无溶剂条件下合成2-[3-氧代-1,3-二(未)取代苯基丙基]-1,2,3,4-四氢萘-1-酮

以3,4-二氢-1-萘酮和查尔酮为原料, 在 K₂CO₃-NaOH 存在下, 无溶剂室温研磨反应, 方便地得到2-[3-氧代-1,3-二(未)取代苯基丙基]-1,2,3,4-四氢萘-1-酮. 该方法具有反应条件温和、操作简单和产率较高等优点, 并通过IR, ¹H NMR, 元素分析确定了产物的结构, 3b晶体结构通过X衍射测定.     

4-(色酮-3-基)-3-乙氧羰基-1,4,5,6,7,8-六氢-5-氧代-2,7,7-三甲基喹啉的一步合成

报道了用3-甲酰基色酮、5,5-二甲基-1,3-环己二酮、乙酰乙酸乙酯与醋酸铵一步法合成4-(色酮-3-基)-3-乙氧羰基-1,4,5,6,7,8-六氢-5-氧代-2,7,7-三甲基喹啉类化合物, 对其结构进行了表征, 并分析了代表性化合物2f的晶体结构. 2f晶体属于单斜晶系, P2/c空间群, 所得晶胞参数为: a＝2.0255(4) nm, b＝0.9132(2) nm, c＝1.4066(3) nm, β＝121.60(3)°, V＝2.2159(8) nm³, Z＝4, D_c＝1.335 g/cm³, μ＝0.209 mm^－1, F(000)＝736, R₁＝0.0556, wR₂＝0.1248.     

无溶剂条件下5,6-二取代-2,3-吡啶二酮的合成

在无溶剂条件下, 由3-羟基-2(1H)-吡啶酮与取代苯胺在NaIO₃作用下合成了一系列5,6-二取代-2,3-吡啶二酮, 产物结构由元素分析, ¹H NMR, MS, IR得到确认. 该方法具有反应条件温和、操作简单和产率高等优点.     

铝离子对α-酮戊二酸的催化脱羧作用

为了研究铝(Ⅲ)与生命体中重要的有机分子α-酮戊二酸的作用机制,我们采用了电位滴定、核磁共振、拉曼光谱和分子力学计算对酸性溶液中的反应体系的配位作用和互变异构进行了分析, 并采用电喷雾质谱以及固体和溶液核磁共振谱表征了浓溶液反应体系中的沉淀,来说明铝(Ⅲ)对α-酮戊二酸的催化脱羧反应过程。得到如下实验结论:(1)配位作用:铝(Ⅲ)与α-酮戊二酸在酸性溶液中配位形成1∶1[AlLH²⁺,AlL⁺,AlLH_-1]和1∶2[AlL₂]-,AlL₂]H_-2]^3-]的单核形态以及2∶1[Al₂]L⁴⁺]的双核形态。(2)互变异构:在酸性溶液中Al³⁺通过配位作用促进α-酮戊二酸烯醇化,生成易于脱羧的β、γ-不饱和酸的结构。(3)催化脱羧:由于铝(Ⅲ)的电子沉降作用,使β、γ-不饱和酸更易脱羧,如果是1∶2的形态,则脱羧生成沉淀。     

含1,6-二氢-6-哒嗪酮的1,3,4-噁二唑啉和噻唑烷-4-酮类化合物的合成

以1,6-二氢-6-哒嗪酮-3-甲酰肼(1)与芳香醛反应得到相应的1,6-二氢-6-哒嗪酮-3-羰基芳香醛腙(2a～2e). 再将2a～2e与乙酸酐作用, 合环得到一系列含有1,3,4-噁二唑啉环的衍生物3a～3e; 在DMF中用HSCH₂COOH合环, 得到含有4-噻唑烷酮的衍生物4a～4e. 所有化合物的结构均经元素分析, IR, ¹H NMR 和MS谱得以证实.     

4-(1,2,4-三唑-5-酮-4-基)-3-硫代脲酸乙酯的合成、晶体结构及理论计算

4-氨基-1,2,4-三唑-5-酮(ATO)与硫氰酸钾、氯甲酸乙酯在乙酸乙酯中反应, 合成了4-(1,2,4-三唑-5-酮-4-基)-3-硫代脲酸乙酯, 在室温下采用缓慢蒸发溶剂二甲基甲酰胺得到合适的可用于X射线衍射的单晶. 晶体属六方系, 空间群为R-3, 晶体结构参数为a＝2.60524(7) nm, b＝2.60524(7) nm, c＝0.82579(6) nm, γ＝120°, V＝4.8540(4) nm³, D_c＝1.442 g/cm³, μ＝0.300 mm^－1, F(000)＝2190, Z＝18, R₁＝0.0569, wR₂＝0.1424. 选取标题化合物的一个结构单元作为初始模型, 运用Gaussian 03程序对化合物进行了HF/6-311G, MP2/6-311G和B3LYP/6-311G水平的几何全优化，并对其原子电荷及自然键轨道(NBO)进行了分析.     

