[1－苯基－3－甲基－5－氧－4－吡唑啉基）α-呋喃次甲基]邻苯二亚胺（（HPMαFP）2Pen)的配合物。研究了配合物的结构,一般性质和抗菌活性。     

1,5-双(β-羟基萘亚甲基)硫代二氨基脲及其配合物的合成

硫代氨基脲衍生物具有抗癌、抗肿瘤、抗结核、抗病毒和防止某些霉菌生长的活性[1-5]，其羰基和硫羰基能与过渡金属离子配位形成配合物。     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.