2-苯基-4-硒唑甲酸过渡金属配合物的合成、结构及生物活性研究

合成了2-苯基-4-硒唑甲酸配体(HL)和相应的6个过渡金属配合物[ML2(H2O)2](M=Co,Ni,Cu,Cd)1～4,[ZnL2](5),[CuL2(py)2](6).用元素分析、红外光谱、热重分析等表征手段确定了配合物的组成;用单晶X射线衍射测定了配合物3和6的结构;用溴化乙锭荧光探针初步研究了它们与DNA作用的强度和模式;考察了配体和配合物对大肠埃氏杆菌(E.coliJM109)、大肠杆菌(E.coli,DH5α)、表皮葡萄球菌(S.epidermidis)、金黄色葡萄球菌(S.aureus)、鲍曼不动杆菌(baumanii)、草绿色链球菌(S.viridans)6种细菌的抗菌活性及对正常细胞293T和肿瘤细胞RAW264.72的体外增殖抑制作用.     

2-苯基-4-硒唑甲酸的铜(Ⅱ)配合物的合成、晶体结构和生物活性

采用水热法合成了一种新型铜(Ⅱ)配合物[Cu₂(NO₃)₂L(phen)₂(H₂O)] NO₃(HL=2-苯基-4-硒唑甲酸, phen=1,10-邻菲啰啉)。用元素分析、红外光谱等表征手段确定了配合物的组成;用单晶X-射线衍射测定了配合物的晶体结构。配合物C₃₄H₂₄Cu₂N₈O₁₂Se属于三斜晶系, 空间群P1。用溴化乙锭荧光探针法研究了配合物与DNA的相互作用。分别考察了配体和配合物对五种细菌:大肠埃氏杆菌(E.coli), 表皮葡萄球菌(S.epidermidis), 草绿色链球菌(S.viridans), 金黄色葡萄球菌(S. aureus), 鲍曼不动杆菌(A.baumanii)的抗菌活性。同时也考察了配体和配合物对人类胰腺癌PANC-28细胞和人类肝癌HuH7细胞的体外增殖抑制作用。实验结果表明配合物具有良好的生物活性。     

4-[(1,3-二氧代丁基)氨基]苯甲酸稀土配合物的合成、表征及发光性质

在乙醇体系中,由主配体4-[(1,3-二氧代丁基)氨基]苯甲酸(H2L,C11H11NO4)、稀土硝酸盐及辅助配体邻菲啰啉(phen)反应合成了两个系列8个配合物[Ln2(L)3(H2O)4]n(Ln=Sm(1),Eu(2),Tb(3),Dy(4));[Ln2(NO3)2(L)2(phen)2]n(Ln=Sm(5),Eu(6),Tb(7),Dy(8))。用元素分析、红外光谱、摩尔电导、热重分析进行表征,确定了产物的化学组成,推断了相应的结构。测定了室温时固体产物的激发和发射光谱,结果表明:由主辅配体共同配位的三元配合物的发光强度好于无辅助配体参与的二元配合物。测定了三元配合物的荧光寿命,其中铕和铽配合物显示较长的荧光寿命。     

基于2-苯基-4-硒唑甲酸镍配合物的合成、晶体结构及生物活性

由2-苯基-4-硒唑甲酸(HL,C10H7O2NSe)、硫酸镍和乙二胺(en)合成了相应的配合物[Ni(en)3](L)2.3H2O。用元素分析、红外光谱、热重分析等表征手段确定了配合物的组成;用单晶X-射线衍射测定了配合物的晶体结构。配合物C26H42N8NiO7Se2属于三斜晶系,空间群P1,晶胞参数:a=1.15673(3)nm,b=1.21755(3)nm,c=1.26326(3)nm,α=86.096(2)°,β=89.461(1)°,γ=69.321(1)°,晶胞体积:V=1.66046(7)nm3,晶胞内结构基元数Z=2,式量Mr=795.29。用溴化乙锭荧光探针法研究了配合物与DNA的相互作用。考察了配体和配合物对大肠埃氏杆菌(E.coli JM109)、大肠杆菌(E.coli DH5α)、表皮葡萄球菌(S.epidermidis)、金黄色葡萄球菌(S.aureus)、鲍曼不动杆菌(baumanii)、草绿色链球菌(S.viridans)六种细菌的抗菌活性及对正常细胞293T和肿瘤细胞RAW 264.7的体外增殖抑制作用。     

铜(Ⅱ)-N-(2-羟苄基)-DL-α-苯丙氨酸-2,2′-联吡啶(或1,10-邻菲咯啉)三元配合物的合成、晶体结构及抑菌活性

合成了铜"与N-(2-羟苄基)-DL-α-苯丙氨酸(H2sphe)和2,2′-联吡啶(2,2′-bipy)及1,10-邻菲咯啉(phen)的三元配合物[Cu(Hsphe)(phen)](ClO4)·3H2O(1)、[Cu(Hsphe)(2,2′-bipy)](ClO4)(2)、[Cu(Hsphe)(2,2′-bipy)](NO3)(3)。用X射线单晶衍射测定了配合物的晶体结构。3种配合物中Cu"离子配位数均为5,处于变形四方锥配位环境中。抑菌活性试验结果表明,3种配合物均对金黄色葡萄球菌、铜绿假单胞菌和枯草杆菌有一定的抑制作用。配合物1还对大肠杆菌、伤寒杆菌有较强的抑制作用,而配合物3对伤寒杆菌亦有一定的抑制作用。     