KF/Al2O3催化下芳醛和4-羟基喹啉-2-酮的反应研究

以芳醛和4-羟基喹啉-2-酮为原料, 在KF/Al₂O₃催化下以乙醇为溶剂, 在80 ℃合成了一系列新的双(4-羟基-2-氧代喹啉-3-基)-芳基甲烷衍生物, 反应条件温和, 产率较高, 并通过IR, ¹H NMR和元素分析确证产物的结构.     

两个基于苯并噻唑-2-硫酮的银(Ⅰ)配合物的合成、晶体结构和光谱性质

合成了2个含有杂环硫酮的银(Ⅰ)配合物,[AgCl(PPh₃)₂(BTZT)]₂ (1),[Ag(PPh₃)₂(BTZT)₂](NO₃)CH₃OH (2)(PPh₃=三苯基膦; BTZT=苯并噻唑-2-硫酮),并通过红外光谱、X射线单晶衍射、荧光光谱和核磁共振氢谱进行表征和分析。杂环硫酮存在化学活性基团-N(H)-C(=S)-,在平衡中与其硫醇形式可以相互转化。2个配合物是在含有2-巯基苯并噻唑(MBT)的甲醇与二氯甲烷混合溶液中,AgCl或AgNO₃与三苯基膦反应得到的。配合物1的每个不对称单元中包含2个相同的分子结构,但是它们具有不同的键长和键角。配合物2是一个简单的单核杂配配合物,它的主体结构通过氢键作用连接游离的CH₃OH和NO₃^-离子。配合物1和2发射峰的红移源于配体中的π-π^*跃迁。     

3-(水杨酰肼)-丁基-2-酮肟和两个镍的酮肟配合物的合成和晶体结构

合成了3-(水杨酰肼)-丁基-2-酮肟H₂L(1，C₁₁H₁₃N₃O₃)和2个镍的3-(水杨酰肼)-丁基-2-酮肟化合物[Ni(HL)(CH₃COO^-)(C₅H₅N)₂](2)和[Ni(HL)₂]·2C₃H₇NO（3）。化合物1晶体属单斜晶系，空间群为P2₁/n，晶体学参数为：a=0.451 87(2) nm，b=2.086 8(1) nm，c=1.224 48(9) nm，β=94.974(3)°，V=1.150 3(1) nm³，Z=4，D_c=1.358 g·cm^-3，μ=0.101 mm^-1，F(000)=496，R=0.0435，wR=0.142 5。化合物2晶体属单斜晶系，空间群为P2₁/n，晶体学参数为：a=1.362 39(8) nm，b=1.345 37(6) nm，c=1.438 54(7) nm，β=113.138(3)°，V=2.424 6(2) nm³，Z=4，D_c=1.398 g·cm^-3，μ=0.843mm^-1，F(000)=1 064，R=0.042 4，wR=0.116 6。化合物3晶体属单斜晶系，空间群为P2₁/c，晶体学参数为：a=1.104 22(7) nm，b=2.860 1(1) nm，c=1.114 13(7)nm，β=114.589(5)°，V=3.199 5(3) nm³，Z=4，D_c=1.398 g·cm^-3，μ=0.667 mm^-1，F(000)=1 416，R=0.057 6，wR=0.1535。在化合物1晶体中，酮肟分子之间通过分子间氢键形成二维网状结构。在化合物2中，每个镍(Ⅱ)离子由1个3-(水杨酰肼)-丁基-2-酮肟的2个氮原子和1个氧原子，2个吡啶分子中的2个氮原子和1个乙酸根中的1个氧原子形成畸变的NiN₄O₂八面体配位构型，存在分子内氢键O-H(肟)…O(乙酸根)和O-H(酚)…N(酰肼)。在化合物3晶体中，每个镍(Ⅱ)离子由2个3-(水杨酰肼)-丁基-2-酮肟的4个氮原子和2个氧原子配位，形成畸变的NiN₄O₂八面体配位构型。晶体中存在O-H…O和O-H…N两种分子内氢键和O-H…O分子间氢键。     

微波辐射下合成3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物

在微波辐射和对甲基苯磺酸的催化作用下, 5-芳基-1,3-环己二酮与邻氨基苯甲腈进行缩合反应, 得到了N-取代的2-氨基苯甲腈衍生物, 在K₂CO₃和Cu₂Cl₂的催化作用下进一步合环, 得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-酮衍生物, 用LiAlH₄还原羰基得到3-芳基-9-氨基-1,2,3,4-四氢吖啶-1-醇衍生物. 新合成化合物的结构均经元素分析、红外光谱和核磁共振光谱予以确认.     

Spectroscopic,electrochemical and X-ray crystallographic properties of a novel palladium(II) complex of thioamide deprotonated di-2-pyridyl ketone thiosemicarbazone (dpktsc-H)−

The reaction between di-2-pyridyl ketone thiosemicarbazone (dpktsc) and PdCl₂(CH₃CN)₂, generated in situ from the reaction between PdCl₂ and CH₃CN, gave the unprecedented [Pd₂Cl₃(κ⁵-N_py,N_im,S,N_py,N_am-dpktsc-H)]·2CH₃CN (1) complex (py = pyridine, im = imine and am = amide). The identity of 1 was confirmed via its elemental analysis and spectroscopic properties. Infrared and ¹H-NMR spectra confirmed the coordination of (dpktsc-H)^? to the palladium ions. The electronic absorption spectra measured in dmso and dmf and density functional theory (DFT) calculations revealed metal-to-ligand charge-transfer (MLCT), d–d and intra-ligand charge-transfer (ILCT) electronic transitions. X-ray structural analysis on a crystal of [Pd₂Cl₃(κ⁵-N_py,N_im,S,N_py,N_am-dpktsc-H)]·H₂O (2) grown from dmf solution of 1 confirmed its formulation and showed the solid-state structure contains a web of molecules locked via a network of non-covalent interactions. Electrochemical measurements on 1 in dmf revealed metal- and ligand-based redox processes. In contrast to the electrochemical decomposition of uncoordinated dpktsc, coordinated (dpktsc-H)^? in 1 does not undergo electrochemical decomposition. Electrochemical titrations of 1 with p-toluenesulfonic acid monohydrate (p-TSOH) revealed electro-catalytic proton reduction. Over-potential (η) of 180 mV for the H₂ evolution was observed and is comparable to several molecular electro-catalysts for proton reduction. Controlled-potential electrolysis confirmed the electro-catalytic proton reduction by the Pd-complex. Electrochemical reactions of CO₂ in the presence of 1 exhibited a proton dependence, and metal- and ligand-based electrochemical reaction.     

Synthesis,characterization and DNA-intercalation studies of two ferrocene-based Fe-Sn heterobimetallic compounds,and crystal structure of trimethyltin (p-ferrocenyl)benzoate

In this article, we report the synthesis of two (A3 and A4) new ferrocene-based heterobimetallic compounds of Fe and Sn. Both compounds are structural isomers with formula (C₅H₅)Fe(C₅H₄C₆H₄COO)Sn(CH₃)₃ and have been characterized by elemental analysis, cyclic voltammetry, FTIR, UV–Vis and NMR spectroscopy. Additionally, the structure of A3 was confirmed by single-crystal XRD studies. XRD studies confirmed that in the solid phase A3 exists as a unidirectional polymeric material. DNA-binding potential of these compounds was evaluated by UV–Vis spectroscopy, cyclic voltammetry, and viscosity measurements. These interaction assays conclude that A3 (binding constant ~10⁴ M^?1) and A4 have good attraction toward DNA and bind with DNA in intercalative manner.     

Titanyl complexes with 1,10-phenanthroline-based diols

The reaction of the O,N,N,O-type ligands, namely, 4,7-bis(4-tert-butylphenoxy)₂-2,9-(HOCRR’CH)₂-1,10-phenanthrolines, LH₂ (R = R′ = Ph (1), RR′ = ?(CH₂)₅? (2), 2,2-adamantylene (3)), with an equimolar amount of Ti(OPrⁱ)₄ in toluene under mild conditions afforded the mixtures of the corresponding titanium LTi(OPrⁱ)₂(4–6) and titanyl complexes LTi=O (7–9). Subsequent reflux of these mixtures in toluene gave pure derivatives 7–9, which were characterized by ¹H and ¹³C NMR spectroscopy and elemental analysis. The presence of the Ti=O fragment in molecules 7–9 was unambiguously confirmed by IR spectroscopy data and was found to be consistent with the data of quantum chemical calculations. The new ligand 3 was obtained by sequential treatment of 4,7-di(4-tert-butylphenoxy)-2,9-dimethyl-1,10-phenanthroline with an excess of lithium diisopropylamide and adamantan-2-one. The titanyl complex 7 was found to be moderately active as an initiator of ε-caprolactone polymerization.

     

KF/Al2O3催化下取代水杨醛与达米酮的反应

取代水杨醛与5,5-二甲基-1,3-环己二酮(达米酮)在KF/Al₂O₃催化下反应生成一系列苯并吡喃的衍生物. 产物的结构通过红外光谱、核磁共振氢谱和元素分析进行表征, 并通过X单晶衍射分析进一步证实产物的结构.     