钐、铕-2,4-二氯苯氧乙酸的二元、三元配合物的合成及荧光性能

以2,4-二氯苯氧乙酸为第一配体、1,10-菲罗啉为第二配体,合成了钐、铕的二元、三元配合物。通过元素分析、EDTA络合滴定及热重分析,确定了配合物的通式为RE(DCP)3.H2O,RE(DCP)3phen(RE=Sm,Eu;DCP=2,4-二氯苯氧乙酸根;phen=邻菲罗啉);测定了配合物红外光谱、紫外光谱、荧光光谱;研究了配合物的热稳定性。结果表明,三元配合物较二元配合物稳定;Eu(DCP)3.H2O和Eu(DCP)3phen具有荧光性能。     

六核(3,3,4,5)-连接2-(4’-羧基苯基)咪唑-4,5-二羧酸金属有机配合物

用缩合氧化反应,成功合成了一个新的咪唑羧酸配体2-(4’-羧基苯基)咪唑-4,5-二羧酸(H4CPhIDC)。在水热条件下以H4CPhIDC为主配体,邻菲咯啉(phen)为辅助配体,合成了镉的六核金属有机配合物[Cd6(CPhIDC)(HCPhIDC)2(H2CPhIDC) (phen)6]?H2O (MOF)。H4CPhIDC配体在该配合物中呈现出不同的去质子模式H2CPhIDC2-、HCPhIDC3-、CPhIDC4-,从而形成了一个新的六核(3,3,4,5)-连接拓扑结构。测定了配体和配合物的固体荧光光谱,并用溴化乙锭荧光探针测定了配体和配合物与DNA及BSA的作用,结果表明,配合物对生物大分子的作用更强些。CCDC：969815。     

6-甲基-2,3,5-吡啶三甲酸构筑的两个银配合物的合成、结构与性质

以6-甲基-2,3,5-吡啶三甲酸,菲咯啉为配体与AgNO3反应,合成出2种银配合物[Ag(H2mptc)(phen)]·2H2O(1)和[Ag(H2mptc)(phen)](2)(H3mptc=6-甲基-2,3,5-吡啶三甲酸,phen=菲咯啉),并对其进行了红外光谱分析,元素分析,热重分析,X-射线粉末衍射分析,荧光光谱分析及X-射线单晶衍射结构分析。配合物1中的Ag(Ⅰ)采取三配位的配位方式与配体H2mptc-及phen中的N原子结合,在2中,除了3个N原子配位外,邻位羧基的O原子也参与了配位。通过计算得知配合物2是热力学上更稳定的结构。固体荧光光谱表明,1和2在475 nm左右有最大吸收,相对配体有75 nm左右的红移,均可归属于配体到金属间的电荷转移。     

[Cu(L-Ile)(Phen)(H2O)(ClO4)]的合成、结构及稳定性研究

合成了三元混配配合物[Cu(L-Ile)(Phen)(H20)(ClO4)](L-Ile=L-异亮氨酸,phen=1,10-邻菲咯啉),通过红外光谱、紫外-可见光谱、摩尔电导率、X射线单晶结构分析,对配合物进行了表征.该晶体属单斜晶系,P21空间群,晶胞参数:a=1.1704(5)nm,b=0.8090(5)nm,c=2.1822(5)nm,β=98.061(5)°,Z=2,Dx=1.60Mg·m-3,R1=0.0462,wR2=0.1225.每个配合物分子中Cu(Ⅱ)离子与一个L-Ile(N,O)配体、一个Phen(N,N)配体、一个H2O(O)配体及一个ClO4-(O)形成六配位的畸变八面体构型.本文还用电位滴定法测定了配合物的稳定常数,结果表明,配合物具有高的稳定性.     

2,2′-二硫代二苯甲酸、2,2′-二羧苯基硫醚及含氮配体构筑的2个配合物的合成、结构与热稳定性研究(英文)

使用2,2′-二硫代二苯甲酸和2,2′-联吡啶(2,2′-bipy)、硝酸铜在水热条件下发生的原位反应合成了一个铜配合物,即[Cu2(C14H8O4S)2(C10H8N2)2](1)(C14H8O4S=2,2′-二羧苯基硫醚,C10H8N2=2,2′-联吡啶);然后又利用2,2′-二硫代二苯甲酸和菲咯啉(phen)、氯化钙在水溶液中合成了一个钙配合物,即{[Ca(C14H8O4S2)(C12H8N2)2]·(H2O)2}n(2)(C14H8O4S=2,2′-二硫代二苯甲酸根,C12H8N2=菲咯啉),并对它们分别进行了元素分析、红外光谱、热稳定性、X射线粉末衍射和X射线单晶衍射的表征。结果表明:配合物1由2,2′-二羧苯基硫醚配体连接形成了一个双核的化合物,通过氢键和氮杂环之间的π…π作用形成三维超分子网络结构。配合物2由二硫代二苯甲酸配体桥联形成了一个一维链状结构,通过氢键和氮杂环之间的π…π作用也形成三维超分子网络结构。并且,对这2个配合物的热稳定性分别进行了研究。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

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.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

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.