First optically active <Emphasis Type="Italic">PC</Emphasis>-palladacycle bearing a phosphorus atom in an axially chiral environment

Direct aromatic C—H bond activation in the (S _a)-BINOL-derived phosphite (S _a)-HL afforded the dimeric cyclopalladated complex (S _a,S _a)-{Pd(η²-L)(μ-Cl)}₂ (2) which is the first optically active PC-palladacycle bearing a phosphorus atom in an axially chiral environment. ortho-Palladated structure of dimer 2 was confirmed by spectral (¹H and ³¹P NMR) examination of its mononuclear derivatives and by X-ray diffraction analysis of the phosphine adduct (η²-L)PdCl(PPh₃) (4). The enantiomeric purity of the starting ligand remained unchanged in the PC-palladacycle under the thermal conditions used for the cyclopalladation (∼110 °C); this fact was confirmed by the ³¹P NMR spectroscopy after chiral derivatization in situ of dimer (S _a,S _a)-2 with the (R _C )-valinate chiral auxiliary (Val). trans(N,C)-Configuration of the valinate complex (η²-L)Pd(Val) (5) was established by ¹H NMR and supported by DFT calculations. The chirality transfer in the new PC-palladacycle was discussed on the basis of X-ray diffraction data for the phosphine adduct rac-4 and DFT calculations performed for both phosphine and valinate mononuclear derivatives.     

Reusable Amperometric Immunosensor for the Determination of Cortisol

Abstract

A novel reusable amperometric immunosensor was developed for the determination of cortisol by co-immobilizing horseradish peroxidase (POD) and cortisol-antibody on a chemically activated affinity membrane which is mounted over the tip of an oxygen electrode. The enzymatic electrocatalytic current response to the respective substrate is inhibited by the association of the antigen to the co-immobilized antibody. The sensor can be regenerated to facilitate several assays by washing with dilute hydrochloric acid solution. The advantages of the sensor include rapid-response, simple analysis methodology and high selectivity. The calibration curve for cortisol is linear in the concentration range of 1 × 10^?7 – 1 × 10^?5M. The optimal conditions of immobilization and pH have been studied. The inhibition of enzymatic activity was confirmed by luminescence measurement utilizing the luminol- H₂O₂-POD system.     

Synthesis and characterization of a novel η 2-iminoacyl monocyclopentadienyl titanium(IV) complex

An unusual complex, [CpTi(η²-(C,N)-2-ArNH–C₆H₄C=NAr)Cl₂] (Ar?=?2,6- ⁱ Pr₂C₆H₃) (1) has been synthesized and characterized by elemental analysis, NMR spectra, and single crystal X-ray diffraction. The ¹³C NMR resonance of the imine carbon atom of 1 at δ?221?ppm is consistent with the η²-(C,N) binding. This was confirmed by single crystal X-ray diffraction study of 1. In the complex, Ti atom is five-coordinate with a η²-bound iminoacyl ligand and one Cp ligand occupying the axial position in a distorted square pyramid.     

Antimicrobial efficiency of diorganotin(IV) bis-[3-(4-chlorophenyl)-2-methylacrylate]

Abstract

Four new diorganotin(IV) carboxylates, [n-Bu₂SnL₂] (1), [Et₂SnL₂] (2), [Me₂SnL₂] (3) and [n-Oct₂SnL₂] (4), where L?=?3-(4-chlorophenyl)-2-methylacrylate, were synthesized and characterized by elemental analysis, FT-IR, multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn) and X-ray single crystal analysis for 1. A chelating bidentate ligand and six-coordinate tin centers were confirmed in the solid state by IR for all complexes and for 1 by X-ray single crystal analysis. The NMR study has shown a decrease in the coordination number of tin in solution. The complexes were screened for their in vitro antibacterial and antifungal activities. A compromised lipo/hydrophilicity and a diffusion controlled antimicrobial activity was shown by the complexes in the order 1?>?2>3?>?4. Molecular docking studies have shown hydrogen bonding and hydrophobic interactions for 1 with the target proteins of the antimicrobial strains.     

Syntheses and characterizations of trinuclear and dinuclear “half-sandwich” zirconocene phosphates and phosphonates

A series of six-coordinate “half-sandwich” zirconocene phosphates and phosphonates have been synthesized by the reaction of Cp₂ZrCl₂ with (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid under different conditions. All of the complexes were characterized by elemental analysis, FT-IR and NMR (¹H, ¹³C) spectroscopy. Except for complex 3, the structures of complexes 1, 2, 4, 5, and 6 were confirmed by X-ray crystallography. The structure analyses reveal that complexes 1, 2, and 3 are trinuclear complexes with fascinating μ₃-oxygen bridging ligands, central to a Zr–O backbone (Cp₂ZrCl₂:ligand is 1:1) while complexes 4, 5, and 6 are centrosymmetric dinuclear complexes built up about the trapezoidal Zr₂(μ₂-OH)₂ unit (Cp₂ZrCl₂:ligand is 1:2).